S. K.

Sharma
Khuram Ali Editors

Solar Cells
From Materials to Device Technology
Solar Cells
S. K. Sharma Khuram Ali
•

Editors

Solar Cells
From Materials to Device Technology

123
Editors
S. K. Sharma Khuram Ali
Department of Physics, Faculty of Science Department of Physics
and Technology University of Agriculture Faisalabad
The University of the West Indies Faisalabad, Pakistan
St. Augustine, Trinidad and Tobago

ISBN 978-3-030-36353-6 ISBN 978-3-030-36354-3 (eBook)

https://doi.org/10.1007/978-3-030-36354-3
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Preface I

Solar cell is designed to convert sunlight into electrical power using photovoltaic
properties. The advantage of a solar cell resides in a nearly permanent, uninter-
rupted power source at a minimal operating cost. Moreover, it has the ability to
convert sunlight directly into electricity instead of some intermediate form of
energy. A higher power to weight ratio is another advantage the solar cells have as
compared to other power sources such as batteries. On the other hand, the low
power to unit area of sunlight ratio (which necessitates using large area arrays), the
relatively low efficiency, and the degradation that takes place in hostile high-energy
radiation environments are some of their main disadvantages. The role played by
solar cells in a wide range of resource investigation, meteorological, broadcast,
communications, scientific, and space development research cannot be denied. It
can be rightly commented that without the development of solar cells, we would not
have the sophisticated weather, communications, military, and scientific satellite
capabilities that we have today. Increased life, improved conversion efficiency, and
reduced cost are the basic objectives for research and development of solar cell
materials.
Thin-film technology has been significantly improved since the last few years.
For sufficient absorption of the solar spectrum, it is required that the wafer thickness
should be >700 µm. It is not desirable for commercial or large-scale production of
solar cells because it is a large thickness for a Si wafer in terms of cost and effective
collection of photo-generated carriers. This type of solar cell is generally made by
depositing one or more thin films, on a glass, plastic, or metal substrates. Initially,
wafers of up to 200 µm thickness were used to fabricate silicon-based thin-film
solar cells. This technique allows thin-film cells to be flexible and lower in weight.
However, it is also mandatory to have a general understanding of the problems that
appear when the thickness of a silicon wafer is decreased. Incorporating quantum
dots is an updated approach to harness solar cells. Efficiency of thin-film-based
solar cells has been remarkably increased with the addition of quantum dots. They
have properties of band gap tunability, which makes them suitable for multijunction
solar cells. Quantum dots have energy levels that are tunable by altering their size.
These tunable energy levels, in turn, determine the band gap. Quantum dots in

v
vi Preface I

semiconductors are nowadays a subject of great importance primarily due to their

electronic structures and tunable optoelectronic characteristics. In addition, band
gaps for single-junction solar cells using lead sulfide (PbS) colloidal quantum dots
(CQD) can be fabricated which can operate on far infrared frequencies. Such
configuration is difficult to achieve with conventional solar cells. Currently,
quantum dot-based nanostructures have been primarily restricted to lasers, sensors,
and LEDs, etc. However, the blue shift in the band gap energy and the
size-dependent increase in oscillator strength are the characteristics that can be used
for promoting better photovoltaic devices as compared to traditional photovoltaics.
Solar cells with multiple stacked p–n junctions are made with multiple layered
semiconducting materials from III–V compound semiconductors. These types of
III–V cells have the highest conversion efficiency under concentrated sunlight.
Since their evolution, the multijunctions solar cells have achieved great attention in
the photovoltaic industry due to broad choice of materials with direct band gaps and
high absorption coefficients. However, manufacturing price and process complex-
ities are also involved with the high efficiencies gained in III–V multijunction solar
cells.
Recently, organic–inorganic hybrid solar cells have gained a rapid improvement
in their performance. Their overall power conversion efficiency (PCE) has exceeded
20% because of high charge carrier mobility, efficient light harvesting, and long
carrier lifetime. A perovskite absorption layer is sandwiched between a hole contact
layer and an electron contact layer in a typical planar heterojunction perovskite
solar cell. Irrespective of the compatibility of low-temperature sputtered NiOx films
with flexible devices, their low PCE (below 10%) makes them unappealing to the
research community. Therefore, for flexible perovskite solar cells, it is very pur-
poseful to explore low-temperature processed NiOx films with effective hole
extraction capabilities. It is observed that on an ITO glass substrate, a
solution-derived NiOx hole contact layer-based inverted planar heterojunction
perovskite solar cell can gain a PCE of as high as 16.47%. Before this technology is
fully accepted in the market, many hurdles need to be overcome. At this time,
organic photovoltaics (OPVs) are applicable only in limited markets that require
lightweight, flexibility, stability, and variable angle performance. The continuous
development of OPV with the improvement in their light harvesting ability and the
management of active layer materials will occasion widely applicable technologies
for electrical generation.

St. Augustine, Trinidad and Tobago S. K. Sharma

Faisalabad, Pakistan Khuram Ali
Preface II

Reducing the cost and increasing the conversion efficiency are the crucial tasks in
order to make solar cell energy competitive. Though important progress has been
made in recent years, a complete auxiliary of traditional energy sources by solar
cells still requires improvement in device performance.
This book is devoted to the rapidly developing class of solar cell materials and
designed to provide much needed information on the fundamental scientific prin-
ciples of these materials, together with how these are employed in photovoltaic
applications.
Moreover, a special emphasize has been given for their space applications by
thorough study of radiation-tolerant solar cells. This book will present compre-
hensive research outlining progress on the synthesis, fabrication, and application of
solar cell materials from fundamental to device technology.

St. Augustine, Trinidad and Tobago S. K. Sharma

vii
Contents

Synthesis and Processing of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . 1

Muhammad Yasin Naz, Shazia Shukrullah, Abdul Ghaffar, Khuram Ali
and S. K. Sharma
Perspective of Nanomaterials in the Performance of Solar Cells . . . . . . 25
Hafiz Muhammad Asif Javed, Wenxiu Que, Muhammad Raza Ahmad,
Khuram Ali, M. Irfan Ahmad, Anam ul Haq and S. K. Sharma
Materials for Solar Cell Applications: An Overview of TiO2, ZnO,
Upconverting Organic and Polymer-Based Solar Cells . . . . . . . . . . . . . . 55
Navadeep Shrivastava, Helliomar Barbosa, Khuram Ali and S. K. Sharma
Recent Advances in Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Marcio A. P. Almeida
Photovoltaic Materials Design by Computational Studies:
Metal Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Edan Bainglass, Sajib K. Barman and Muhammad N. Huda
Photovoltaic-Based Nanomaterials: Synthesis and Characterization . . . . 139
Kanwal Akhtar, Naveed Akhtar Shad, M. Munir Sajid, Yasir Javed,
Muhammad Asif, Khuram Ali, Hafeez Anwar, Yasir Jamil
and S. K. Sharma
Carbon Nanotubes: Synthesis and Application in Solar Cells . . . . . . . . 159
Shazia Shukrullah, Muhammad Yasin Naz, Khuram Ali and S. K. Sharma
Basic Concepts, Engineering, and Advances in Dye-Sensitized
Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
Mohan Chandra Mathpal, Promod Kumar, F. H. Aragón,
Maria A. G. Soler and H. C. Swart
Quantum Dot Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Hafeez Anwar, Iram Arif, Uswa Javeed, Huma Mushtaq, Khuram Ali
and S. K. Sharma

ix
x Contents

Organometal Halide Perovskite-Based Materials and Their

Applications in Solar Cell Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Amna Bashir and Muhammad Sultan
Effect of Oxygen Vacancies in Electron Transport Layer for
Perovskite Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
Mohamad Firdaus Mohamad Noh, Nurul Affiqah Arzaee
and Mohd Asri Mat Teridi
Solar Cells and Optoelectronic Devices in Space . . . . . . . . . . . . . . . . . . 307
Khuram Ali, Syedda Shaher Bano, Hasan M. Khan and S. K. Sharma
Multi-junction (III–V) Solar Cells: From Basics to Advanced
Materials Choices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Khuram Ali, Afifa Khalid, Muhammad Raza Ahmad, Hasan M. Khan,
Irshad Ali and S. K. Sharma
Synthesis and Processing
of Nanomaterials
Muhammad Yasin Naz, Shazia Shukrullah, Abdul Ghaffar, Khuram Ali
and S. K. Sharma

Abstract Nanomaterials have emerged as a distinct class of modern materials. These

materials are of significant importance due to their unique optical, electrical, thermal,
and magnetic properties. Due to their tunable physical and chemical characteristics,
including melting point, electrical conductivity, wettability, heat conductivity, light
absorption, catalytic activity, and scattering, these materials have also gained recog-
nition in high-tech engineering applications. These characteristics reflect better per-
formance and working efficiency of nanomaterials relative to their bulk counterparts.
Although there are many naturally occurring nanomaterials, most nanomaterials are
engineered in laboratories. Such materials are purposefully synthesized in accor-
dance with the industrial requirements. This chapter deals with the fundamentals of
nanomaterials, their history, properties, and industrial applications. Different meth-
ods of synthesis of nanomaterials, their merits, demerits, and scale-up potential are
also discussed in this chapter.

Keywords Nanomaterials · Properties of nanomaterials · Synthesis routes ·

Chemical vapor deposition

1 Fundamentals of Nanomaterials

1.1 Introduction to Nanomaterials

Nanomaterials are representing a major area of science and technology with full
growth in numerous application domains. These materials have gained fame in high-
tech advancements due to their tunable physical and chemical traits, including melt-
ing point, electrical conductivity, wettability, thermal conductivity, light absorption,

M. Y. Naz (B) · S. Shukrullah · A. Ghaffar · K. Ali

Department of Physics, University of Agriculture, Faisalabad 38040, Pakistan
e-mail: [email protected]
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago

© Springer Nature Switzerland AG 2020 1

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_1
2 M. Y. Naz et al.

catalytic activity, and scattering. These traits reflect the improved performance of
nanomaterials as compared to their bulk counterparts. The International Organiza-
tion for Standardization defines the nanomaterial as a “material having external or
internal nanoscale dimensions or surface structure” [1, 2]. Presently, the following
scientific terms are being used for the materials with nanoscale dimensions [1–3].
• Nanoscale: Roughly, the sizes in the range of 1–100 nm.
• Nanoscience: The study of materials at nanoscale to understand their size and
structural properties, to compare the advent of individual atoms and molecules,
and to understand the bulk material related differences.
• Nanotechnology: Practical use of the scientific knowledge to manipulate and
control the matter on the nanoscale dimensions for different industrial applications.
• Nanomaterial: A material with external or internal dimensions on the nanoscale.
• Nano-object: A material possessing one or more peripheral dimensions at
nanoscale.
• Nanoparticle: An object with all three external dimensions grown at nanoscale
is called nanoparticles. If the shortest and longest axes lengths of the object are
different, then it is referred to as a nanorod or nanoplate instead of nanoparticles.
• Nanofiber: A nanomaterial with two similar dimensions, extending at nanoscale,
and a longer third dimension is called nanofiber.
• Nanocomposite: A multiphase material having at least one phase on nanoscale.
• Nanostructure: Arrangement of interconnected constituent parts in the nanoscale
region.
• Nanostructured material: A material with nanoscale structural dimensions.
Nanomaterials are the keystones of nanoscience and technology. Nanotechnology
is widely known as an interdisciplinary research area, which has been recognized
worldwide during the past few years. Nanotechnology has shown substantial com-
mercial impact, which will grow exponentially in the coming years [4]. Figure 1
depicts the evolution of science and technology of materials over time [1, 5, 6]. This
chapter is aimed at a review of the progress to date in the science and technology
of ultrafine particles, which form the building blocks of nanomaterials. An attempt
is made to outline the progression of nanomaterials from fundamental research and
commercial standpoint.

1.2 History of Nanomaterials

The nanomaterials, driven from nanoparticles, have evolved as a distinct class of

materials [7]. These materials are of special interest due to their unique optical,
electrical, thermal, magnetic, and other properties [4]. Materials with dimensions in
micrometers mostly reveal the physical characteristics same as the bulk materials.
Contrarily, materials with dimensions in nanometers exhibit physical characteristics
totally different from the bulk. In this size range, the materials exhibit some amazing
properties since transitions from bulk form to atoms and/or molecules take place. For
Synthesis and Processing of Nanomaterials 3

Fig. 1 Evolution of science and technology over time

example, nanosized crystals may have very low melting points and the difference
can be up to 1000 °C. Also, lattice constant may decrease due to the appearance
of surface atoms or ions as a significant fraction of a total number of atoms or
ions. The surface energy, associated with these species, plays a substantial role in
thermal stability of the material [5]. Very first scientific report on nanomaterials was
published by Michael Faraday in 1857. He was the first who synthesized colloidal
gold particles. Nanocatalysts have also remained under investigation for the last
70 years. In early the 1940s, the nanoparticles of precipitated and fumed silica were
being sold in Germany and America as rubber reinforcement. The silica was being
used as a substitute for ultrafine carbon black. The nanosized silica has found many
applications in everyday consumer products, including nondairy coffee creamer,
optical fibers, automobile tires, and catalyst supports.
During 1960–70, nanopowders of metals were developed for magnetic recording
tapes. Granqvist and Buhrman, 1976, reported the production of nanocrystals from
an inert gas evaporation technique. In recent years, several structural and functional
materials have been developed through nanophase engineering for manipulation of
catalytic, mechanical, electrical, magnetic, electronic, and optical functions. These
materials include both organic and inorganic structures [4, 8].

1.3 Nanomaterials Are All Around Us

Although many nanomaterials exist naturally, majority of the nanomaterials are engi-
neered. They are designed and synthesized according to the needs of commercial pro-
cesses and products. Synthetic nanomaterials are being used in sunscreens, sporting
goods, cosmetics, stain-resistant tires, clothing, electronics, and many other everyday
4 M. Y. Naz et al.

items. In medicine, these materials are being used for imaging, diagnosis, and drug
delivery. The unique properties of nanoscale are attributed to an increase in relative
surface area and appearance of new quantum effects. The high surface area to volume
ratio of nanomaterials improves their mechanical strength and chemical reactivity.
Also, the quantum effects at nanoscale become more significant in determining the
characteristics of the materials [4].
Nanoparticles can be treated as a common type of materials in many different envi-
ronments. These particles pass by almost undetected unless somebody is looking for
them. Nanoparticles are being produced through different physical and chemical pro-
cesses. The volcanic ash, fine sand, dust, ocean spray, and even biological matter are
the natural sources of nanoparticles [9]. The synthetic or anthropogenic nanoparti-
cles are classified into incidental nanoparticles and engineered nanoparticles. The
size and shape of the incidental nanoparticles are poorly controlled. These are
the by-products of human activities and are made of a hodge-podge of the elements.
The major sources of incidental nanoparticles are diesel engines, fire, and large-scale
mining [9]. Figure 2 shows the common sources of incidental nanoparticles.
Engineered nanoparticles are specifically designed and synthesized through dif-
ferent physical and chemical processes. It is possible to control their size, shape, and
compositions by deliberately choosing the synthesis technique. Although engineered
nanoparticles are becoming more sophisticated over time, the simple nanoparticles
produced through relatively easy chemical reactions [9]. The nanophase ceramics,
nanostructured semiconductors, nanosized metallic powders, single nanosized mag-
netic particles, nanostructured metal clusters, nanostructured metal-oxide thin films,
and polymer-based composites are few examples of engineered nanomaterials.

Fig. 2 Few sources of incidental nanoparticles

Synthesis and Processing of Nanomaterials 5

2 Properties of Nanomaterials

The factors making the nanomaterials considerably different from their bulk
counterparts are:
I. Large surface area to volume ratio.
II. Quantum confinement effect.

2.1 Surface Area of Nanomaterials

Nanomaterials possess the large surface area to volume ratio. The ratio of the atoms
at the surface to those within the body changes dramatically on a successive division
of a macroscopic object into smaller ones [5]. The constituent particles exhibit a
relatively larger surface area to volume ratio when compared to same mass of the
material in bulk form. Figure 3 shows a cube of 1 m3 volume 6 m2 surface area.
If divided into eight smaller cubes, the surface area would increase to 12 m2 . The
surface area would increase further by cutting down the cube in a large number of
smaller particles. In response, the surface atoms will increase by making the materials
chemically more reactive.

Fig. 3 Illustration of surface area to volume ratio

6 M. Y. Naz et al.

2.2 Quantum Confinement

The bulk materials are known for continuous electronic energy levels. Contrarily, the
nanomaterials do not have continuous energy levels due to confinement of electronic
wave function in one, two, or three physical dimensions. The quantum confinement
of nanomaterials can be classified as:
I. 1-D confinement—thin film, quantum well.
II. 2-D confinement—nanotubes, nanorod, and quantum wire.
III. 3-D confinement—precipitates, colloids, and quantum dots.

2.3 Structural Properties of Nanomaterials

The mechanical properties of nanomaterials are of quite basic interest since it is prob-
lematic to grow macroscopic objects of high density and grain size less than 100 nm.
However, two materials have attracted the interest and achieved the industrial impor-
tance. These materials are plastic-deformed metals and the polymers composited
with nanotubes or nanoparticles. However, earlier is not accepted as a nanomaterial
due to its larger grain size. The experimental investigations on structural traits of bulk
nanomaterials are impaired by the main experimental problems in synthesizing the
specimens of fairly defined porosities and grain sizes. Therefore, molecular dynam-
ics and model calculations are of key importance for understanding the structural
properties of such materials [10].
The addition of nanoparticles, nanorods, or nanotubes into polymers significantly
improves their structural properties. Possible changes in structural properties depend
on the filler type and the method of conducting filling. The filling method is of great
importance because the anticipated advantages filling may lose if the filler particles
aggregate into larger particles. The polymers filled with nanofillers exhibit a wide
range of failure strengths and strains, depending on the shape and particle size of
the filler and the degree of agglomeration. The polymers reinforced with silicate
platelets have shown the best structural properties of economic relevance. Although
nanofibers or nanotubes added polymers are the best composites, sometimes these
composites exhibit the least ductility. On the other hand, the composites filled with
carbon nanotubes may exhibit high mechanical strength and strain at rupture [4, 11].

2.4 Chemical Properties of Nanomaterials

The small atomic clusters exhibit high ionization energy as compared to the corre-
sponding bulk material. Owing to different crystallographic structures and high sur-
face area to volume ratio, the nanomaterials exhibit high radical alteration in chemical
Synthesis and Processing of Nanomaterials 7

reactivity. The catalysis, utilizing nanoscale systems, can significantly increase the
selectivity, rate, and efficiency of a chemical reaction. Porosity and surface area
of nanomaterials are important physical properties influencing the utility, quality,
and handling of the nanomaterials. Therefore, these materials should carefully be
engineered to carry out specific functions. For example, surface chemistry of car-
bon nanotubes is driven by the surface defects and basal and edge carbon atoms.
The structural defects of graphene layer or nanotubes act as active sites because of
increased density of unpaired electrons. These active sites determine the rate and
efficiency of the reactions [12, 13].

2.5 Magnetic Properties of Nanomaterials

Magnetite nanoparticles are found in animal cells, which help them in cruising. The
most fascinating characteristic of magnetic nanoparticles is the lessening of multi-
domains into a single domain with a reduction of particle size to some limit [14].
These materials have multifunction applications, such as color imaging, ferrofluids,
bioprocessing, magnetic storage devices, and refrigeration. A high proportion of
surface atoms in magnetic nanomaterials develops different magnetic coupling with
neighboring atoms and consequently different magnetic properties than the bulk
counterpart. As shown in Fig. 4, the bulk ferromagnetic materials have multiple
magnetic domains. In contrast, magnetic nanoparticles often have a single magnetic
domain exhibiting the superparamagnetism phenomenon [4, 15].
The gold and platinum are non-magnetic in bulk form and magnetic at nanoscale.
In such materials, the surface atoms not only differ from bulk atoms but also exhibit
different properties due to interaction with other species. The interaction of nanopar-
ticles with other chemical species modifies their physical characteristics by capping
them with molecules.

Fig. 4 Illustration of
superparamagnetism in
nanomaterials
8 M. Y. Naz et al.

The large spin–orbit coupling of these noble metals can yield to a large anisotropy
and therefore exhibit high ordering temperatures. More surprisingly, permanent mag-
netism was observed up to room temperature for thiol-capped Au nanoparticles. For
nanoparticles with sizes below 2 nm, the localized carriers are in the 5d band. Bulk
Au has an extremely low density of states and becomes diamagnetic, as is also the
case for bare Au nanoparticles. This observation suggested that modification of the
d band structure by chemical bonding can induce ferromagnetic like character in
metallic clusters [4].

2.6 Optical Properties of Nanomaterials

The optical aspect of nanomaterials is also fascinating for many communication

applications. The most important applications utilizing the optical properties of nano-
materials are the optical detectors, sensors, lasers, imaging devices, optical displays,
phosphor, solar cell, photocatalysis, biomedicine, and photo-electrochemistry [4].
The optical absorption and emission in bulk materials depend on transitions between
valence bands and conduction bands. The low dimensional metals and semiconduc-
tors exhibit large changes in their optical properties, such as color. For example, the
colloidal solution of gold nanoparticles has typical deep red color when particle size
is very small. However, the color of solution changes to yellow with an increase in
particle size. This change in color with size is attributed to the resonance of surface
plasmons, which normally occurs in low dimensional materials.
The frequency and intensity of light, emitted from the nanoparticles, also depend
on the size of the particle. The size of the nanoparticles of semiconductors in the
form of quantum dots effects their nonlinear optical properties and gain for cer-
tain emission wavelengths. Other characteristics influenced by the small dimensions
include photocatalysis, photoemission, photoconductivity, and electroluminescence.
The spacing between energy levels increases with a decrease in particle size, which
helps confining the system and enhancing the surface plasmon resonance. The reso-
nance of surface plasmons is related to the coherent excitation of free electrons in the
conduction bands, which results in in-phase oscillations. The free electrons polarize
relative to cationic lattice due to electric field of incoming light. A net charge differ-
ence appears at the boundaries of nanoparticle, which acts as a restoring force. This
force sets the electrons into dipolar oscillation at a certain frequency. The energy of
surface plasmon resonance is governed by the dielectric medium around the nanopar-
ticles and free electrons’ density. The resonance sharpens with increase of particle
size. The larger particles enhance the scattering length. The resonance frequency of
all the noble metals falls in the visible region of the light spectrum [5, 11].
Synthesis and Processing of Nanomaterials 9

2.7 Electronic Properties of Nanomaterials

How the particle size influences the electrical conductivity of nanomaterials is a com-
plex phenomenon? The electrical conductivity is based on distinct mechanisms which
are classified into grain boundary scattering, surface scattering, quantized conduc-
tion, ballistic conduction, widening and reduction of band gap, Coulomb charging
and tunneling and a change in microstructures. An increased perfection, reduced
impurity, minimum dislocation, and low structural defects also influence the elec-
trical conductivity nanomaterials [5]. Only one electron wave mode is observed in
electrically conducting carbon nanotubes. This mode transports the electrical cur-
rent through the nanotubes. Since orientation and length of carbon nanotubes vary,
these tubes would touch the mercury surface at different times by providing a set of
information. This information is about the resistance of different nanotubes and the
effect of tube length on resistance [4].
Changes in electronic properties of low dimensional materials are related to the
wave-like properties of the electrons and scarcity of the scattering centers. When
the system size is comparable to the de Broglie wavelength of electrons, the energy
states exhibit a more pronounced discrete nature. In some cases, the conductors
change to insulators when the size is well below the critical length scale. Conduction
in extremely enclosed structures such as quantum dot is very susceptible to the
presence of other charge carriers, and hence, the dot charge state is known as the
Coulomb blockade effect. This results in single electrons conduction procedures that
in turn require a minimum quantity of energy to run the switch, memory elements,
or transistor [15].

3 Common Synthesis Techniques

Nanomaterial synthesis techniques are split into two primary groups, namely top-
down approaches and bottom-up approaches. These methods are used for assembling
atoms together or disassembling or dissociating bulk materials into finer parts made
up of very few atoms. The top-down approach begins with larger objects as shown
in Fig. 5, which are reduced to lower sizes to achieve fine features and nanoscale
materials. This strategy was originally adopted for the microelectronics sector, but
with the development of nanopatterning and thin-film deposition methods, this strat-
egy entered the nanofabrication regime. This regime includes physical vapor depo-
sition, thin-film deposition, chemical vapor deposition, plasma-enhanced chemical
vapor deposition, laser ablation, etc. [16]. Nanoscale materials are manufactured
in a bottom-up strategy in the form of building blocks that combine to form big-
ger nanoparticles for various uses [16, 17]. Nanoparticles or nanospheres synthesis
and assembling into macroscopic particles are some bottom-up approach material
development techniques.
10 M. Y. Naz et al.

Fig. 5 Top to bottom and

bottom to top synthesis
techniques for nanomaterials

3.1 Sol–Gel Technique

This technique is used for condensation and hydrolysis of metal alkoxides or liquid
precursors into solid nanomaterials [16–20]. As illustrated in Fig. 6, a sol–gel method
includes the development of inorganic networks through sol formation (colloidal
suspension) and sol gelation into gel [17], which is a continuous liquid phase network.
Metals or metalloid components surrounded by reactive ligands are the prevalent
precursors used to synthesize these colloids. In contact with water or diluted acids,
the starting materials are processed to produce dispersible oxides and sol. The liquid
is separated from the sol to produce gel and the size and shape of the nanomaterials
are governed by this sol–gel transformation. On calcination, the gel shifts to oxide.
The reactions for synthesis of nanomaterials through sol–gel technique by hydrolysis
and condensation metal alkoxide are defined as:
Hydrolysis: MOR + H2 O → MOH + ROH
Condensation: MOH + ROM → M–O–M + ROH.
The sol–gel process is performed by a sequence of separate steps such as:
• Formation of stable metal alkoxide solutions or precursors of solved metal.
• The formation of bridged networks of oxide or alcohol also known as gel.
• Network gelation by a polycondensation reaction. This reaction increases the
solution’s viscosity.
• Gel aging to achieve solid mass. The polycondensation reactions continue unless
the gel becomes solid. This stage involves the contraction of gel networks and the
expulsion of solvent from gel pores.
Synthesis and Processing of Nanomaterials 11

Fig. 6 Illustration of synthesis of nanomaterials through sol–gel technique [17]

• Ostwald ripening and phase transitions may occur at the same time as syneresis.
Gel aging may take seven days. It is essential to avoid cracks in the cast gel.
• Water removal and drying of volatile liquids from the gel network. The drying step
involves constant rate period, critical point, falling rate period, and second falling
rate period.
• The gel densifies and decomposes at higher temperatures (T > 8000 °C). The pores
in the gel collapse and other organic species volatilize.
Sol–gel is an effective technique for synthesis of nonmetallic inorganic com-
pounds at very low temperature. These materials include ceramics, glass, and glass
ceramics. Sol–gel processing is preferred over high-temperature counterparts based
12 M. Y. Naz et al.

on firing ceramics and melting of glass. The major problems associated with bottom-
up approach, however, are least control over particles’ growth and agglomeration of
the particles. It is also essential to ensure that the growth reaction is complete and that
the product does not contain any unwanted reactants. The production rate of nano-
materials is comparatively small through this technique [17]. The other problems
associated with such a method are costly raw materials and long drying and sinter-
ing [18–25]. The sol–gel technique could not attain its complete industrial potential
because of these constraints.

3.2 Co-precipitation Technique

Co-precipitation is the most widely used technique of synthesizing nanomaterials

among all known techniques [20–26]. Nanoparticles have been produced through
co-precipitation of aqueous solutions of raw materials. This method involves the
thermal decomposition of the solids and the formation of the precipitates. The com-
plete process is broken into nucleation, growth, coarsening, and agglomeration of
the particles. Nucleation and development steps should be well controlled for the
synthesis of monodispersed nanoparticles. Both nucleation and synthesis steps can
be controlled by altering the mixing ratio of reactants, adjusting the reaction param-
eters, adding surfactants, changing solvents, and changing the injection sequences.
Relatively fast nucleation and steady growth of particles result in monodispersed
nanoparticles. Nanoparticles’ molecules follow the Oswald ripening during slow
growth mode, while fast-growth mode results in dispersed distribution of nanopar-
ticles’ size and uneven morphology. Smaller particles disappear during the Oswald
ripening phase while bigger particles continue to grow. This trend is ascribed to the
least stable molecules on the particle surface. The molecules within the particles
are already packed and well-ordered. The large particles have reduced volume-to-
surface ratios, hence the low energy states. When the process attempts to reduce its
energy, molecules at the surface of smaller particles tend to spread into the solution
and attach to the bigger particles [27–30].
The method of co-precipitation is widely used in biomedical applications as it
includes less harmful materials and processes. In this method, metallic nanoparticles
are made from aqueous salt solutions in this method. In an inert atmosphere, a base is
added to the solution at room temperature. The response to co-precipitation is merely
expressed as:

Fe2+ + 2Fe3+ + 8OH− → Fe (OH)2 + 2Fe(OH)3 → Fe3 O4 + 4H2 O

The ferrous hydroxide suspensions are partly oxidized with separate oxidizing
agents for the production of spherical nanoparticles in solution or the aging of
stoichiometric mixtures of ferrous and ferric hydroxides takes place in aqueous
media [31]. The size and shape of the particles depend on salt type, pH value, reaction
temperature, ratio of ferric and ferrous ions, stirring rate, and dripping speed of the
Synthesis and Processing of Nanomaterials 13

basic solution and ionic strength of the media. The particle size can also be controlled
over one order of magnitude by changing pH and ionic strength of the medium of
precipitation. Sometimes co-precipitation yields particles with wide a distribution of
sizes, which often requires selection of secondary sizes [20, 32–34].

3.3 Green Synthesis Technique

The method of green synthesis is preferred over physical and chemical methods.
This method is cost-effective, simple to scale, and environmentally friendly for bulk
synthesis. Additional green synthesis can be performed at comparatively low pres-
sure, temperature, and energy without the use of toxic chemicals [21, 35]. However,
biosynthesis of plant-based metal nanoparticles is in its infancy and needs further
research efforts to be known as a fully developed process. The synthesis of nanopar-
ticles from the plant extract, exudates, inactivated plant tissues, and other parts is
a non-toxic and safer approach as compared to other well-known synthesis tech-
niques. Other biological techniques for the production of nanoparticles include fungi,
microorganisms, enzymes, and plant extracts [20]. The use of plants in biosynthesis
is primarily due to the existence of reducing agents, which play a crucial part during
the synthesis process [20]. The commonly known plant-based reducing agents are
flavonoids, citric acid, ascorbic acids, extracellular electron shuttles, reductases, and
dehydrogenases.

3.4 Microwaves Assisted Synthesis

Microwaves are a form of electromagnetic energy in the electromagnetic spec-

tral range of 300–300,000 MHz. Microwave heating is the best process whereby
microwaves are directly coupled with the molecules of the reaction mixture. This
process ensures fast heating, short reaction time, and clean chemistry of the reac-
tion. Microwave chemistry is also referred to as green chemistry because it produces
no hazardous material such as gas fumes or heat using internal energy sources.
Microwaves utilize electromagnetic radiations that pass-through material and pro-
duce heat via molecular oscillation. Microwave heating generates the same amount
of heat in the whole material at a high speed and at a high reaction rate at the same
time. Synthesis aided by microwaves has become a tool of significant importance
for fast organic synthesis. Some of the main benefits include a dramatic reduction in
reaction time, enhanced conversion efficiency, clean product formation, and a wide
scope of development of new reaction conditions [22].
Water is a good microwave absorber and a polar solvent. Figure 7 shows a sim-
plified schematic illustration of heating mechanism of the water molecules through
microwaves [23]. Polarized water molecules attempt to orientate during microwave
14 M. Y. Naz et al.

Fig. 7 Water molecules under microwave irradiation in an alternating electric field

heating with the quickly changing alternating electric field. In response, heat pro-
duces due to the rotation, collision, and friction of the water molecules. When ionic
salts are dissolved in water, they affect the structure of the water molecules. The
relaxation time of the molecules at lower concentrations initially reduces and then
rises. The presence of the ions is assumed to cause a breakage of the hydrogen bond-
ing in water. Those water molecules that are aligned with the ions are relatively fixed,
but those that are not coordinated do not experience such powerful intermolecular
hydrogen-bonding impacts, and thus have reduced relaxation times in this free state.
The impacts are reversed at higher concentrations and the relaxation time of water
in concentrated salt solutions is higher than that of pure water, probably owing to
a higher ordering of water molecules when there is a large amount of ions in the
solution.
The metallic nanomaterials of different morphologies, including nanospheres,
nanopolygonal plates, nanosheets, nanorods, nanowires, nanotubes, etc. can be pre-
pared within few minutes through microwave heating. The morphology and size of
nanostructures can be regulated by changing multiple experimental parameters such
as metal salt concentration, surfactant chain length, solvent, and temperature of the
reaction.

3.5 Plasma Synthesis Technique

Different kinds of plasma reactors that can be used to synthesize nanocrystals have a
number of common characteristics to help understand suitable conditions for plasma
formation and growth of nanocrystals. The main characteristics are:
• Reactor vessel: It describes the plasma volume and separates the mixture of
precursor gases (often diluted in an inert carrier gas) from the surrounding air.
Synthesis and Processing of Nanomaterials 15

• Electrical power: An electric power supply is used to convert the gas mixture into
plasma through direct current electric field or time-varying radio or microwave
frequencies.
• Plasma electrodes: These are the means of plasma coupling such as electrodes,
resonant cavities, or antennas.
• Gas controllers: Such devices are attached to the plasma reactors for controlling
the supply of precursor gases or vapors and to create the desired gas pressure in
the plasma reactor [18].
In low-pressure plasmas, two distinct types of synthesis strategies are adopted:
batch reactors and flow-through reactors. The performance of batch type reactors
depends on ability of the discharge plasmas to trap the negatively charged species
produced during gas ionization. The charged species may be subjected to a constant
flow of gases and allowed to expand to larger dimensions. Particles are gathered after
switching off the plasma and enabling the particles to drop down on a substratum by
gravity or through the gas flow to a filter. In a flow-through reactor, nanoparticles are
transported through the reactor in a gas flow soon after they nucleate and develop.
As the nanoparticles grow, the precursor will be depleted and particle growth will
ultimately be limited in the gas stream by the available precursor. Particles are brought
into the gas that flows out of the reactor and gathered on a substratum or using filters
[21].

3.6 Simple Heating Method

The easiest way to produce the nanoparticles is to heat the precursor material in a
heat-resistant crucible. Figure 8 shows a schematic representation of the gas phase
synthesis method of single-phase nanomaterials from a heated crucible [4]. This
method is only suitable for materials with high vapor pressure at temperatures of
up to 2000 °C. The energy is supplied to the precursor material through arc heating,
Joule heating, or electron-beam heating. The atoms evaporate into an atmosphere that
is either inert or reactive (so that a compound is formed). In order to perform reactive
synthesis, materials with very low vapor pressure must be fed into the furnace in the
form of an appropriate precursor such as organometallics, which decomposes into
the furnace to produce a condensable material. The atoms of the evaporated material
lose energy by collision with the cold gas atoms and undergo condensation through
homogeneous nucleation into tiny clusters. The precursors react in the gas phase
when a compound material is synthesized. The precursors form a compound with
the material that is injected independently into the reaction chamber. If they remain
in a supersaturated region, the clusters would continue to grow. To control their size,
a carrier gas is used to remove them quickly from the supersaturated environment.
Three parameters play a key role in controlling the cluster size and its distribution:
i. Evaporation rate, which depends on energy input.
ii. Condensation rate, which depends on energy removal.
16 M. Y. Naz et al.

Fig. 8 Schematic
representation of the gas
phase synthesis method for
single-phase nanomaterials
from a heated crucible

iii. Gas flowrate, which for removal of clusters.

This method can be extended from laboratory to industrial scale due to its inherent
simplicity [4].

3.7 Solvent Evaporation Technique

The first technique established for the preparing of nanoparticles was solvent evapo-
ration. Using this technique, polymer solutions were formed in volatile solvents and
emulsions were formulated with the use of dichloromethane and chloroform. Nowa-
days, ethyl acetate is preferred for the stated purpose due to its better toxicological
profile for obtaining the polymeric particles with dimensions smaller than 500 nm.
During the preparation stage, the emulsion is transformed into a nanoparticular sus-
pension when the solvent is evaporated, after which the solution can be diffused
through the continuous emulsion phase by performing some standard procedures.
The procedures involve high-speed ultrasonication or homogenization and evapora-
tion of the solvent through magnetic stirring at room temperature or under reduced
pressure. The magnetic stirring results in solidified nanosized particles, which are
collected through ultracentrifugation and washed to remove surfactants. Finally, the
product is lyophilized [24] (Fig. 9).
This technique comprises of the preparing of nanoemulsions, formulated in a
volatile solvent solution with a polymer dissolved. Dichloromethane and chloroform
are the commonly used solvents, but are often substituted by ethyl acetate, a less toxic
solvent, and therefore much more suited to the synthesis of the controlled release
systems in which the encapsulation of drugs is involved. This technique is performed
under vacuum where suspension is developed by evaporating polymer solvent from
Synthesis and Processing of Nanomaterials 17

Fig. 9 Illustration of a solvent evaporation technique

emulsion droplets, which can be diffused through the continuous phase. This slow
method includes a rapid evaporation period in which at least 90% of the remaining
solvent is removed, followed by a slow evaporation period in which the remaining
solvent is extracted. Due to the elevated solvent loss, droplet size dramatically reduces
during the first step to reach a minimum value. On the contrary, a substantial rise in
droplet diameter due to coalescence characterizes the second step. In polymers with
interfacial adsorption characteristics, this coalescence process can be accentuated,
whereas in polymers with bad surface-active characteristics, coalescence is low.
Furthermore, partly miscible solvents can be used in emulsion precipitation and
evaporation conditions can be changed. In this case, the removal of volatile solvents
can be done by distillation [25].

3.8 Mechanochemical Process

Mechanical attrition is a technique established in 1970 to produce fresh alloys and

phase mixtures from powder particles as an industrial process. The quantity limita-
tions for nanocrystalline preparation can possible be controlled through this tech-
nique; therefore, nanocrystalline powders can be produced on large scale. It also
provides many options in the preparation of various structures in nanostructured
powders such as crystalline–crystalline or amorphous–crystalline and atomic bond-
ing like metal–metal, metal–semiconductor, and metal–ceramic materials. The most
significant benefit is that mechanical milling can be performed at lower temperatures,
allowing the newly shaped grains to grow very slowly [6]. The high mechanical force
leads to the destruction of materials and creates a distinct structure. Mechanochem-
ical technique has been commonly used in advanced material synthesis, covering
nearly all aspects of material science.
18 M. Y. Naz et al.

Planetary ball mill is a typical mechanical process whereby the planetary ball
mill is used for grinding of the materials by rotating the big plate continuously and
simultaneously rotating the containers. The speed of the plate revolution and the
speed of the container rotation can be adjusted independently [26]. Particles larger
than 100 nm cannot, therefore, be excessively cold welded. As a consequence, the
average grain size can be reduced by up to 2–20 nm. The mechanism of formation
of microstructure is very distinct from other techniques of synthesis, but it is very
comparable to the final microstructure. Due to mechanical attrition, a severe plastic
deformation happens, resulting in a constant refinement of the inner composition of
the powder particles to nanometer scale [27].
Mechanical milling is susceptible to contamination; it is possible to use atmo-
spheric control for chemical reactions between atmosphere and milled powders.
This has resulted in a novel and cost-effective technique for production of nanopow-
ders. A conventional ball mill can be used as a chemical reactor at low temperatures
for mechanochemical processing. Ball milling improves the reaction kinetics of the
reactants due to intimate mixing and refinement of grain structure to nanometer
scale. Since reaction takes place during actual milling, a suitable reactive gas (oxy-
gen or nitrogen, atmospheric air) and a suitable precursor are used during milling
stage. A variety of metals can be used in reactive milling where metal powders are
transformed to nanocrystalline metal–ceramic composites [6]. Reducing the process
cost and product industrialization can be achieved using a variety of precursors such
as carbonates, fluorides, oxides, hydroxides, sulfates, chlorides, etc. For mechani-
cal attrition, various ball mills such as tumbler mills, shaker mills, planetary mills,
vibratory mills, etc. have been developed. The material powder is put in a sealed
container with tungsten carbide or steel coated balls. Kinetic energy of balls depends
on their mass and velocity. Since steel or tungsten is high-density materials, they are
preferred as a milling material [6].

3.9 Sonochemical Technique

Sonochemistry is a technique in which the application of strong ultrasound radia-

tion causes molecules to undergo a chemical reaction. Acoustic cavitation, which
involves the formation, growth, and fall of bubbles in an ultrasonically irradiated
liquid, is the driving force responsible for the sonochemical process. Although in the
construction of reactors cavitation is prevented, still acoustic cavitation is the key to
sonochemical processing owing to its capacity to regulate and restrict its impacts to
the reaction rather than the reactor. This technique has been used widely to create
extraordinary characteristics of nanosized materials. Unique process conditions such
as elevated temperature, elevated pressure, and elevated cooling rates make it easier
to form smaller particles and different product sizes compared to other techniques.
In conducting sonochemical experiments, the primary benefit is that it is very cheap
[6].
Synthesis and Processing of Nanomaterials 19

Fig. 10 Schematic of a chemical vapor deposition reactor

3.10 Chemical Vapor Deposition Technique

Chemical vapor deposition (CVD) is referred to as activating chemical reactions

between a substrate surface and a gaseous precursor in order to deposit a thin solid
film onto the substrate. Surface activation and growth activity can be achieved either
with increased temperatures (thermal CVD) or with plasma (plasma-enhanced CVD).
A PECVD process is carried out at significantly lower temperatures compared to the
thermal CVD process [6]. CVD is a widely used technique in material processing
industry due to its low set-up cost, high production yield, and ease of scale-up. As
shown in Fig. 10, CVD has been developed as a novel manufacturing process in
many industrial sectors such as semiconductors and ceramic industry [28].
A typical CVD process involves the mass transportation of reactants delivered by
the gaseous or liquid precursor to the substrate surface, adsorption of reactants at
substrate surface, chemical reaction of the reactants at the substrate surface to form
thin film, desorption of by-products of the reaction from substrate surface and removal
of by-products and unreacted reactants. The deposition rate of a film in CVD process
is mainly controlled by the slowest step in this serial process [16]. Since adsorption
and desorption at the substrate surface usually occur at relatively faster rates, the
deposition rate is anticipated from the competition between mass transportation of
reactants in the first step, by-products in the last step, and the surface reaction rate
in the third step. The whole process is illustrated in Fig. 11. Mass transportation is
a function of gas flowrate and its partial pressure while surface reaction rate is an
exponential function of process temperature [16].
20 M. Y. Naz et al.

Fig. 11 Illustration of a typical CVD process involving five growth steps

The chemical response of the surface is dominant at elevated temperatures. As

soon as it hits the surface, the precursor will react with the substrate and form a
thin film. Therefore, mass transportation controls this process. By raising the supply
of reactants such as gas or liquid precursors, mass transportation can be improved
and consequently the rate of deposition. Usually, the deposition occurs at various
nucleation sites and expands and coalesces together.
Since deposition rate is governed by the mass transportation, if the surface has
a pronounced topography, the film tends not to be conformal and the deposition
rate is also usually difficult to control. On the other side, the surface reaction rate is
slow for a low-temperature regime and becomes the dominant phase. In this case,
the deposition rate will remain the same regardless of any change in the flowrate
of reactants. The surface will have an adequate supply of reactants due to the slow
reaction rate, and reactions generally occur concurrently in all surface fields, resulting
in a very uniform and conformal deposition. However, if the temperature is too low for
thermodynamic reasons, the reaction may not happen at all. It reveals that for a CVD
method, selecting the right temperature is of significant importance.
CVD reactors are classified into normal CVD reactors and PECVD reactors. In a
normal CVD process, reactants can be either gases or liquids and there can be more
than one reactant. The reactant generally has a thermal decomposition reaction at
the surface of the substrate if there is only one reactant involved in a CVD process.
If more than one reactant is involved, these would be the precursor and a reducing
agent. The normal CVD reaction temperature varies from case to case; however, it
should be high enough to initiate the decomposition of the precursors and activation
of the substrate surface [16].
Like a PVD method, DC or RF plasma is also used in many modern thin-film
deposition methods involving CVD reactors. The plasma helps in breaking down the
precursors before they reach the surface of the substrate. Therefore, it considerably
Synthesis and Processing of Nanomaterials 21

reduces the surface temperature needed for the chemical reactions. The plasmas are
generated and sustained under very low pressures [16].
A typical CVD reactor includes gas delivery system, loading/unloading sys-
tem, reaction chamber, vacuum system, energy system, process control system, and
exhaust gas treatment system. The gases are fed into the reaction chamber at temper-
atures in the range of 500–1200°C. Other than the precursor gas, argon and nitrogen
are used as carrier gases. When gases come into contact with the heated substrate
in the reactor they react and form a strong layer on the surface of the substrate.
The critical operating parameters of this method are the temperature and working
pressure [6]. Finally, CVD is being widely used for synthesis of carbon nanotubes
and is the most promising technique as compared to arc discharge and laser abla-
tion techniques. Recently, a swirled floating catalyst CVD reactor is developed for
up-scaling nanotubes’ production capacity. A vertical reactor was placed inside a
furnace and cyclones for collecting the final product [6]. It is worth mentioning that
although CVD is a flexible technique, it requires numerous experimental works for
standardization of the appropriate growth parameters [6].

4 Applications of Nanomaterials

Nanotechnology is being implemented through a range of applications from opti-

cal communications, electronics, biological systems, and automotive engineering
to new materials. Many possible applications have been explored and a number of
nanomaterials’-based devices and systems have been studied previously [29, 30, 36,
37]. These applications are based on (i) the peculiar physical properties of nanosized
materials, for example, gold nanoparticles used as inorganic dye to introduce colors
into glass and as low-temperature catalyst, (ii) the huge surface area, such as meso-
porous titania for photo-electrochemical cells, and nanoparticles for various sensors,
and (iii) the small size that offers extra possibilities for manipulation and room for
accommodating multiple functionalities [5]. Future applications of nanomaterials
include next era laptop chips, better insulation materials, kinetic power penetrators,
lethal weapons, phosphors for high definition televisions, low cost flat panel display,
cutting tools, pollution remediation, high-density materials, powerful magnets, high
performance batteries, highly sensitive sensors, aerospace additives with superior
performance, advanced weapon platforms, satellites, medical implants, machinable
ceramics, drug delivery, smart buildings, etc.
22 M. Y. Naz et al.

5 Conclusions

While replication of natural phenomena is one of the most promising research areas
of nanotechnology, researchers are still attempting to understand their amazing com-
plexities. Nanotechnology is a rapidly expanding area of research where novel proper-
ties of materials manufactured on nanoscale can be used to benefit humanity. Nano-
material always performs better than their bulk counterparts due to some tunable
physical and chemical properties. By selecting suitable conditions and synthesis
method, it is possible to tune the melting point, electrical conductivity, wettability,
thermal conductivity, light absorption, catalytic activity, and scattering properties
of nanomaterials. Conclusively, chemical vapor deposition provides good control
over structural parameters during synthesis of nanomaterials. This method can be
extended from laboratory to industrial scale due to its inherent simplicity and low
process cost.

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Perspective of Nanomaterials
in the Performance of Solar Cells

Hafiz Muhammad Asif Javed, Wenxiu Que, Muhammad Raza Ahmad,

Khuram Ali, M. Irfan Ahmad, Anam ul Haq and S. K. Sharma

Abstract Solar cells have a great promise to solve the world energy crises in a sus-
tainable way. In recent years, numerous efforts have been devoted on different aspects
and performance of solar cells with a common task of achieving higher efficiency
to compete with the traditional energy resources. Cost-effectiveness and enhancing
power conversion efficiency are the major tasks in the photovoltaic technology. New
field of nanotechnology has developed promising possibilities to improve the quality,
stability, and performance of solar cells. Nanomaterials can contribute to solar cell
design in different ways, which play an important role in their performances. Devel-
opments of nanomaterials-based solar cells could reduce the cost and stability for
bulk power generation as well as enhance the power conversion efficiency. This book
chapter reviews the performances of traditional solar cells and focuses on different
contribution of advanced nanomaterials in solar cell advancement.

Keywords Generation and classification of solar cells · Nanotechnology ·

Performance parameter · Stability · Light harvesting efficiency

H. M. A. Javed · K. Ali · M. Irfan Ahmad · A. Haq

Department of Physics, University of Agriculture Faisalabad, Faisalabad 38000, Pakistan
H. M. A. Javed (B) · W. Que (B)
Electronic Materials Research Laboratory, International Center for Dielectric Research, Key
Laboratory of the Ministry of Education, School of Electronic and Information Engineering,
Xi’an Jiaotong University, Xi’an 710049, Shaanxi, People’s Republic of China
e-mail: [email protected]
W. Que
e-mail: [email protected]
M. R. Ahmad
Center for Advanced Studies in Physics (CASP), GC University Lahore, Lahore, Pakistan
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago

© Springer Nature Switzerland AG 2020 25

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_2
26 H. M. A. Javed et al.

1 Introduction

The demand for energy is swelling year to year in all over the world and the handling
of this demand will be the biggest challenge in the near future. Particularly, energy
demand has become a serious issue in third world countries. These countries are
focusing to find the proper solution of this issue because it is considered very impor-
tant for their development. Scientists and researcher are more interested in renewable
energy sources than the non-renewable energy sources. Out of these renewable energy
sources, solar energy is the most interested area of the researcher. The use of solar
energy is always considered as the most beneficial, infinite, and environment-friendly
source [1]. Researchers are trying to find an inexpensive and clean energy method to
use the solar energy [2]. The most common effort for fulfilling the demand of energy
is the use of solar cells which convert the sunlight into electrical energy [1, 2]. The
traditional solar cell is consisting of silicon wafers which traps the fallen sunlight on
it and converts it into electricity. Researchers are trying to synthesize the new mate-
rials that are inexpensive and eco-friendly. Generally, these materials have different
physical and chemical characteristics which depend upon their size and shape. When
their size is less than 100 nanometers (100 nm), they are considered as nanoscale or
nanotechnology. So, at nanoscale, their magnetic, chemical, optical, and electronic
properties along with reactivity response are entirely different from their bulk scale.
Due to these qualities, the concept of nanotechnology or nanoparticles (NPs) is used
in the manufacture of solar cells as it reduces the manufacturing costs as a result
of a low-temperature processing similar to printing instead of the high-temperature
vacuum deposition process typically used to produce conventional cells made with
crystalline semiconductor material. These NPs have also reduced the installation cost
of solar cells because at nanoscale they can be rolled like a sheet which is not possible
with conventional crystalline panels. This rolling characteristic has been developed
in solar cells due to semiconductor thin films. Currently, available nanotechnology
solar cells are not as efficient as traditional ones. Researchers have improved the
efficiency level using quantum dots [3].
The conventional solar cells depend upon the silicon wafers are known as first-
generation solar cells and have the power conversion efficiency of about 25.6%.
The second-generation solar cells were fabricated with thin films and CdTe-based
solar cells have the efficiency of about 19.6% [4]. Third-generation solar cells are
also called nanomaterials-based solar cells, e.g., dye-sensitized solar cells (DSSCs),
quantum dot solar cells, hybrid solar cells, organic solar cells, and perovskite solar
cells (PSCs). DSSCs and PSCs are unique due to their performance in the research
field of photovoltaic and can approach the theoretical efficiency limit [5].
Perspective of Nanomaterials in the Performance of Solar Cells 27

2 The Generations and Classifications of Solar Cells

2.1 Solar Cell Technologies

2.1.1 First-Generation Solar Cell Technologies

First silicon-based solar cell was manufactured in Bell laboratories 1954 with 6%
efficiency. Solar cells based on silicon materials are the mostly used according to
the single-cell PV device, more sufficient element on earth is silicon. Silicon is
a semiconductor material and it is appropriate for photovoltaic applications with
1.1 eV energy bandgap. Crystallites silicon solar cells are divided into three main
types based on arrangement of Si wafers. Different types of silicon are used to make
the different solar cells with different efficiency, specifically:
• Polycrystalline (poly c-Si)
• Monocrystalline (mono c-Si)
• Amorphous silicon cells.
The earliest technology of solar cell is still very important and valuable for solar
cells. Solar cells are manufactured from thin silicon wafers. These solar cells are
called monocrystalline solar cells. Early in 1963, c-Si modules were produced com-
mercially, when Sharp Company of Japan started the manufacturing photovoltaic
modules commercially and produced a 242 W PV [5]. This solar cell has more effi-
ciency (up to 26%) which means more electric energy from the specific area of panels.
Czochralski process is used to single crystal wafers of silicon; it covers about 30% of
the PV market. Amorphous and polycrystalline silicon are less pure than that of a sin-
gle layer of crystalline silicon, less expensive, and most favorable. Monocrystalline
solar cells are much expensive as compared to the polycrystalline materials because
this is made by a single layer of crystal. Polycrystalline silicon solar cells have the
highest efficiency of about 21% [6]. Silicon solar panel typically contains two layers:
a p-type positive layer and n-type negative layer. The pure crystalline silicon is a poor
conductor of electricity because none of its electrons are free to move about. Other
atoms are purposefully mixed in with the silicon atoms, such as phosphorous that
have five electrons in its outer shell. It bonds with its silicon neighbor atoms, but in
a sense, the phosphorous has one electron that does not have anyone to hold hands
with. It does not form part of a bond, but there is a positive proton in the phosphorous
nucleus holding it in place [7]. Impure silicon with phosphorous atoms takes less
energy to knock loose one of our “extra” phosphorous electrons because they are not
tied up in a bond. The process of adding impurities on purpose is called doping, and
when doped with phosphorous, the resulting silicon is called N-type because of the
prevalence of free electrons. N-type doped silicon is a much better conductor than
pure silicon. The other part of a typical solar cell is doped with the element boron,
which has only three electrons in its outer shell instead of four, to become P-type
silicon. Instead of having free electrons, P-type has free openings and carries the
opposite (positive) charge [8].
28 H. M. A. Javed et al.

2.1.2 Second-Generation Solar Cell Technologies

The second generation of solar cell is also called thin film solar cells. In this genera-
tion, solar cells are manufactured from very thin layers in few micrometers. Thin film
solar cells could actually deliver electricity with lower cost than c-Si wafer-based
solar cells. Thin films can be arranged into lightweight and flexible structures, which
easily combined into structural component building-integrated PV (BIPV) [9]. There
are three basic types of thin-film solar cells that have been commercialized:
• Amorphous silicon
• Cadmium telluride
• Copper indium gallium selenide (CIGS).
Numerous tiny electronic devices and calculators can be operated by amorphous
silicon solar cells. A biggest disadvantage of amorphous silicon-based panels is that
those are less efficient per unit area. There are limited major differences between
second-generation solar cells and first-generation solar cells. The most prominent
difference is the direct bandgap and the indirect bandgap types of the semiconductor
materials, but both types depend on the p-n junction model. Copper indium gallium
selenide (CIGS) solar cells, CdTe solar cells, and amorphous solar cells have highest
efficiency of 21%, 21.4%, and 11.8%, respectively [8–13].

2.1.3 Third-Generation Solar Cell Technologies

The third-generation solar panels are totally changed from other first and second
generations as their efficiency do not depend on the design of p-n junction. The
third generation of solar panels is being fabricated by different types of nanoma-
terials, polymers, and organic dyes. First-generation solar cells are very costly and
toxic. On the other hand, in the second-generation solar cell, a very limited number
of materials are available for second-generation solar cell. Recently, scientists are
working on third-generation solar cells to improve the power conversion efficiency
by developing new nanomaterials and techniques. In 1991, Gratzel introduced a new
kind of solar cells, called Gratzel cells. Later on, they are called dye-sensitized solar
cells. The main parts of dye-sensitized solar cells contain a nanostructured semicon-
ductor oxide, an organic dye sensitizer, a redox electrolyte, and a counter electrode.
Nowadays, studies on the features of dye-sensitive solar cells are very extensive to
overcome the production cost and to get very high performance. Performance of
solar cell depends on many parameters, for example, size of particle, bilayer TiO2
photo-anode, nature of organic dye, and liquid electrolyte. However, due to the liquid
electrolytes in dye-sensitized solar cell, many difficulties are observed, for example,
short-term stability due to evaporation of organic solvent, leakage, electrode oxi-
dization, and limited inorganic salts solubility [14–20]. The most advanced type of
third-generation family is perovskite solar cell. Perovskite solar cells demonstrate
more advantages than other solar devices, due to their transparency, simple manufac-
turing process, cost-effective, high efficiency, environmental friendly, and flexibility.
Perspective of Nanomaterials in the Performance of Solar Cells 29

Perovskite solar cells perform very well in terms of factors such as lifetime, effi-
ciency, and recombination rate under laboratory conditions as compared to other
solar cells, so the price could be controlled for commercial applications [21–30].

2.2 Classifications of Third-Generations Solar Cells

2.2.1 Organic Solar Cells

The organic solar cells practice organic nanomaterials that manage semiconductors,
organic polymers, and organic elements, which deliver power and lightweight. It
is also known as flexible solar cells that use electrical phenomenon impact to gen-
erate power. Organic solar cells are actually manufactured from organic chemical
compound materials [31–34]. Organic solar cells have attained importance due to
their unique parameters, such as less weight, flexibility, and affordable. Researchers
analyzed and mentioned the 3D organic photovoltaic cell structures with rear connec-
tion electrical diversions that have a complete extended capability [35–40]. Scientists
introduced an advanced model of organic solar cell with graphene, and the graphene
is synthesized by different strategies, e.g., a biochemical vapor method, a surface
oxidization treatment at the earlier step of the graphene advancement. After that, the
graphene was turned to polythene terephthalate substrate. In addition, researchers
introduced an advanced structure of organic solar cells by which effectiveness has
extended from 5.8 to 7.11% in integrated Au/Ag bimetallic nanocomposite which
is highly sensitive plasmonic material [41–45]. The Au/Ag bimetallic nanocompos-
ites distinctly feature converging dual plasmon resonance peaks to a single plasmon
resonance peak, strongly depending on the packing density and the unit size. It is
expected to achieve high open-circuit voltages in organic solar cells. The best result
of voltage attained after several attempts is 0.44 V, and the efficiency improves from
3.1 to 4.4% [44–50].

2.2.2 Dye-Sensitized Solar Cells

Dye-sensitized solar cell (DSSC) was invented by Michel Gratzel and his colleagues
in 1991 [44]. The DSSC is still in evolutionary process. Researchers are improving the
electrical properties and performance of DSSC by incorporating the suitable materials
into TiO2 film. Recently, Fe3 O4 has earned good name in the field of biomedical and
as a photocatalyst because of its high specific surface area, biocompatibility, and good
dispersion. Now, this material (Fe3 O4 ) has attained attention of researchers to modify
the optoelectronic devices. There are many reports of enhancing the photovoltaic
properties in DSSC [45–50]. So, this new DSSC has produced power conversion
efficiency of 3.54% [51]. Some researchers used pigment of TiO2 nanoparticles and
multiwall carbon nanotubes in DSSCs. The photo-anode carbon-based TiO2 has also
30 H. M. A. Javed et al.

been reported for DSSCs [52, 53] by achieving the capability of 5.45% that is 61%
more as compared to untreated photo-anode.
Multi-walled carbon nanotubes (MWCNTs) are hollow, cylindrical-shaped
allotropes of carbon that have a high aspect ratio (length to diameter ratio). MWNTs
consist of multiple rolled layers of concentric nanotubes of graphene inside other nan-
otubes. Carbon nanotubes can also be effective semiconductors with the right
arrangement of atoms. Researchers have created discrimination in the photocurrent
–voltage characteristics of DSSCs by using chemical treatment of multi-walled
carbon nanotubes (MWCNTs) on TiO2 films [54–59].

2.2.3 Nanocrystals Solar Cells

Nanocrystal solar cells (NSCs) are fabricated on a substrate with a coating of

nanocrystals. The substrates are generally silicon or various organic conductors. In
spite of considerable approach, the nanocrystals solar cells were not suitable for
bulk scale production due to lower efficiency, high cost and effectiveness above Si
based Solar cells [60, 61]. Researchers introduced a nanostructured semiconducting
material on exterior of crystalline Si(C-Si) by metal-helped biochemical engraving
(MCE) method [62]. Structure is most fitting to stop the ultraviolet light in lightweight
mode. Nanocomposite is enclosed by zinc oxide with traditional dye [Laali, Zobo]
and designed dye, dye employed nanocomposite exhibits a lot of vital activity.

2.2.4 Polymer Solar Cells

Polymers-based solar cells are also the part of third generation and also named as
plastic solar cell. The recorded highest energy conversion efficiency currently is
10% [63]. In order to further improve the performance, new polymers with vari-
ous molecular structures and their applications in photovoltaic devices are under
intensive investigations. These cells are fabricated which have greater skillful-
ness with ease of fabrication. Regardless, it needs further advancements to extent
efficiency since it is so much lingering behind the normal solar cells [63–68].
The researchers define a unique poly (3-hexylthiophene)(P3HT)/C-70 photoactive
composite by heptane/o-dichlorobenzene and modified effectiveness of 24% was
achieved [69]. Nickel/Titania nanocomposite with poly(3-hexylthiophene)/[6,6]-
phenyl-C70-butyric has been achieved, which could be used for chemical opto-
electronic devices. Execution of polymer chemical compound-based solar cell is
much better by presenting gap conditions among dynamic coated metal sheets.

2.2.5 Perovskite Solar Cells (PSCs)

Perovskite is unique in all photovoltaic devices to build up an advanced PV structure.

Perovskites are class of blends pictured by the structure ABX3 , where X addresses
Perspective of Nanomaterials in the Performance of Solar Cells 31

halide group as anion, for example, I− , Br− , Cl− , A and B are cations of novel
estimations [70]. The distinctive resources are employed to fabricate the device and
focused on the importance of perovskite solar cells [71] by continuing progressions
in perovskites solar cells and thus lead-free salt perovskites [72]. Perovskite solar
cell was organized by comprising Si p-i-n nanowire cluster loaded up with alkyl
radical ammonium ion lead halides. The efficiency of 13.3% was obtained as a result
of their additional features and lightweight [73].

3 Nanomaterials- and Nanocomposites-Based Solar Cells

Nanoscale devices and objects have provided a revolutionized opening in the field
of solar energy. Now, the conversion of solar energy has become highly efficient
and low cost through nanostructured devices. New challenging tasks associated to
demonstrate high level of efficiency and stability are now being addressed in the
research community. Nanostructured materials have recognized themselves as an
inexpensive energy absorbing option and have overridden the traditional resources.
These materials have ability to manipulate light and control energy flow at nearly
the atomic level. Nanostructured solar cells are a type of third- or next-generation
solar cell and include those that are based on nanostructures and/or nanostructured
interfaces such as nanowire, mesoscopic, and quantum dot solar cells as shown in
Fig. 1a–c. They hold great promise toward new approaches for converting solar
energy into either electricity (in photovoltaic devices) or chemical fuels [74].
The conventional solar cells are fabricated from bulk semiconductors. The semi-
conductor absorbs the light as a result of electrons and holes are generated. After
creation of electrons and holes, they apart from each other and move toward dif-
ferent contacts to produce voltage V and current I and thus power (P = I × V ).
These materials have large dielectric constants due to this property the electrons and
holes are speedily partitioned from one another and do not interact. Nanostructuring
eliminates the need of high-dielectric-constant semiconductors and opens the new
paths for synthesizing new types of materials and for designing the new designs. For
example, two dissimilar materials, where one is n-type (conducts electrons) and other
is p-type (conducts holes), can be intermixed with nanoscale morphology. It is under-
stood that absorption of light causes an excited state (exciton) that undergoes rapid
charge transfer producing electrons and holes in separate phases, making their inter-
action less probable. Based on this mechanism, two types of solar cell are designed:
organic photovoltaic devices (OPD) and dye-sensitized solar cells (DTSCs).
Another next-generation approach for photovoltaics is based on semiconductor
nanocrystals. The most important properties for photovoltaic applications are the
strong size-dependence of the bandgap, and the large modification of the relaxation
dynamics of photo-excited charge carriers that are created by the absorption of pho-
tons within energies larger than the band gap. The bandgap of the absorber layer could
be optimized to improve the absorption of photons and to limits the output voltage
of the solar cells. Because only the radiation with higher energy than the bandgap is
32 H. M. A. Javed et al.

Fig. 1 Potential benefits as well as of the scientific challenges that need to be overcome in nanos-
tructured solar cells are a quantum dot solar cell, b nanowire solar cell; holes (h+ ) are extracted
from the outer layer (red) and electrons (e– ) flow through the core of the nanowire (blue), and
c mesoscopic solar cell
Perspective of Nanomaterials in the Performance of Solar Cells 33

absorbed, narrower bandgap materials absorb more solar photons, resulting in higher
photocurrents. However, the output voltage is linearly proportional to the bandgap,
and thus wider bandgap materials allow higher voltages. In the Shockley–Queisser
analysis, there is an optimal bandgap that achieves the highest efficiencies and ranges
between 1.2 and 1.4 eV. Semiconductors with bandgaps lower than 1 eV are generally
not employed in single-layer solar cells. Quantum confinement effects in quantum
dots (QDs) can increase the bandgap by more than 1 eV compared with the bulk
value, expanding the range of semiconductor materials viable for photovoltaics. A
prototypical example is PbS. Bulk PbS has a bandgap of 0.4 eV but PbS QDs can
have bandgaps from ~0.6 to ~2 eV depending on their size.
Quantum dot solar cells (QDSCs) (Fig. 1a) are treated from colloidal suspensions
at ambient air temperatures and relatively have low fabricating costs. One approach to
relax such requirements has been explored by using radial p-n junction Si nanowires.
A core-annular p-n junction (Fig. 1b) is created along the length of the wire. When the
incident light generates charge carriers at the junction, minority carriers only need to
traverse the nanowire diameter in order to be collected. With less strict requirements
on the minority carrier lifetimes, lower-grade silicon can be used. Two different
substances, first is n-type and second is p-type, are combined at nanoscale structural
morphology (Fig. 1c).
Sweetening of NMs as energy resources has tough excellent headway, particularly
within zone of top-notch energy gathering solar cells. For quick progression as for
energy process and developments, distinctive methodologies are planned for the
arrangement which has set a trend to use of nanocomposite materials widely. New
methodologies are in use for upgrading the reaction rate in batteries anodes [75].
Nanomaterials will grasp reversible reaction, create a hopeful instrument for fresh
energy, and ensure large storage cutoff points. NMs have benefits of wellbeing eco-
friendship with supportability attitude and have potential for money saving [76–84].
Different materials are tried as photo-anode in DSSC. Titanium dioxide is the
most abundantly used photo-anode in DSSC due to its unmatched characteristics.
The band structure of Titania describes the valence band composed of O 2p states
and the conduction band mostly consists of Ti 3d states. At the same time, the density
of states shows other less important contributions, notably from Ti 3d states in the
valence band [85–88]. Titanium dioxide is most fitting for DSSC because of its
greater physical phenomenon band edge, exterior region, dyes filling, and lepton
disposition. Titanium dioxide nanoparticles based solar cells generally show the
efficiency of about 13% that was the most amazing among the other materials [88].
Zinc oxide is another wide bandgap semiconductor large lepton flexibility that is
most correct for photo-electrode in dye-sensitized solar cell [86].
Nb2 O5 -based cells indicate high electric circuit potential and effectiveness on
account of the nice physical phenomenon band edge [88]. Among the most Nb2 O5 -
based cells, a proficiency of sixth has been practiced to this point utilizing nanorods
[89]. Different nanostructured metal oxide, for example, Al2 O3 , SnO2 , V2 O5 ,
ZrO2 , CeO2, and Fe2 O3, are analyzed as photoanodes in DSSC’s [90–93]. Doped-
semiconductor materials exhibit an improvements in I-V characteristics because of
different band edges.
34 H. M. A. Javed et al.

Many researchers reported that one of the planner selective layers of mesoporous
electrons is used for simplification of perovskite solar cells for constructing the solar
panels art large scale. The conversion efficiency power can be enhanced in perovskite
solar cell by doping the titanium dioxide with electron selective layer (ESL). In this
way, titanium dioxide limits the conduction band. It can be done with different
techniques.
The simplification of perovskite solar cells (PSCs), by replacing the mesoporous
electron selective layer (ESL) with a planar one, is advantageous for large-scale
manufacturing. PSCs with a planar TiO2 ESL have been demonstrated, but these
exhibit unstabilized power conversion efficiencies (PCEs). The planar PSCs using
TiO2 are naturally limited due to conduction band misalignment. It has demonstrated
with a variety of characterization techniques. Latest studies showed the potential of
SnO2 -based ESLs. These devices have not shown high efficiency without hysteretic
behavior. For the first time, SnO2 achieves a barrier-free energetic configuration,
obtaining almost hysteresis-free PCEs of over 18% with voltages of up to 1.19 V
[94].
Many researchers have reported to prepare lithium doped titanium dioxide
nanoparticles by hydrothermal method with assist of ionic liquids. For organic oxida-
tion, potential is consumed as photocatalysts. For the good assistance of ionic liquids,
Cr6+ , a toxic element, is converted into Cr3+ , a non-toxic element. The microstructural
studies of Li doped titanium dioxide nanoparticles are investigated through Fourier-
transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The optical
properties are observed with UV-Visible spectroscopy. The synthesized Li doped tita-
nium dioxide has anatase phase. The photocatalytic activity of Li-TiO2 nanoparticles
results showed better degradation as compared to the TiO2 nanoparticles [95].
It is reported that three-dimensional (3D) perovskite structures are not much stable
than that of two-dimensional (2D) perovskite structure due to organic legends which
acts as a counterpart. A method in which 3D perovskite structure is chemical reacted
with n-butylamine (BA) to produce the rational structure of 2D and 3D structure.
Different forms of 2D perovskite layers are produced by different mechanism with
the reaction of n-butylammonium iodide (BAI). (BA)2PbI4 was produced by the
chemical reaction of n-butylamine (BA) and MAPbI. The 2D perovskite mixture
has less protection than the (BA)2PbI4 due to the number of organic ligands. BA
treatment has much smoother two-dimensional perovskite layer on three-dimensional
layer that results good exposure. The stacking structure of two-dimensional and three-
dimensional structure shows the better photovoltaic stability as compared to three-
dimensional counter parts to bear the heat stress [96–107]. The inorganic solar cells
provide some central focuses over regular daylight-based cells regarding soundness,
assimilation properties, lifetime, and capability with less reliance on social gathering
adapt [109–113].
Perspective of Nanomaterials in the Performance of Solar Cells 35

4 Central Features of Nanomaterials

Nanomaterials can be categorized into three types according to their source: natu-
ral, incidental, and engineered. The engineered nanomaterials (NMs) are specially
designed for many commercial goods and processes. These NMs have many appli-
cations, such as stain-resistant clothing, cosmetics, sunscreens, electronics, sporting
goods, tires, as well as many of real-life daily items, and are used in medicine for pur-
poses of diagnosis, imaging, and drug delivery. Nanophase engineering has flourished
rapidly and is producing variation in the structure of materials. Nano-engineering has
capability to manipulate the catalytic, mechanical, optical, electrical, magnetic, and
electronic functions in organic and inorganic materials. The final productive outcome
is the designing of advanced nanomaterials, which is mostly based on the functional
and efficient nanostructures [115–118] (Table 1).
Important applications of nanomaterials have been tabulated in Tables 2 and 3
along with practical illustrations. Ideally, these postulates show the convenient appli-
cation, notably in several cells as well as battery-controlled metal cells, skinny film
cells (e.g., adaptable, printable, or perhaps clean cells), fluid powered cells, reac-
tion stream cells, customary cells, super-capacitors, and sun-based/imperativeness
sections [119–125]. In any case, the running with subjects still ought to be essen-
tially surveyed, notably regarding the usage of ordinary materials, such that common
place standard and inorganic materials for imperativeness applications [126–136]:
• Failure to change inanimate assertion frameworks to trademark constituents
because of complexities related with configuration incited or seeded progression
dealing with methodology.
• Influence of electric arrangement and charge carriage properties on atomic
introduction and requesting at the trademark material boundary.
• Restricted stimulating spread sizes owed to vague or semicrystalline pattern of
standard materials.
• Trouble with respect to monitoring sub-atomic introduction, pressing, and crys-
tallization at the substrate boundary owed to imperfect working of typical and
inorganic constituents.

5 Focal Points of Nanostructured Materials

Nanotechnology is an approving advancement that provides larger opportunities for

selecting the linked matters. The creation parts and machines are less than 100 nm pro-
viding the fine styles to manage an imperative and safe trade. It can help to overcome
current performance barriers and substantially improve the collection and conversion
of solar energy. A number of nanoscale physical phenomena have been identified
that can improve the collection and conversion of solar energy. Nanoparticles and
nanostructures have enhanced the absorption of light, increased the conversion of
 36

Table 1 Primary highlights and focal points of nanostructured materials

S. No. Nanostructure structures Examples Role References
1 Nanospheres Sn, SnO2 , Sb, Fe3 O4 , LiFeO4 , etc. Massive negated volumes and [115, 119, 120, 123]
connective electron paths consider fast
electron and molecule trade and
moreover keeping up a vital separation
from aggregate with the amazing pads
related with volume changes
2 Nanowires Si, SnO2 , TiSi2 , etc. Improved energy over steady electron [118, 120, 123, 124]
pathways
3 Nanotubes or nano-arrays MnO2 core/PEDOT shell coaxial High molecule movement through [75, 118, 120, 135]
nanowires, Cu nanowires with Fe3 O4 , straightforward invasion of the
etc. electrolyte, which can garbs
fluctuations in the material in the
volume midst of cycling
4 Porous 3D nanostructured networks Polyaniline, graphene and its interrelated pores and nanothickness [116, 117, 121, 125]
composites, MOFs, etc. suggest high molecule change, little
molecule scattering lengths, simple
electron and molecule get to (in view
of broad imperativeness thickness by
methods for the high surface region),
high mechanical characteristics with
long cyclical times, and great rate
capacities
5 Nanofilms, nanosheets, or nameplates High likelihood of rational applications [125, 127, 129]
in light of clear electron and molecule
trade given by high essentialness
densities
H. M. A. Javed et al.
Table 2 Arrangement of nanostructured materials for energy applications dependent on their auxiliary measurements
S. No. Nanostructure course Resources/example Welfares for energy resources References
1 1-D Carbon nanotube, carbon/metal-based Very much well-ordered development simple and [79, 84]
nanowires/nanotubes, etc. productive automated exchange.
High ionic transition can oblige fluctuations in the
material volume for enhanced cyclability. No
requirement for additional covers or conductive
constituents. Negated volume among adjacent ID
NMs takes into account simple entrance of the
electrolyte
2 2-D Graphene carbon-secured nameplates, polymers, High explicit capacitance Enhanced cyclability [77, 136]
etc. Not thoroughly researched as an electrochemical
call Energy stockpiling material
Perspective of Nanomaterials in the Performance of Solar Cells

3 3-D Mesoporous and micro porous materials (i.e., Indistinguishable advantages from 1D materials [79, 119, 136]
metal regular structures, 3D graphene, nanohybrid yet without a significant number of their
materials, etc. confinements (i.e., high inner opposition because
of little size and totals and higher perspective
proportions without interconnections)
37
38 H. M. A. Javed et al.

Table 3 A relative study of several solar cell materials [160, 161]

III Generation
Amorphous Nanocrystal Dye Polymer Perovskite
semiconductor sensitized
Efficiency 4–8 7–8 ~10 ~3 to 10 31
(%)
Temperature Stable at high Stable at Not stable Not stable Stable at
dependency temperature high at very high at very high high
temperature temperature temperature temperature
Energy 1.1–1.5 ~3 ~3 ~2 ~1
bandgap
(eV)
Merits Merits riveting Versatile, Versatile, Versatile, Versatile,
capability is high, tough tough tough tough, more
efficient potency
acknowledgements
to low price of
materials and
producing method
Energy ~0.1 ~5 ~0.01
(TWy)
Demerits Reliability is a Demand of Demand of Demand of Demand of
smaller amount fixing fixing fixing fixing
once it’s use for period and period and period and period and
outside requests area is high area is high area is high area is high

light to electricity, and provided better thermal storage and transport. The technolo-
gies fall short of potential performance because of poor control over feature size
and placement, unpredictable micro/nanostructure, poor interface formation, and in
many cases, short lifetimes of laboratory devices. Among various contraptions, the
sun-based pro, the imperativeness part, photocatalysis, and sun-based photovoltaic
have utilized the nanomaterials to build the ability [134–136]. It is discovered that
by utilizing nanomaterials, the scene radiation can be stretched out by various events
while the ampleness of the sunlight-based gatherer has 10% higher showed up dis-
tinctively in connection to that of a standard measurement plate sun-based master.
From the past research, it has been shown that nanotechnology is a principal asset
for an enormous social occasion of the adjacent planetary system in help of able,
sensible imperativeness change, aggregating, and confirmation, to the degree [137].
• Adapting the correspondence of light with materials which empowers the
insignificant effort of semiconductors into contraptions, for example, photovoltaic.
• Making progressively incredible photostimuli for changing over daylight into built
fills.
• Developing new materials and layers for encapsulating the packages on situational
requests.
Perspective of Nanomaterials in the Performance of Solar Cells 39

• Creating the variable powers into electrical essentialness (and the alternate way),
imperativeness and power thickness in cells.
• Improving the capacity in zones from highlights and strong state.
Most of the future progress in clean energy will be relating to nanotechnology.
Scientists have achieved fruitful outcomes in advanced clean energy materials in
recent years. The positive roles of nanostructures in clean energy research are well
accepted, and there are still some fundamental issues debated in real applications.
For example, high surface area leads to self-discharge, poor cycling, and calendar life
of batteries and their inferior packing of nanoparticles also lead to lower volumetric
energy densities. Small particle size of photocatalysts results in their poor cycling
performance due to their instability [137–139].
In solar cell research, carrier multiplication is the key phenomenon for the excita-
tion of multiple electrons from valence band to conduction band. This phenomenon is
different from the theory of a conventional solar cell. The carrier multiplication princi-
ple takes place in nanostructure material and enhances the work. The carrier multipli-
cation effect in quantum dots (QDs) can be understood as creating multiple excitons
and is named as multiple exciton generation (MEG). MEG increases the energy con-
version efficiency of nanocrystal-based solar cells [140–143]. Quantum confinement
(QC) improves the Coulombic interaction that drives MEG [144, 145].
Down-conversion (DC) intends to utilize the free energy of photons with energy
higher than the bandgap of the solar cell, which is otherwise lost to thermal reaction.
In DC process, a separate material from the solar cell is used to split photons with
energy at twice the bandgap energy into two lower energy photons, which are better
matched to the solar cell’s bandgap. Photons with a lower energy than the bandgap is
lost in a normal solar cell. The principle of the up conversion technique is that two or
more photons are converted into a photon with energy higher than the bandgap energy.
High energy photons will lose the energy above the bandgap energy limit. Down-
conversion is a process where a high-energy photon is converted into several lower-
energy photons with energies above the bandgap. This process intends to increase
the current of the solar cell by increasing the number of absorbed photons imposed
upon the solar cell while retaining its voltage characteristics. This increase in current
subsequently increases the overall efficiency of the system. The DC process can be
considered as modifying the solar spectrum to better match the solar cell properties,
as opposed to changing the solar cell itself, enabling the efficiency increase of the
underlying solar cell beyond the Shockley–Quiesser limit [139–149].
40 H. M. A. Javed et al.

6 Performance Parameters of Nanomaterials-Based Solar

Cells

6.1 Stability

Solar cells are lightweight, flexible, and they boost light harvesting by absorbing
lights. Although special attentions were given to the existing solar cells in terms of
efficiency, stability, and cost, but still, there is great demand for novel technologies
that can simultaneously improve both PCE and stability while using an inexpensive
electrode material. An imaginative golden triangle is shown in Fig. 2 for a better
understanding of the technical gauge for commercialization photovoltaic technology.
Silicon photovoltaic solar cells are looking to capture the 90% of the total mar-
ket because of their excellent efficiency of 21% with lifetime of 25 year more at
reasonable cost. On other hand, nanomaterials-based solar cells have high efficiency
more than 23% and low manufacturing cost, with considerable half life of that crystal
structure. However, perovskite solar cell has problem of stability. So for one year is
a longest life time of nanomaterials-based solar cell which is very short time as com-
pared to 25 years. Many factors are involved in determining the lifetime of perovskite
solar cell and can be divided in two groups. One is called extrinsic and other is called
intrinsic. Extrinsically, environmental condonation such as oxygen and moisture can
be removed or controlled by encapsulation but the most important critical issue is
the large size of perovskite materials. For intrinsic, there is the movement of charge
at interface between layer and perovskite. There are three main intrinsic factors,
i.e., instability of perovskite hygroscopicity, ion migration, and thermal instability
[150–189].

Fig. 2 Golden triangle of

solar cell performance
Perspective of Nanomaterials in the Performance of Solar Cells 41

6.2 Light Harvesting Efficiency

Harvesting of light is a performance parameter of solar cells. The effective harvesting

of sunlight has become a big challenge in the field of PV solar cell. The understand-
ing to increase the path length of photon and for photoexcitation improvement in
less absorbing material like that of silicon is helpful for knowing the optimum oper-
ation of this structure. The resulting bandgap of photonic in solar cell cannot achieve
harvesting efficiencies. Light harvesting of solar cell is similar to the process of
photosynthesis. The process of separation of charges is similar like photosynthesis
process which is photochemical reaction. The ability to capture the solar energy
cannot occur by recombination of separate charges. The light harvesting at semi-
conductor junction is the process at nanoscale at which light interacts with matter.
The conversion of solar energy to electrical energy by using photovoltaic (PV) cells is
one of the key elements of the future energy supply of mankind. By optimizing the
optics, the number of photons which are converted by the semiconductor material can
be maximized. First of all, optical approaches are necessary to avoid losses by reflec-
tion or unwanted absorption which does not generate charge carriers. The light has to
be trapped efficiently within the cell. And the photon energy is far away from being
optimized. Due to the large range of wavelengths in the solar spectrum almost all
photons have the wrong energy because the photon energy may exceed the bandgap
energy of the semiconductor or fall below that. In the first case, the photon generates
an electron-hole pair and the excess energy is thermalized, and in the second case,
the photon is transmitted or absorbed without generating an electron-hole pair, e.g.,
by free carriers. Only photons with exactly the energy of the bandgap of the semi-
conductor are generating electron-hole pairs with the maximum efficiency. Thus, the
researchers are facing the need the spectral control of the incident photons. At all
the basic levels, it is understood that more energy can be attained by separating into
light capture charging in conversion photonic process. Different materials with dif-
ferent structures shape new technology which brings efficient and cheap solar cells
in coming generation of solar cells [188–190] (Table 4).

6.2.1 X-Ray Diffraction (XRD)

X-ray diffraction (XRD) may be a standout among the foremost essential non-ruinous
devices to study a large variety of issues ranging from liquids, to powders and pre-
cious stones. From analysis to creation and engineering, XRD is an irreplaceable
technique for materials portrayal and internal control. XRD analysis is based on
constructive interference of monochromatic X-rays and a crystalline sample: The X-
rays are generated by a cathode ray tube, filtered to produce monochromatic radiation,
collimated to concentrate, and directed toward the sample. Rigaku has engineered up
the newest and most novel high-resolution X-ray diffractometer (XRD). Due to its
versatile approach, it can be used for thin films, nanomaterials, powders, or liquids
and allows mapping measurements within suitable samples [149].
42 H. M. A. Javed et al.

Table 4 A relative study of various photovoltaic cell materials [150–159]

Parameters I Generation II Generation
Mono Poly semiconductor CIGS CdTe
semiconductor
Efficiency 14–17.5 12–14 10–12 9–11
(%)
Temperature Not stable at Not stable at very Smart at high Smart at high
dependency very high high temperature and low and low
temperature temperature temperature
Energy 1.1 1.1 Eg > 1.2 1.5
bandgap
(eV)
Merits Merits Efficiency cheap Versatile, tough, Versatile, tough,
handiness of related to high potency
raw materials mono-semiconducting
in masses, material
eco-friendly,
decent in terms
of consistency,
steadiness,
Energy ~2.5 ~2.5 0.02 0.02
(TWy)
Demerits Interval Potency is a smaller Amount riveting Toxic to
intense and capability is less presence of Cd
difficult
producing
procedure
Cost Luxurious Luxurious Needs solely Needs solely
fiftieth of fiftieth of
expense of expenditure of
traditional customary
semiconducting semiconducting
material-based material-based
cells cell

6.3 Higher Surface Area

A typical silicon PV cell produced around 0.5–0.6 V DC current under open circuit
and no load condition. The electronic circuit output of a PV cell depends upon the
efficiency and size (surface area), and this is directly proportional to the intensity or
glancing of the striking sunlight on the surface of cell. The surface area-to-volume
ratio increases as the diameter of the nanoparticle decreases or vice versa. It means
that when a given volume of material is made up of smaller particles, the surface
area of the material increases. The working performance in a full sunny day, with
commercially available PV cell with surface area of 160 cm2 will produce a power of
approximately 2 W. But this can be changed if the sunlight decreases in a cloudy day
Perspective of Nanomaterials in the Performance of Solar Cells 43

during day time. Its intensity is 40% of peak value, and the cell would produce about
0.8 W of power. This can be taken in terms of length. Length is directly proportional
to the resistance. Short distance creates lower resistance, so that smaller cells will
waste less energy and be a little more efficient. That is why smaller size cell exceeds
larger size cell because smaller size has greater efficiency [183–185]. Typically,
silicon solar cells are about 5 or 6 inches square to match the size of the new silicon.

6.3.1 BET Analysis

Brunauer–Emmett–Teller (BET) theory explains the mechanism of physical adsorp-

tion of gas molecules on a solid surface and serves as the basis for an impor-
tant analysis technique for the measurement of the specific surface area of mate-
rials. In 1938, Stephen Brunauer, Paul Hugh Emmett, and Teller distributed the
first article regarding the BET hypothesis within the Journal of the Yankee Chemical
Society.
The specific surface area of a powder is determined by physical adsorption of a
gas on the surface of the solid and by calculating the amount of adsorbate gas corre-
sponding to a monomolecular layer on the surface. Brunauer–Emmett–Teller (BET)
theory aims to explain the physical adsorption of gas molecules on a solid surface
and serves as the basis for an important analysis technique for the measurement of
the specific surface area of materials.
Therefore, normal BET examination is usually crystal rectifier at the boiling tem-
perature of N2 (77 K). The BET strategy is generally utilized in surface science for the
computation of surface territories of solids by physical sorption of gas particles. The
mixture surface territory express surface region in units of volume to boot the units
of the monolayer volume of the adsorbate gas is Avogadro’s number [186].

6.3.2 SEM Analysis

Scanning electron microscope (SEM) pictures are useful for examining the fine
structure of solar cells. Even in large area commercial devices, for example, an SEM
photograph can show the depth of the rear surface aluminum alloyed layer. Many of
the solar cell features are of the order of microns and so not possible to view with an
optical microscope. An additional advantage of an electron microscope is its higher
depth of field. With an electron microscope, it is possible to have the whole device
in focus at once, whereas in an optical microscope at high magnification, only parts
of the device will be in focus at any time [187].
SEM is also used as a diagnostic tool for analyzing the degradation of a poly-
crystalline photovoltaic cell. The SEM characterizes the surface morphology of hot
spot regions (degraded) cells in photovoltaic solar cells. In recent years, production of
hetero and multi-junction solar cells has experience tremendous growth as compared
to conventional silicon (Si) solar cells. Thin film photovoltaic solar cells generally
are more prone to exhibiting defects and associated degradation modes. To improve
44 H. M. A. Javed et al.

the lifetime of these cells and modules, it is imperative to fully understand the cause
and effect of defects and degradation modes. Many researchers have used SEM to
study poly-Si cells before, and after reverse biasing, the reverse biasing was done to
evaluate the cells’ susceptibility to leakage currents and hotspots formation. After
reverse biasing, some cells were found to exhibit hotspots as confirmed by infrared
thermography. The surface morphology of hotspot regions was characterized using
SEM. The preliminary result indicated that hotspots are formed in the regions of high
inhomogeneity [188].
Before analyzing, the samples of solar cells were placed on the stubs using car-
bon double side tab. The JEOL JSM-6390LV (SEM) device is considered with an
accelerated voltage of 12 keV. This uniform acceleration voltage helps to maintain
uniform sample electron beam interaction across the sample morphology. The SEM
micrographs revealed the defected region in the cell. Each region of interest is diag-
nosed with electron dispersive X-ray spectroscopy (EDX) for chemical composition
analysis. The elemental composition at various regions plays a major part in PV
cell defect formation. Though the elemental composition of the module might have
change form, due to impact ionization, moisture and electrolytic process after a long
exposure in the case of outdoor deployment.
For ancient imaging within the SEM, examples should be electrically
semiconductor, in any event at the surface, and electrically grounded to stay the
aggregation of electric charge. SEM should be extra ordinary clean with metal
articles and conductively mounting to an example stub. Non-conducting materials
are usually lined with an ultrathin coating of electrically conducting material, unbro-
ken on the instance either by low-vacuum sputter coating or by high-vacuum evap-
oration. Semiconductive materials in current use as an example coating incorporate
gold, gold/palladium compound, platinum, iridium, tungsten, chromium, osmium,
and carbon. Coating with substantial metals might expand signal/clamor proportion
for tests of low nuclear range (Z) [188].

6.4 Recombination Rate

Open-circuit voltage and short-circuit current are greatly affecting by surface recom-
bination. At the top of the surface, there exists a very high recombination rate which is
mostly creating unfavorable influence on current of short circuit. The upper surface is
also considered to the highest region of carrier generation in the solar cell. Reduction
in upper surface recombination is consistently passivating layer insult by reducing
the number of dangling silicon bonds at the top surface. The electronics industry
mostly use passivate layer by growing dioxide layer on silicon. Silicon nitrate are
mostly used as a dielectric layer in commercial solar panels [189].
However, silicon solar cells are using the passivating layer as insulator. The sur-
face is passivated as silicon dioxide layer which cannot use on Ohmic metal contact.
Instead, under the upper interactions, the influence of the recombination of sur-
face can be reduced by enhancing the doping. While high doping creates damages
Perspective of Nanomaterials in the Performance of Solar Cells 45

Fig. 3 Techniques for reducing the impact of surface recombination

the diffusion length. The interaction areas do not involve in carrier generation and
hence the effect on carrier gathering becomes unimportant. In addition, junction
is closed by very high recombination area; possible doping is increased to lower
the recombination option [190]. Figure 3 is illustrating the surface recombination
mechanism.

7 Challenges in Nanostructured Solar Cells

Nanostructured solar cell systems exhibit different properties and have allowed new
ways of approaching solar energy conversion for electricity generation or fuels. The
large surface-to-volume ratio of nanomaterials provides various benefits. Though
nanostructured solar cells have many advantages, some limitations are still tagged
with them. In general, there are two main limitations for every solar cell. Firstly,
at night, solar energy cannot harvest. Secondly, all time solar radiated energy is
not same. A large amount of energy is necessary to photovoltaic device to produce
electric energy. Moreover, the intensity of solar energy is fluctuated in whole day.
Solar radiations have to bear a lot of hurdles for reaching the surface of earth. These
are traveling time from Sun to surface of earth, weather conditions, and location
during summer season as to the winter season. The radiation of sun is very less
intense in winter season. Scientists and researchers are trying to overcome these
limitations of solar technology. They are trying to develop high-efficiency solar cell
with capability of energy storage for night usage [191, 192].
46 H. M. A. Javed et al.

Nanostructured solar cells have attractive features for commercial point of view
but these devices have also additional challenges. For nanostructured devices,
improper passivation of internal surfaces can hinder long-term stability. Device sta-
bility is obviously an important consideration for photovoltaic technologies as longer
the photovoltaic system operates, the lower is the total cost. Stability issues are being
appeared due to the chemistry [193–195] or due to device configuration [196]. The
commercial viability of the nanostructured solar cell product is made possible by
encapsulation route which helps to settle the stability issues. Further efforts are being
made on the stability and low maintenance. The overall cost and efficiency are kept
in a satisfactory range of the customer [197]. The characteristics of nanostructures
for photovoltaics are based on two approaches: (i) significant reduction in material
usage and/or associated final costs; (ii) photovoltaic devices with a higher limiting
efficiency than that determined by the Shockley–Queisser analysis. Both approaches,
individually or in combination, can lead to significantly lower costs per kWh.
For household energy consumption, the energy is measured in rated cost per peak
watt. This energy depends upon the power conservation efficiency which is calculated
by the fraction of the energy converted by solar cell to total energy irradiance. The
total consumption cost per peak watt is two times greater than the module (cost
per peak watt) and it is inversely proportional to power conservation efficiency.
For calculating the overall cost per rate, another factor is also included that is the
brightness of sun which changes day by day. For numeric value, the value of cost rate
is calculated by multiplying the cost per peak watt with 0.05. Currently, photovoltaic
conversion cost is 1 and the mean value of this cost 1-0-10$/watt which is comparable
with the grid energy which is called grid purity [195, 196].

8 Summary and Future Perspectives

A device that produces electrical energy directly from sunlight by photocatalytic

effect, physicochemical process, is called a solar cell. Many solar cells are con-
nected with each other to form solar modules also called solar panels. In the 1960s,
single-junction silicon photovoltaic cells can produce ~0.5 to 0.6 V, and then, it
was improved gradually. Initially, it has high cast users that work for space inves-
tigations. The solar cells also depend upon semiconductor industry and after the
invention of integrated circuits, their prices had been decreased substantially in late
1971, normally its cost was some $100 per watt. The efficiency of solar cells has
been distinguished into thermodynamic efficiency, reflectance efficiency, conductive
efficiency, and separations of charge carrier efficiency, and they are responsible for
the overall efficiency of solar cells. The conversion of incident light power into elec-
trical power is known as power conversion efficiency, and also it has some other
parameters to check the efficiency limits such as temperature coefficients, shadow
angles, and temperature dependent curve for efficiency.
It is hard to measure directly such parameters, so some other parameters such
as integrated quantum efficiency, quantum efficiency, fill factor and VOC ratio, and
Perspective of Nanomaterials in the Performance of Solar Cells 47

reflectance ratio are substituted into external quantum efficiency. The materials that
have single layer of light absorbing material are known as single junction otherwise
multi-junction. The separation and absorption mechanisms are different in single and
multi-junction materials. Till now, the solar cell family is divided into three genera-
tions called first, second, and third generation. The first generation consists of wafer-
based solar cells and photovortices technologies. The second generation consists of
thin film solar cells. The third generation is considered as the emerging photovor-
tices which also include on the thin film solar cells technologies. The third-generation
solar cells are in evolutionary development phase, in which organic, inorganic, and
organometallic compounds are often tested. The third-generation solar cells have
high efficiencies but also have stability issues. Beside these major disadvantages,
it has bright future to achieve high efficiency for commercial applications. Among
third-generation solar cells, perovskite solar cells and dye-synthesized solar cells
have great future because of their increasing efficiency. These cells have increased
their efficiency up to 20% till 2014 and it is predicted its efficiency will approach
to 27.3% by the end of 2018. In conclusion, next-generation solar cells must meet
demanding desires regarding the power conversion efficiency (PCE), price cost, and
life stability of ten to fifteen years. We have confidence in that nanostructured solar
cells (NSCs) have great potential capability to attain such mentioned objectives.

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Materials for Solar Cell Applications:
An Overview of TiO2 , ZnO, Upconverting
Organic and Polymer-Based Solar Cells

Navadeep Shrivastava, Helliomar Barbosa, Khuram Ali and S. K. Sharma

Abstract The present chapter gives an overview of third-generation solar cells with
special emphasize on important synthesis protocol for ZnO, TiO2 , and rare earth-
based upconverting materials for their utilization in the field of solar cells. Moreover,
we have discussed working principle and basic requirements for organic-based solar
cells, which is in major focus of research worldwide. This is booming research field
and has enormous scope to serve humankind to combat energy scarcity and futuristic
application for harvesting the solar energy.

Keywords Solar cells · Upconversion · TiO2 · ZnO · DSSC · Polymer solar cells

1 Introduction

The whole world is suffering from the sustainable energy sources as large dependency
is on petroleum, coal, and hydro energies. This is leading to CO2 emission and
finally ending to global warming scenario. This also affects the social–economic–
health issues. The fossil fuels are not able to meet the future need due to their
reserved resources and rapid increasing prices. In the modern world, energy issues
have become urgent problem facing by habitants as the energy requirements are
growing ever faster. Hence, it is important to find clean, renewable, and sustainable
energy sources and considered as one of humanity’s greatest challenges. The sun

N. Shrivastava
Institute of Physics, Federal University of Goias, Goiania, GO, Brazil
H. Barbosa
Institute of Chemistry, Development of Inorganic Materials with Rare Earths (DeMITeR),
Laboratory of Photoluminescent Materials (LAMAF), Federal University of Uberlândia,
Uberlândia, MG 38400-902, Brazil
K. Ali
Department of Physics, University of Agriculture, Faisalabad 38040, Pakistan
S. K. Sharma (B)
Department of Physics, Faculty of Science and Technology, The University of the West Indies, St.
Augustine, Trinidad and Tobago
e-mail: [email protected]
© Springer Nature Switzerland AG 2020 55
S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_3
56 N. Shrivastava et al.

emits an enormous and endless energy, and our planet receives this solar energy
each year more than twice as energy of petroleum and nuclear resources. Hence,
solar energy is great alternative compared to these traditional energy sources and has
potential to meet our energy demands, with no exception.
In general, solar energy can be harvested using two classes of technologies: pho-
tovoltaic (PV) and solar thermal (ST). PV converts solar photons absorbed by PV cell
into charge which can be collected and used to generate electrical power, whereas
ST technology utilizes heat energy from the sun to heat a fluid. Harvesting energy
directly from sunlight using PV technology is considered as being one of the most
important ways to address growing global energy needs using a renewable resource
[1]. Solar PV technology is increasingly being deployed globally leading to approxi-
mately 500 GW installed capacity at the end of 2018, and this is expected to continue
toward multi TW levels within a few decades. PV has been reported to be a net con-
tributor to greenhouse gas emission reduction, while module efficiency is gradually
increasing, getting closer and closer to the Shockley–Queisser limit, and the lev-
eled cost of electricity is plummeting to much less than traditional sources in some
regions. Solar thermal technology is not the major focus of the present chapter, and
hence, it is not discussed here. PV can be found in a variety locations; from the PV
cells on a calculator to vast multi-mega Watt generating power stations, there are
numerous ways of implementing the technology such as building-integrated photo-
voltaic (BIPV), concentrator photovoltaics (CPV), and space photovoltaics (SPV),
floating PV, and others (Fig. 1).

(a) (b)
Global New investment in renewable
energy , by region in 2017, $BN

Fig. 1 a Solar energy distribution and capture [2]. The AM0 and AM1.5 solar irradiation spectra
show the solar energy distribution outside of the Earth’s atmosphere (white line) and at the Earth’s
surface (black line), respectively. The colored bars show the absorption range of green plants, purple
bacteria, red algae, and typical silicon PV (photovoltaic) panels, as these are the most prevalent
light-harvesting systems. The absorption peak maxima (where available) are depicted by darker
shading in each colored band. The energy contained in the 300–350 nm and 1000–4045 nm regions
is only captured by black absorbers and corresponds to 1.37% and 26.31% of the total energy in
each spectrum, respectively. b Global new investment in 2017, in $BN, by the major economies in
the world [3]
Materials for Solar Cell Applications: An Overview of TiO2 … 57

We can divide PV devices into three major groups [4]: (i) first-generation solar
cell, (ii) second-generation solar cell, and (iii) third-generation solar cell often also
termed as future generation solar cells. First-generation solar cells are composed
of silicon (Si) wafers (monocrystalline and polycrystalline). The monocrystalline Si
homojunction and heterojunction cells have 25.1% and 25.6% efficiencies, respec-
tively, whereas the polycrystalline Si cells have 20.8% efficiency [5]. The maxi-
mum efficiency of Si-based single-junction solar cells (the absence of non-radiative
recombination) is limited to 33.5% for AM1.5G spectrum at 25 °C according to
Shockley–Queisser (SQ) limit [6]. At present, silicon solar cells (wafer technology)
dominates and taking up ~93% of the global PV installation market with power
conversion efficiency (PCE) of commercial modules of around 20% and lifetime
of more than 20 years. The cost of silicon modules dropped down significantly
from ~70$/WP in 1970s to ~0.36$/WP in 2017. However, the main disadvantage
is that Si technology needs expensive materials with higher processing tempera-
ture, which means that the production is still expensive [5]. Second-generation solar
cells are based on “thin-film” technology that consists of semiconductor materi-
als such as copper indium gallium diselenide (CIGS—21.7%), single-crystalline
gallium arsenide (GaAs—28.8%) and polycrystalline cadmium telluride (CdTe—
21.5%) showing promising efficiencies [5]. Multi-junction solar cells surpass SQ
limit due to several absorber layers for harvesting light in different regions of the
solar spectrum and have reached highest PCE of 38.8% under one sun condition
with a five junction (GAInAs/GAInP/GaAS/AlGaInAs/AlGaInP) tandem geometry.
However, a big challenge for the PV community with these solar cells is the high
production cost [4, 5]. Researchers have pushed toward new kinds of solar cells and
developed “third-generation” solar cells to overcome the limitations of the previous
solar cells and tried to reduce high production cost [4]. Though the efficiencies of
third-generation solar cells are relatively low as compared to Si/multi-junction solar
cells, they have low production cost due to cheap fabrication processing techniques.
This makes third-generation solar cells appealing to the PV community.
In recent years, solution-based/processed PVs have attracted significant inter-
est due to their high PCE, cost-effective fabrication, and added functionality such
as flexibility, being aesthetic and lightweight. The first development was based on
dye-sensitized solar cells (DSSCs) [7], which now demonstrate 14.3% efficiency [8,
9]. The most recent breakthrough in the field of third-generation solar cells is the
development of organic–inorganic halide perovskite solar cells that now demonstrate
efficiency about 22% [10]. Progress of perovskite solar cells (PSCs) has been remark-
ably impressive as these can be fabricated by solution processing at low temperatures,
and the production requires less energy than Si solar cell. Another potential market
advantage of the PSCs is the deployment of flexible PV technology. It is not only
interesting due to the quest for low-cost manufacturing and high throughput (out-
put/efficiency) but also by considering its properties of being lightweight, flexible and
thin that would make it easy to integrate on any surface (e.g., building-integrated pho-
tovoltaics (BIPV), automotive integrated photovoltaics (AIPV) or structure (either
curved, rigid, or flexible), and even in portable and indoor electronics [11].
58 N. Shrivastava et al.

Despite the high-efficiency reports, the PSCs still suffer from issues such as long-
term operational stability, toxicity (the most efficient device employ lead, Pb), and
reproducibility. The reproducibility arises from their rapid crystallization, which
largely depends on the processing conditions and also the substrate or the selective
contacts underneath [11]. For a high-efficient device, the choice of selective con-
tacts is crucial for efficient charge extractions as well as its stability as perovskite
deposition on metal oxides such as ZnO and TiO2 has shown degradation due to a
possible interfacial reaction [12, 13]. In the present chapter, we mainly deal with the
fabrication and importance of new solid-state and organic solar cells based on the
third generation.

2 Synthesis of Materials

2.1 Synthesis of Material-Based (TiO2 , ZnO) Solar Cells

Rising world population and industrial growth have led to accelerated energy con-
sumption, while the uncontrolled release of toxic and industrial wastes in the air and
water has resulted in pollution associated diseases worldwide as well as abnormal cli-
mate changes. It is therefore imperative to develop sustainable clean energy-efficient
and environmentally friendly technologies for the serious environmental problems
that have become a major concern. Titanium dioxide (TiO2 ) that exhibits multifunc-
tionality has attracted intense effort worldwide due to its potential applications in
harvesting, storage and transfer of energy, removal of air pollutants, and applications
in biomedicine [14, 15]. However, wide band gap (3.0–3.2 eV) of TiO2 restricts
its optical activity only to the ultraviolet (UV) radiation, corresponding for only
~5% of the solar radiation and thus resulting in inefficient photocatalytic proper-
ties [16]. Nowadays, co-doping of TiO2 nanomaterials with different elements has
received considerable attention to further improve their photocatalytic activity. The
high ratio of the surface area caused by the small particle size brings many benefits
in the photocatalytic field for many TiO2 -based devices, since it facilitates the reac-
tion/interaction between the devices and the interactive media, which occurs mainly
at the external interface of the particle and depends heavily on the surface area of the
material.

2.1.1 Synthetic Methods for TiO2 Nanostructures

Sol–Gel Method: In a typical sol–gel process, a colloidal suspension is formed from

the hydrolysis and polymerization reactions of the precursors which are composed
of inorganic metal salts or organic metal compounds, such as metal alkoxides. The
complete polymerization and the consequent solvent outlet lead to the transition of
the liquid sol into a solid gel phase. TiO2 nanomaterials have been synthesized with
Materials for Solar Cell Applications: An Overview of TiO2 … 59

the sol–gel from the hydrolysis of a titanium precursor [17]. This process normally
proceeds via an acid-catalyzed hydrolysis step of titanium (IV) alkoxide followed by
condensation. Anatase TiO2 nanoparticles with different sizes and shapes could be
obtained with the polycondensation of titanium alkoxide in the presence of tetram-
ethylammonium hydroxide [18]. In a typical preparing method, titanium alkoxide is
added to the base at 2 °C in alcoholic solvents in a three-neck flask and is heated
at 50–60 °C for 13 days or at 90–100 °C for 6 h. A secondary treatment involving
autoclave heating at 175 and 200 °C is performed to improve the crystallinity of the
TiO2 nanoparticles. A prolonged heating time below 100 °C for the as-prepared gel
can be used to avoid the agglomeration of the TiO2 nanoparticles during the crys-
tallization process, obeying the kinetics of the reaction [19]. By heating amorphous
TiO2 in air, large quantities of single-phase anatase TiO2 nanoparticles with average
particle sizes between 7 and 50 nm can be obtained.
Micelle and Inverse Micelle Methods: Aggregates of surfactant molecules dis-
persed in a colloidal liquid are called micelles when the surfactant concentration
exceeds the critical micelle concentration (CMC). CMC is the concentration of sur-
factants in free solution in equilibrium with surfactants in aggregate form [16].
In micelles, the carbonic chains with hydrophobic characteristics of the surfac-
tant are oriented toward the interior of the micelle, while the hydrophilic groups
are oriented toward the aqueous medium. The lipid concentration determines the
self-organization of the surfactant/lipid molecules. The values of H2 O/surfactant,
H2 O/titanium precursor, ammonia concentration, feed rate, and reaction temper-
ature are significant parameters in controlling TiO2 nanoparticle size and shape.
Amorphous TiO2 nanoparticles with diameters of 10–20 nm were synthesized and
converted to the homogeneous anatase phase at 600 °C and to the more thermody-
namically stable rutile phase at 900 °C. Li et al. prepared TiO2 nanoparticles with
the chemical reactions between TiCl4 solution and ammonia in a reversed micro-
emulsion system consisting of cyclohexane and polyphenols [20]. The produced
amorphous TiO2 nanoparticles are converted into anatase when annealed at tem-
peratures from 200 to 750 °C and into rutile at temperatures higher than 750 °C.
The crystallinity of TiO2 nanoparticles initially (prepared by controlled hydrolysis
of titanium alkoxide in reverse micelles in a hydrocarbon solvent) could be enhanced
by annealing in the presence of the micelles at temperatures considerably lower than
those required for the traditional calcination in resistive furnace.
Hydrothermal Method: Hydrothermal synthesis is conducted in steel pressure
vessel (autoclaves) under controlled temperature and pressure with reaction in aque-
ous solutions. The temperature can be elevated above the boiling point of water,
increasing the pressure of vapor saturation. This method is widely used to prepare
nanoparticles [21]. For instance, the nanoparticles can be prepared by adding a 0.5 M
isopropanol solution of titanium butoxide into deionized water ([H2 O]/[Ti]: 150) and
then peptized at 70 °C during 1 h in the presence of tetraalkylammonium hydroxides
(peptizer). After filtration and heat treatment at 240 °C for 2 h, the as-prepared pow-
ders are washed with deionized water and absolute ethanol and then dried at 60 °C.
TiO2 nanowires have also been successfully obtained with the hydrothermal method
by various researchers [22]. Normally, TiO2 nanowires are obtained by treating TiO2
60 N. Shrivastava et al.

white powders in a 10–15 M NaOH aqueous solution at 150–200 °C for 24–72 h

without stirring in an autoclave.
Solvothermal Method: This is almost identical to the hydrothermal method with
only exception that the used solvent here is non-aqueous. Moreover, the temperature
can be elevated much higher than that in hydrothermal method, since a variety of
organic solvents with high boiling points can be chosen. For instance, TiO2 nanoparti-
cle was prepared using titanium (IV) n-butoxide (purity 97%) as the starting material.
Titanium n-butoxide is suspended in toluene and placed in autoclave, in a test tube.
The same solvent was filled in the gap between the test tube and the autoclave wall.
The autoclave was purged completely by nitrogen; after that, it was heated up to
the desired temperature at 573 K with the rate of 2.5 K/min. The temperature of
the autoclave was held constant at 573 K for 2 h and then cooled down to room
temperature. The obtained TiO2 powder was washed by methanol for several times
and finally dried in air [23].
Electrodeposition: Electrodeposition is applied to produce a homogeneous, usu-
ally metallic, coating on a surface by the reduction action on the cathode. The sub-
strate to be coated is used as a cathode and immersed in a solution containing a salt of
the metal to be deposited. The metallic ions (Ti3+ ; TiIV ) are attracted to the cathode
and reduced electrolytically to the metallic form. With the use of the template of an
anodic alumina membrane (AAM), TiO2 nanowires can be prepared by electrode-
position [24]. In a typical synthesis, the electrodeposition was carried out in 0.2 M
TiCl3 solution with pH = 2 with a pulsed electrodeposition approach, and titanium
and/or its compound are deposited into the pores of the AAM. By heating the above-
deposited template at 500 °C for 4 h and removing the template, pure anatase TiO2
nanowires can be obtained.
Sonochemical Method: Ultrasound production is a phenomenon based on the
process of creating, expanding, and imploding cavities of vapor and gases. The
implosion of these gaseous cavities is called cavitation, promoting activation effects
in chemical reactions [25]. The cavitation produces intense local heating (~5000 K)
and high pressures (~1000 atmosphere). The origin of the cavitation is due to the
fact that, during the expansion, the gases adsorbed in the liquid around the cavity
or at the interface evaporate resulting in the expansion of the cavity [25]. The bub-
bles propagate the expansion according to the oscillation of the ultrasound pressure.
Sometimes, the collapse of the bubble becomes very violent due to the converging
spherical geometry and the inertia of the liquid moving into that collapsed bubble.
Yu et al. have applied the sonochemical method in preparing highly photoactive TiO2
nanoparticle photocatalysts with anatase and brookite phases using the hydrolysis
of titanium tetra isoproproxide in pure water or in a 1:1 EtOH-H2 O solution under
ultrasonic radiation [26].
Microwave Method: Microwave irradiation is electromagnetic radiation in the
frequency range 0.3–300 GHz, which corresponds to wavelengths of 1 mm to 1 m
[27]. Due to the fact that the electromagnetic radiation produces an oscillating field,
the dipoles or ions continuously attempt to realign themselves in the electric field.
Depending on the timescales of the orientation and disorientation phenomena rel-
ative to the frequency of the irradiation, different amounts of heat are produced
Materials for Solar Cell Applications: An Overview of TiO2 … 61

through molecular friction and dielectric loss. Thus, the electric dipoles of solid
systems change their orientation with a lag time because of crystalline lattice or
short-distance interactions. If the microwave radiation has a frequency of the same
order of magnitude as this time of lag, the dipole realignment suffers only a small
lag with the oscillating electric field, and the solid can absorb the radiation and con-
vert it to heat [27]. Thus, in the use of microwave-assisted dielectric heating for
solid-state synthesis, it is necessary that at least one species absorb microwave radi-
ation [27]. However, in the frequency of domestic microwave apparatus and at room
temperature, few refractory materials can generate heat since they are called low
dielectric loss insulators. When the dielectric loss of a substance is high, absorption
of microwave radiation occurs and decay of excited vibrational states, releasing the
energy absorbed as heat [27, 28]. This method is also known as microwave-assisted
solid-state (MASS) method. Thus, it is necessary to use a material with high dielec-
tric loss, also called microwave susceptor (charcoal or Fe2 O3 ), to promote the spot
heating of the sample. Once heated, the dielectric loss of the precursor material under-
goes changes, and microwave radiation engages directly with the ceramic material,
warming it up punctually. This makes it possible to reach very high temperatures
(~1500 °C) in a very short time, reducing the average time of synthesis to a few
minutes. Microwave radiation is applied to prepare various TiO2 nanomaterials [29].
Corradi et al. found that colloidal titania nanoparticle suspensions could be prepared
within 5 min to 1 h with microwave radiation, while 1–32 h was needed for the
conventional synthesis method of forced hydrolysis at 195 °C [29].

2.1.2 Synthetic Methods for ZnO Nanostructures

Zinc oxide (ZnO) nanoparticles have a wide range of multiple applications as the
materials promising candidate due to its various applications like optoelectronic
devices [30], cosmetics [31], gas sensors [32], biosensors [33], solar cells [34],
superconductors [35], varistors [36], photodetectors [37], photocatalyst [38], etc.
ZnO is distinctive electronic and photonic wurtzite n-type semiconductor with a
wide direct band gap of 3.43 eV at 2 K and a high exciton binding energy (60 meV)
and deep violet/borderline ultraviolet (UV) absorption of the solar spectrum when
compared to TiO2 [39–42]. Moreover, ZnO nanoparticles can be prepared by simple
low-temperature processes.
For the preparing of ZnO, a variety of techniques have been developed (Table 1)
such as sputtering [43], sol–gel [44–46], vapor–liquid–solid growth [47], physical
vapor deposition [48] zinc–air (Zn–air) system [49], coprecipitation [50], micro-
emulsion [51], thermal evaporation [52], microwave-assisted hydrothermal synthesis
[53], metal organic chemical vapor deposition [54], molecular beam epitaxy [55],
solvothermal [56], sonochemical [57], wet chemical [58, 59], and electrochemical
deposition [60]. Among these methods, the wet chemical has a promising potential for
device applications because it is very simple at ambient conditions, low temperature,
no catalyst, low cost, and high yield. Additional advantages of ZnO are that it can be
easily prepared by wet chemical synthesis, presenting excellent stability under high
 62

Table 1 Summary comparison of synthetic methods taken from [65]

Synthetic method Synthesis Reaction Reaction period Solvent Size distribution Shape control Yield
temperatures (°C)
Coprecipitation Very simple, 20–90 Min–h Water Relatively narrow Not good High/scalable
ambient
conditions
Thermal Complicated, 100–320 Hours–days Organic Very narrow Very good High/scalable
decomposition inert atmosphere compound
Micro-emulsion Complicated, 20–50 Hours Organic Relatively narrow Good Low
ambient compound
conditions
Hydrothermal Simple, high 100–220 Hours–days Water–ethanol Very narrow Very good Medium
synthesis pressure
N. Shrivastava et al.
Materials for Solar Cell Applications: An Overview of TiO2 … 63

energy radiation [61]. ZnO exhibits a tetrahedral configuration and large ionicity at
the borderline between that of covalent and ionic semiconductors [62]. A ZnO crystal
can exhibit three different forms: hexagonal wurtzite, cubic zinc blende, and rocksalt
[63]. ZnO hexagonal wurtzite is the most thermodynamically stable structure. Cubic
zincblende, however, can be stabilized by growing ZnO on cubic substrates. ZnO will
exist in the rocksalt structure only at higher pressures [64]. ZnO is generally an n-
type semiconductor with the presence of intrinsic or extrinsic defects such as oxygen
vacancies (VO ), zinc interstitials (Zni ), and zinc vacancies VZn and affect its optical
properties and electrical behavior [61]. The intrinsic point defects of ZnO drawing
a fundamental role in the electrical behavior of this material. Regarding Zni , it is
generally considered to act as a donor. On the other hand, VZn is usually considered
to act as an acceptor. When ZnO is photo-induced by solar radiation with photonic
energy (hv) equal to or higher than the excitation energy (Eg) electrons from the
filled valence band (VB) are promoted to an empty conduction band (CB) [62]. This
photo-induced process produces electron-hole (e- /h+ ) pairs. The electron-hole pairs
can migrate to the ZnO surface and be involved in redox reactions. The mecanism
can generate ecb - and hvb + where ecb - = electrons in the conduction band and hvb + =
electron vacancy in the valence band, respectively. Both of these entities can migrate
to the catalyst surface, where they can enter in a redox reaction with other species
present on the surface.
ZnO has been shown that to exhibit higher absorption efficiency across a larger
fraction of solar spectrum compared to TiO2 . The photo-activity of a catalyst is gov-
erned by its ability to create photogenerated electron–hole pairs. The major constraint
of ZnO as a photocatalyst, however, is the rapid recombination rate of photogenerated
electron–hole pairs, which disturbs the photo-degradation reaction. Additionally, it
has also been noted that the solar energy conversion performance of ZnO is affected
by its optical absorption ability, which has been associated with its large band gap
energy. Therefore, researches have been devoted to improving the optical proper-
ties of ZnO in order to minimize band gap energy and inhibit the recombination of
photogenerated electron–hole pairs. A comparison of various synthesis methods to
prepare ZnO-based nanomaterials is given in Table 1.
Improvement of ZnO as photocatalyst: ZnO is usually an n-type semiconductor
mainly due to the oxygen vacancies (VO ), which can provide more electron charge
carriers. The major drawbacks in the fabrication of ZnO semiconductor are the diffi-
culties in obtaining a stable and reproducible p-type ZnO. The high purity of p-type
ZnO is optimal for various applications due to its high radiative stability. Doping
has been a strategy adopted to improve the physical and chemical properties of
ZnO, incorporating impurities such as metals or non-metals, to shift energy from the
ZnO valence band upwards and reduce the band gap energy to the ultraviolet-visible
region. Metal doping of ZnO can improve the photo-activity of catalysts by increasing
the trapping site of the photo-induced charge carriers and thus decrease the recombi-
nation rate of photo-induced electron–hole pairs [66]. This phenomenon can occur
without causing any large lattice distortion. Besides, energy band gap decreases, and
the ZnO-doped material could be applied in dye degradation and solar cells. However,
64 N. Shrivastava et al.

highly active photocatalysts can be obtained by coupling two semiconductors hav-

ing different band gaps. Higher-efficient charge separation may be achieved due to
photo-induced electrons that are transferred away from the photocatalyst. Therefore,
the heterostructure of nanomaterials acts as an attractive alternative for enhancing
the photo-activity of photocatalysts. For ZnO coupled with other semiconductors,
TiO2 /ZnO, SnO2 /ZnO, SnO2 /ZnO/TiO2 , and Co3 O4 /ZnO are the most investigated
materials for photocatalytic processes [62]. In the ZnO/TiO2−x Ny array, the ZnO elec-
trons are transferred from the conduction band to the TiO2−x Ny conduction band,
while conversely the photogenerated holes are transferred from the valence band of
TiO2−x Ny to the valence band of ZnO [67]. The occurrence of such phenomena sup-
presses the recombination of the electron/hole (e− /h+ ) pairs, increasing the charge
carriers. In this system, ZnO could increase concentration of free electrons in the
CB of TiO2 , which implies that charge recombination is drastically reduced in the
electron transport process. An improvement in the redox processes is expected in
this combination of matrices, since the separation of charges increases the lifetime
of the charge carriers.
Solar cells: Reducing the use of fossil fuels and their consequent production of
gaseous pollutants has been the main target for the search for clean and environ-
mentally friendly sources of energy. Thus, ways to convert sunlight into electrical
energy have become the focus of the global energy field. Since 1991, dye-sensitized
solar cells (DSCs) have attracted attention due to its low cost and simple prepara-
tion. DSCs prepared with TiO2 nanocrystallites sensitized by ruthenium-based dye
have achieved a conversion efficiency above 11% [68]. Zinc oxide has recently been
explored as an alternative material in dye-sensitized solar cells with great potential.
The main reasons for this increase in research surrounding ZnO material include:
(i) ZnO having a band gap similar to that for TiO2 at 3.2 eV and (ii) ZnO having a
much higher electron mobility ∼115–155 cm2 V−1 s−1 than that for anatase titania
(TiO2 ), which is reported to be ∼10−5 cm2 V−1 s−1 [69].
There are reports in the literature that relate about the higher state of nanocrys-
tallite aggregation induces a more effective photon capture in the visible region, as
well as a strong dispersive effect of light. This phenomenon optimizes the absorp-
tion of incident light, weakening the transmittance of thin films, which may present
strong interference in the solar conversion process [69]. ZnO nanocrystallites have
been demonstrated as an effective approach to generate light scattering within the
photo-electrode film of DSCs while retaining the desired specific surface area for
dye molecule adsorption. The maximum energy conversion efficiency of 5.4% was
achieved on photo-electrode films that consist of polydisperse ZnO aggregates of
nanocrystallites. This efficiency is a more than 100% increase over the 2.4% achieved
for films only including nanosized crystallites. The polydispersity in the size distri-
bution of ZnO aggregates was indicated to be positive in causing light scattering in a
broad wavelength region and therefore, in enhancing the light-harvesting capability
of the photo-electrode film. The presence of nanometric material promotes enhanced
light scattering for increased photon absorption.
Materials for Solar Cell Applications: An Overview of TiO2 … 65

3 Rare Earth-Based Materials

Rare earths (RE) include 17 elements of the periodic table, the “lanthanide series”—
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu (Z: 57–71) and the
elements Sc (Z: 21) and Y (Z: 39). The term “rare” can be misinterpreted since La,
Ce, and Nd are more abundant than the Pb, Ni, Mo, and As elements, while Tm and
Lu, the least abundant, are found in greater quantity than Au, Ag, Pt, and I. Thus, the
term “rare” refers to the difficulty of chemically separating RE elements from their
minerals, since their chemical properties are very similar [70, 71].
The RE elements (except Sc and Y) exhibit general electronic configuration [Xe]
4fN 6 s2 or [Xe] 4fN−1 5d1 6 s2 (La, Ce, Gd, and Lu), where N represents the number
of electrons in shell 4f, but due to lower values of the first ionization energies [72],
the predominant oxidation state of these elements is trivalent (3+) [73–75]. However,
some RE ions exhibit the divalent (e.g., Eu2+ and Yb2+ ) and tetravalent (e.g., CeIV
and TbIV ) states that can be found with some stability, since these species have
completely empty electronic level (CeIV ), partially filled 4f7 (Eu2+ and TbIV ) or fully
filled 4f14 (Yb2+ ) [76]. Not by chance, these ions have higher ionization energies for
the process RE2+ → RE3+ , in the case of Eu2+ and Yb2+ and lower to the process
RE3+ → REIV for the Ce3+ and Tb3+ ions [72].

3.1 Upconversion Rare Earth Materials for Photovoltaic

Applications

There is plenty of literature available related to down-conversion (DC) phenomenon-

related solar cells. So we discuss a novel experimental results related to upconversion
(UC), which is a phenomenon in which the absorption of two or more low-energy
photons leads to the emission of a higher-energy photon [77]. Trivalent lanthanide
ions, which have many energy-level structures, are good candidates for sensitization
and activation. In this sense, Er3+ , Tm3+ , and Ho3+ ions are generally applied as
activators to give rise to efficient visible emissions under low pump power densities.
In order to enhance upconversion luminescence efficiency, the Yb3+ ion is usually
co-doped as an excellent upconversion sensitizer due to its large absorption cross
section in the 900–1100 nm NIR region, corresponding to the 2 F5/2 → 2 F7/2 (Yb3+ )
transition. In fact, the Er3+ –Yb3+ couple is by far the most studied upconversion
system. For photovoltaic applications, the energy transfer mechanisms are based on
some combination of mechanisms are based on some combination of excited state
absorption (ESA) and energy transfer upconversion (ETU) processes. In this sense,
many groups have pursued new luminescence-based upconversion materials with the
aim to enhance their efficiency.
Er3+ -doped upconversion luminescence materials are the most potential upcon-
verters for c-Si solar cells due to the ground-state absorption (GSA) of Er3+ in the
range of 1480–1580 nm (4 I15/2 → 4 I13/2 transition). Ho3+ ion has a relatively large
66 N. Shrivastava et al.

absorption band in the 1150–1225 nm spectral range due to 5 I8 → 5 I6 transition [72].

The GSA centered at about 1540 nm results in upconversion via an ETU mechanism,
giving rise to four emission bands: 4 I11/2 → 4 I15/2 , 980 nm; 4 I9/2 → 4 I15/2 , 810 nm;
4
F9/2 → 4 I15/2 , 660 nm; and 4 S3/2 → 4 I15/2 , 550 nm. These emission bands match
well with the absorption of c-Si.

4 Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) are next-generation photovoltaic cells that can be
used to create low-cost, environmentally friendly, and flexible solar panels. Unlike
conventional Si-based solar cells, DSSCs primarily consist of photosensitive dyes
and other substances such as an electrolyte solution and metal oxide nanoparticles. In
this sense, Shan and Demopoulos [78] reported in 2010 for the first time, the applica-
tion of rare earth-doped upconversion luminescence materials for improving the NIR
sunlight harvesting in DSSCs. In their studies, the Er3+ , Yb3+ co-doped LaF3 part
of the nanocomposite helps capture near-infrared (NIR) light by converting it into
visible light absorbable by the dye, hence opening the road for the development of
DSSCs with higher conversion efficiency and photocurrent output. The green emis-
sion located at around 543 nm generated by the upconversion nanocomposite can
be efficiently absorbed by the N719 dye, which indeed leads to photocurrent gen-
eration upon 980 nm laser excitation. Different upconversion materials consisting
of NaYF4 :Er3+ /Yb3+ hexagonal nanoplatelets (particle size ~800 nm) were tested
in DSSCs by Shan et al. [79]. The upconverting phosphors were directly placed on
the rear side of a counter electrode. This design enables a dual-mode functionality
that provides both light reflection and NIR light capture. Photocurrent was observed
for the DSSC device when irradiated with a 980 nm laser, clearly demonstrating the
upconverting function of the NaYF4 :Er3+ /Yb3+ nanomaterials. Several other groups
also reported the enhanced NIR response of the DSSCs by using upconverting mate-
rials NaY(MoO4 )2 , doped with Ln3+ (Ln = Er and Ho), exhibiting efficient, visible,
and near-infrared emitting [80]. These materials were prepared by a conventional
solid-state reaction, and sensitization of Ln3+ (Ln = Er and Ho) from the host with
different doping concentrations of Ln3+ was investigated. Under excitation at 310 nm,
the phosphor shows intense and characteristic emission of Er3+ and Ho3+ in both the
visible and NIR region due to sensitization by MoO4 2− group. In the excitation
spectra, there is a broadband ranging from 250 to 380 nm which is associated with
the O2− –Mo6+ charge transfer transition in the MoO4 2− group. An efficient energy
transfer from MoO4 2− to rare earth ions was observed at 410, 531, 553, 658, and
1536 nm (Er3+ ) and emissions at 384, 440, 468, 483, 541, 660, 754, and 1195 nm
(Ho3+ ). As a result, Er3+ or Ho3+ single-doped NaY(MoO4 )2 phosphor may have
potential application in modern lasers and photonic technology.
Yb–Er–F triply-doped TiO2 upconversion nanoparticles (YEF–TiO2 –UCNPs)
composite structures were prepared as photoanodes of the flexible DSSCs by using
Materials for Solar Cell Applications: An Overview of TiO2 … 67

hydrothermal and spin-coating approaches [81]. The as-synthesized YEF–TiO2 -

UCNPs which could enhance the absorption of N719 dyes by converting the near-
infrared light to visible light exhibited better upconversion luminescence properties
than the Yb–Er co-doped TiO2 upconversion nanoparticles. Moreover, the appropri-
ate YEF–TiO2 -UCNPs could enlarge light-harvesting range of the formed flexible
photoanode and improved the photovoltaic performance of the DSSCs. Notably, this
novel DSSC configuration greatly overcomes the drawback of charge recombination
induced by the conducting upconversion layer when used internally.
Phosphors and Glasses: The rare earth-doped luminescence materials exhibit
promising applications which include radiation detection, sensors for structural
damage, optical memory media, identification markers, medical diagnostics, optical
probes for in vivo bioimaging, and solar cell sensitizers [82–85]. Photon manage-
ment by different means opens the opportunity to create new applications in diverse
fields. In particular, the combination of rare earth ions with wide band gap semi-
conductors has attracted a lot of interest and recognized a lot of success in the
technologies of lasers, optical fibers, fluorescent lamps, light-emitting displays, bio-
science and imaging [86]. In the field of solar energy, these combined materials can
act as photon converter structures with functionalities such as down-shifting (DS),
down-conversion (DC), or upconversion (UC), which might enhance the solar cell
efficiency. The concept is that photons from the solar spectrum can be converted to
photons that match better the absorption wavelength range of the solar cell.
Table 2 summarizes the development of phosphors and glasses as down-shifting
layers for a variety of photovoltaic devices. In these studies, the principal strategy

Table 2 Phosphors and glasses used as down-shifting layers for photovoltaic applications
Materials Preparation method Wavelength Wavelength
excitation (nm) emission (nm)
NaY(MoO4)2 :Er3+ ,Yb3+ Solid-state reaction 980 384–754, 1195
TiO2 :Yb3+, Er3+ ,F Hydrothermal method 980 525–800
SrAl2 B2 O7 :Eu3+ , Gd3+ , Glass melting 254, 365 400–700
Sm3+ , Nd3+
Tm3+ /Tb3+ /Sm3+ Melt quenching 358 452–645, 700, 800
co-doped borate glass
La2 O3 :Eu3+ Sol–gel Pechini 285 570–700
method
YVO4 :Bi3+ , Eu3+ Aqueous precipitation 250–400 570–700
YAG:Ce3+ , Cr3+ Solid-state reaction 400–500 688
YAG:Ce3+ , Nd3+ Sol–gel 400–500 850–950, 1062
Cr3+ –Yb3+ -doped Glass melting 300–700 950–1100
fluorosilicate glass
LaVO4 :Dy3+ Hydrothermal method 250–320 450–600
Y2 O3 :Eu3+ Co-precipitation 230–320 570–700
68 N. Shrivastava et al.

has been to convert the ultraviolet-blue radiation into red-NIR (near-infrared) emis-
sion by utilizing Stokes-shifted photoluminescence. Among RE3+ ions, NIR-emitting
Nd3+ and Yb3+ ions have attracted significant researches. Their typical NIR emission
around 1000 nm is just above the band edge of c-Si where the solar cell exhibits the
higher spectral response. With the aim to overcome the weak luminescence of Nd
and Yb ions, several research groups are applying other luminescence species with
higher absorption coefficients to sensitize the Nd3+ or Yb3+ . An example could be
Eu, Gd, Sm, Nd co-doped in SrAl2 B2 O7 nanocrystal phosphors prepared by glass-
ceramic technique [87]. Phosphorescence measurements indicated that the formed
SrAl2 B2 O7 phase is a promising host phosphor for rare earth ions to give differ-
ent emission colors used in different applications. These glasses based on alumina
borates compositions doped with rare earth ions attracted much interest due to its
special properties as high UV transparency, nonlinear properties, exceptional opti-
cal damage threshold, and their ability to withstand the harsh condition in vacuum
discharge lamps or screens [88]. Optical absorption spectra exhibited a character-
istic UV absorption line at 357 nm with no further absorption in visible or NIR
regions. SrAl2 B2 O7 glass doped with Gd3+ also exhibits no visible or NIR absorp-
tion spectra while Eu3+ -, Nd3+ -, and Sm3+ -doped samples exhibited characteristic
absorption bands in both visible and NIR regions. The multicolor phosphorescence
was attributed to the alternation of rare earth in glasses.
Tm3+ /Tb3+ /Sm3+ triply-doped transparent borate glasses (Na2 O–CaO–P2 O5 –
B2 O3 –ZrO2 ) were successfully synthesized via melt-quenching technique [89].
These glasses may be a promising candidate for white light-emitting diodes, lumi-
nescent materials, and fluorescent display devices. Among the various RE3+ ions
doped, Tm3+ /Tb3+ /Sm3+ triply-doped compounds can be employed as good activa-
tors because of their unique spectral characters and emission intensity in glasses.
In this material, while the concentration of Sm3+ ions increasing, both of fluores-
cence decays of Tm3+ and Tb3+ become quicker. This confirms that energy transfer
of Tm3+ → Sm3+ and Tb3+ → Sm3+ occurs [89]. Besides, there are typical spectral
overlapping between the Tm3+ , Tb3+ emission upon excitation at 358 nm, and the
Sm3+ absorption. The overlap of the terbium 5 D3 → 7 F4 and 5 D4 → 7 F6 emission
bands with the Sm3+6 H5/2 → 4 M17/4 , 6 H5/2 → 4 I9/2 , and 6 H5/2 → 4 G7/2 absorption
peaks, respectively.
The emission bands (1 D4 → 3 F4 and 1 G4 → 3 H6 ) of Tm3+ overlap with the
absorption bands (6 H5/2 → 4 G7/2 and 6 H5/2 → 4 I9/2 ) of Sm3+ [89]. Thus, potential
energy transfer processes from Tm3+ to Sm3+ and Tb3+ to Sm3+ are confirmed in the
Tm3+ /Tb3+ /Sm3+ co-doped glass samples upon excitation at 358 nm. With increas-
ing the content of Sm3+ , the luminescent color can be tuned easily from blue to
white. Thus, Tm3+ /Tb3+ /Sm3+ triply doped glass (Na2 O–CaO–P2 O5 –B2 O3 –ZrO2 )
is a promising candidate for the development of white light-emitting diodes, lumi-
nescent materials, and fluorescent display devices. In addition, host sensitization via
energy transfer (ET) from an excited host lattice to rare earth ion (RE3+ ) also offers
an effective way to improve the luminescence signal.
The photoluminescence emission process occurs as a result of a radiative electron
transition in which the electron decays from a more energetic state to a less energetic
Materials for Solar Cell Applications: An Overview of TiO2 … 69

state [76]. First, the electron must be excited to a state of higher energy by UV or
visible light, for example. After the excitation, the nuclei adjust their positions to
the new excited situation, so that the inter-atomic distances are equal to the equilib-
rium distances belonging to the excited state. During the relaxation process, there
is no emission. The system can return to the ground state spontaneously under the
emission of radiation from the lowest energy level of the excited state. The emission
occurs at energy lower than the absorption due to the relaxation process. The energy
difference between the maxima of the absorption and emission bands of the same
transition is called the Stokes shift. The luminescence emission spectrum represents
the luminescence intensity obtained in the visible (or UV, IR) wavelength range
with a fixed excitation wavelength. On the other hand, an excitation spectrum is an
impression of the intensity of luminescence at a given emission wavelength over
a range of excitation wavelengths. Thus, the excitation–emission spectra consist of
a two-dimensional image which displays the intensities of the luminescence as a
function of the excitation and emission wavelengths.
Inorganic solid materials that give rise to luminescence are called phosphors or,
recently, luminescent materials [74]. Luminescent materials generally require a host
lattice crystalline structure that constitutes the bulk of the phosphors. The characteris-
tic luminescence properties are obtained by doping the matrix material with relatively
small amounts of foreign ions (RE ions). The luminescence of inorganic solids can be
classified into two mechanisms: luminescence of localized centers or activators and
luminescence of semiconductors through band-to-band excitation [90]. To improve
the luminescence from an activator without efficient absorption for the available exci-
tation energy, a sensitizer ion is often incorporated into the host material to transfer
its excitation energy to the activator. The emission color can be readily adjusted by
varying the dopant concentration or composition without changing the host lattice.

5 Organic and Polymer Solar Cells

As mentioned earlier various types of solar cells have become an interesting topic in
recent two decades. Most used solar cells are based on silicon but limited by power
conversion efficiency (PCE) of 25% on laboratory scale and 11–16% in commercial
arrays and lifetimes of about 20 years. But thick silicon layers make these cells
relatively expensive. Hence, the needs for the alternative solar energy technologies
and a lot of research efforts have been put into this area. Organic thin-film solar cell
technologies, e.g., polymer solar cells (PSCs), have been shown to be a promising
alternative to the silicon-based solar cells. The word polymer originates from the
Greek words poly (many) and meros (parts). A polymer does indeed consist of
many parts, called monomers, which are linked together in a long chain to form
a polymer. Conjugated polymers consist of a backbone chain of alternating single
and double bonds. Because of this, there will be an overlap of p-orbitals which
in turn enables delocalization of electrons across the polymer backbone, making it
a one-dimensional semiconductor. Normally, polymers are regarded as insulators,
70 N. Shrivastava et al.

unable to conduct electricity or absorb sunlight. For their discovery and contribution
to the development of conjugated polymers, Shirakawa, McDiarmid, and Heeger
were awarded the Nobel Prize in chemistry in 2000. The main advantage of polymer
solar cells (PSCs) is the potential of flexible and lightweight devices that can be
solution processed by cheap and efficient methods such as roll-to-roll processing,
inkjet printing, or spray coating. Nowadays, the efficiency of laboratory-scale devices
is ~9 to 10%. However, in order to compete with silicon-based solar cells and other
energy sources, relatively low stability and short lifetime of polymer solar cells
(PSCs) have to be improved. The active layer of PSCs usually consists of a blend of
a conjugated polymer as light-absorbing material and electron donor and a second
material, often a fullerene derivative, as electron acceptor. The conversion of solar
energy into electrical energy requires the conjugated polymer in a solar cell able to
absorb a substantial amount of the available photons, in which photon energies that
can be absorbed are defined by the band gap (Eg) and absorption coefficient of the
semiconducting polymer. The absorption coefficient is described as the amount of
photons a material absorbs at a given wavelength. Ideally, a material should absorb
all available photons. For the potentially highest power output for a single layer
cell, the band gap should be between 1–1.5 eV and 1250–830 nm, as described by
Shockley–Queisser.
An organic solar cell (OSC) is a photovoltaic device whose active layer comprises
p-conjugated polymers and small molecules. Among the arguments for pursuing
research on OSCs are that most—if not all—of the components can be deposited from
solution in a roll-to-roll manner that the materials are in principal earth-abundant,
that devices can be semi-transparent or aesthetically pleasing, that the devices are
ultra-flexible and even stretchable, and that the materials and whole devices can be
extraordinarily lightweight. Organic photovoltaic devices are thus unique not only in
that they could have low costs per module, but that their thinness and extremely small
mass could also reduce the costs associated with transportation and installation of
modules (part of the balance-of-system costs, which are generally independent of the
particular photovoltaic technology of the module). Organic photovoltaic cells with
a single-component active layer sandwiched between two electrodes with different
work functions only led to very low power conversion efficiency due to poor charge
carrier generating and unbalanced charge transport.
Functional principle of organic photovoltaic cells: Contemporary organic pho-
tovoltaic cells are often based on a heterojunction made of two materials: an electron
donor (D) and an electron acceptor (A). In the molecular case, the basic energy-level
diagram used to describe the operating principle of an OPV cell is shown in Fig. 3.
The molecular energy levels involved in the light conversion into electricity are the
highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular
orbital (LUMO), respectively. The ionization potential (IP) is the energy needed to
remove an electron from a neutral molecule and is related to the HOMO energy
level. The fundamental gap, Efund , or HOMO-LUMO energy gap is defined as the
difference between IP and the electron affinity (EA). The EA is the amount of energy
released when an electron is added to a neutral molecule and is used to estimate the
Materials for Solar Cell Applications: An Overview of TiO2 … 71

Fig. 2 a Basic energy-level diagram and illustration of energy gap in molecular case of an organic
semiconductor, b functional principle of a D/A solar cell

electron-withdrawing ability of a molecule to act as an electron acceptor in an OPV

device and thus linked to the LUMO energy level relative to vacuum.
In the material case, the molecular energy levels are broadened into electronic
bands. The upper occupied band is referred to as the valence band, and the lower
unoccupied band is referred to as the conduction band. The material band gap is
defined as the energy difference between the top of the valence band and the bottom
of the conduction band. As simply described in Fig. 2, the photovoltaic effect of
converting sunlight into electricity in an organic photovoltaic cell can be summarized
as the following four steps: (i) photon absorption and exciton generation; (ii) exciton
diffusion to the D/A interface; (iii) exciton dissociation into free charge carriers
(electrons and holes), and (iv) charge transport and charge collection at the electrodes,
which produce current in the external circuit. A bilayer heterojunction configuration
containing a p-type layer for hole transport and an n-type layer for electron transport
can be implemented to improve the photocurrent of the solar cell device
Generally, the synthesis of polymer solar cells is performed using green synthesis
method following the common reaction as given below: Metal-mediated cross-
coupling reactions: This group can be subdivided by two subgroups of reactions.
Stille polymerization: The most common reaction methodology employed to gen-
erate alternating donor–acceptor, low-band gap polymers is the Stille-based con-
densation [91, 92] and polymerization of bromide-terminated and trimethylstannyl-
terminated monomers and alternatives. Suzuki polymerization: The Suzuki reaction
is in some aspects environmentally preferable to the Stille reaction, though it brings
its own set of potential complications [93, 94]. The base, water, and phase transfer
catalyst that are required for the typical Suzuki reaction to add significant complex-
ity to the reaction setup, which will be exacerbated at large scale where multiphase
reactions are sometimes slower and more difficult to mix. The stability of monomers
is often troublesome, as boronic esters have a tendency to condense into cyclic trim-
mers [93]. For illustration, the following is the palladium-catalyzed cross-couplings
in organic synthesis [46]. The Suzuki cross-coupling reaction involves the formation
72 N. Shrivastava et al.

Fig. 3 Reaction mechanism of a a Suzuki cross-coupling reaction and b a Stille cross-coupling

reaction

of sp2 -hybridized carbon atoms (Fig. 3a). The method employs the use of a palla-
dium catalyst and a base to facilitate the reaction between a halide or a triflate and
a boronic compound [95]. The first step in the mechanism is oxidative addition of
the halide to the palladium (0), forming a palladium (II) complex. The reaction cycle
continues with a transmetallation step with the boronic compound, catalyzed by a
base. In the final step, the product is expelled by reductive elimination, regenerating
the palladium (0) catalyst.
The Stille cross-coupling reaction (Fig. 3b) involves the formation of sp2 -
hybridized carbon atoms. The method employs the use of a palladium catalyst to
facilitate the reaction between a halide or a triflate and an organotin compound. Their
action mechanism is similar to that of the Suzuki cross-coupling; the difference is the
absence of a base in the Stille cross-coupling. This allows for polymerization of base-
sensitive monomers. A problem with the Stille reaction is the toxicity of the organ-
otin compounds [96]. This is a disadvantage compared to Suzuki cross-coupling,
both at laboratory scale and for future up-scaling of the process. Other well-known
Materials for Solar Cell Applications: An Overview of TiO2 … 73

reactions for polymer solar cells (PSCs) are heterogeneously catalyzed polymer-
izations, direct heteroarylation polymerization, conjugated polymers comprising of
biologically derived materials, and water-forming polycondensation reactions

6 Summary

To summarize, we have discussed several important synthesis protocols of TiO2 -

and ZnO-based materials for their significance in solar cell applications. A novel
phenomenon of upconversion solar cell, harvesting rare earth characteristics, has
shown a huge impact to fight the issue-related solar energies. Dye-sensitized solar
cells, incorporating rare earths and other dyes, have shown potential importance and
hence require more attention in the solar cell applications.

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Recent Advances in Solar Cells

Marcio A. P. Almeida

Abstract The last years the growth of the global population has resulted in high
demand for electricity consumption. Photovoltaic devices have shown a big potential
to obtain energy power from solar irradiation when compared with other sources. Cur-
rently, photovoltaic silicon-based technologies are the most used around the world,
but its high cost is still a big problem for global consumption. A short approach to
fundamental concepts to inorganic and organic solar cells will be described in this
chapter. Moreover, it will be showing new models of solar cells as well as advances
and challenges in the development of inorganic and organic solar cells with high
efficiency and stability.

Keywords Photovoltaic devices · Solar cells · Energy

1 Introduction

The high growth of the world population, along with industrial and urban develop-
ment, has resulted in high demand for energy consumption. The use of renewable
energy sources such as biomass, wind, hydroelectric, geothermal, and photovoltaic
(solar energy) is of fundamental importance for the sustainability of the planet.
The photovoltaic systems are one of the fastest-growing renewable sources in
the world, representing 20.5% of power generation. Only in 2017, new installation
totaling more than 100 GW, with highlight to China with 48 GW, which reflects a total
of 4426 TeraW/h (global), an increase of close 35 percent annual when compared
with 2016 [1]. By definition, photovoltaic systems are technologies able to convert
sunlight into electrical power (direct current, DC), from semiconductor materials,
which is measured in watts.
In historical terms, the first functional application of photovoltaic system was
reported by Fritts in 1883 [2], but only in 1954, a researcher at Bell laboratory in
the USA discovered the potential of pn junction diodes to generate voltage when

M. A. P. Almeida (B)
Curso de Ciência e Tecnologia, Universidade Federal do Maranhão, Campus Bacanga, São Luis,
Maranhão 65085-580, Brazil
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 79

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_4
80 M. A. P. Almeida

the light was on, which within a year 6% efficient to Si pn junction solar cell was
achieved [3], which was also made by Reynold et al. to film heterojunction solar cell
based-Cu2 S/CdS [4]. The first application toward photovoltaic system has made to
space solar cells (in the 1960s), which was used to power satellite applications from
the USA and USSR, and only in the 1960s, its commercial production began, with
highlight to Japan and Europe [5].
Currently, dominant technologies for the use of solar cells are supported by silicon
(91%) [6]. However, silicon photovoltaic systems have dominant technology over
the world, and in the long years, its cost still has been high, which results in this being
unfeasible for domestic use. In the last years, research has reported other alternatives
of materials to replace based-silicon solar cells [7]. Several reviews have presented
new classes of inorganic, organic, and hybrid materials as a high potential to solar
cells [8]. In some cases, the power efficiency has been similar to the photovoltaic
based-silicon system, a topic which will be described in the last items.

2 Basic Concepts to Solar Cells

Solar cells are recognized as pn junction. As illustrated in Fig. 1, a basic solar cell
is composed of a junction of two (or more, e.g., tandem solar cells) materials, one
p-type and other n-type, connected by two electrodes. When a solar cell is under
sunlight, its electrons valence bands (VB) are excited to the conduction band (CB),
generating a charge electron/hole pair. The energy between VB and CB is called
bandgap, which due to range sunlight, generally to solar cell systems, low bandgap
values are requested 1.1–2.5 eV [9]. This concept of the bandgap is not applied
to perovskite-based solar cells, (PSC) since in these devices, the perovskite acts as
a sensitizer, which has high bandgap values. In the ideal photovoltaic system, pn
junction and the electrons are concentrated on the n-side, while the holes are all
on the p-side. The electrons on VB in p-type semiconducting are driving to CB
in p-type semiconducting which are collected by an external circuit, an electrode.

Fig. 1 a Illustration of solar cell. Reprinted with permission from Ref. [9]. Copyright 2017 Elsevier.
b pn junction to solar cells
Recent Advances in Solar Cells 81

The electron flow between the two electrodes is responsible for generating electric
current. Therefore, over the world, researchers have concentrated many efforts in the
development of new p-type and n-type materials with the potential to use in solar
cells, a discussion which will be further approached in the next section.
Currently, the photovoltaic technology (PV) can be classified into three large
groups: (1) solar cells of the first generation, (2) solar cells of the second generation,
and (3) solar cells of the third generation, Fig. 2. For solar cells of the first generation,
the silicon-based technologies (single, multi-crystalline silicon) are predominant,
with highlight to crystalline silicon, but that another category of the solar cells as
hydrogenated amorphous silicon (a-Si–H) PV is also widely used. In PV of the second
generation, the highlight concerns thin-film technologies. In this category, GaAs-
based, CdTe (and analogous), and CuInSe (and analogous) are found. Finally, in the
third generation (also of the thin film), new materials are found with the potential
to overcome the technologies currently used, called advanced semiconductors. This
group of the materials falls within the dye-sensitized solar cells (DSSCs), perovskites
and organic-based solar cells, and quantum dot PV.

Fig. 2 Classification of solar cell technologies

82 M. A. P. Almeida

3 Inorganic Photovoltaic Devices

The first solar cell inorganic-based material was developed at Bell laboratory in 1953
with an efficiency of 6% [3], and your first application was in the solar-powered
Sputnik II (US-Soviet Union, USSR) and Vanguard 1 (USA) satellites [10]. Photo-
voltaic devices, from their discovery until their manufacturing toward commercial
purposes, several other solar cells inorganic-based materials have been presented
such as Cu2 S/CdS [4], GaAs [11], GaAlAs/GaAs [11b], and CdTe [12]. However,
only in the 1980s companies in Japan, the USA, and Europe began manufacturing, but
to silicon-based solar cell using the concept of the pn junction it is still predominant
the use of silicon-based.
In a global overview, crystalline silicon (c-Si) solar cells achieve about 25% of
efficiency and dominating almost 90% of the market [13], whereas CdTe-based pho-
tovoltaic technologies cover only 5% (PCE 20%) [14a] and others such as CuInGaSe2
(GIGS, PCE 19.5%) and amorphous silicon (a-Si:H, PCE 10%) represent the remain-
ing share. Although silicon photovoltaic technologies are dominant in the global mar-
ket, much effort has gone to the development of new thin-film-based photovoltaic
technologies with new materials, which has been reported in several reviews [13, 15].
Materials such as GaAs, InP, and their derivates have arisen as new alternatives to
replace silicon in solar cells. These new materials have displayed highest conversion
efficiencies between 18.4 and 37.9% (InGaP/GaAs/InGaAs), which their efficiency
will depend on the method and composition used in the device building [14a].
For example, Moon et al. have shown that GaAs thin-film solar cell obtained by
epitaxial lift-off (ELO) method can achieve a high efficiency of 22.08% [16] (Fig. 3),
while Bauhuis et al. also to GaAs-based solar cell (thin film) presented an efficiency to
24.5% [17] and Kayes et al. to same material (GaAs) have found efficiency to 27.6%
[18]. Although GaAs-based solar cell and its derivate have achieved great results of
efficiency, high cost of producing device-quality epitaxial layers or substrates make
it impracticable for industrial production.

Fig. 3 J–V curve of the

GaAs thin-film solar cell.
a By Moon and co-works.
Reprinted with permission
from Ref. [16]
Recent Advances in Solar Cells 83

Fig. 4 a Diagram of typical dye-sensitized solar cell using ruthenium (II) complex. Reprinted
with permission from Ref. [19e]. Copyright 2010 American Chemical Society. b cyclometalated
bis-tridentate Ru(II) complexe in DSSC. Reprinted with permission from Ref. [21]. Copyright 2011
American Chemical Society. c I–V curve and IPCE spectra for JK-91 and JK-92. Reprinted with
permission from Ref. [22]. Copyright @ Elsevier

Besides the compounds mentioned above, (polypyridyl) ruthenium(II)-based

complexes and its homologs in the last years have also exhibited applications for
solar cells. Differently from photovoltaic devices described before, here the Ru(II)
complex acts as a sensitizer into the device, as illustrated in Fig. 4a, b. These com-
pounds, to their photovoltaic devices, an efficiency between 6 and 11% [19], have
been displayed. These values of PCE are still little expressive when compared with
other photovoltaic devices, for example, perovskite-based ones, which can achieve
PCE of 22.7% [20]. However, this does not impair the studies of Ru(II) complexes
toward the solar cell, since these compounds have a very versatile structure, which
shows that better results to PCE can be achieved. The versatility of application of
Ru(II) compounds at solar cells is related to the 2,2 -bipyridine molecules and their
derivate coordinates on Ru(II) ion. Such molecules can optimize the bandgap values
as well as its stability, which is attributed to the ability that bipyridine ligand has to
make electronic transition metal-ligand type.
84 M. A. P. Almeida

3.1 Perovskite-Based Solar Cells

Currently, among several inorganic materials used with the purpose of developing
photovoltaic technologies, perovskites have been widely studied and reported in
several reviews [23]. The perovskite-based photovoltaic device first arose in 2007
with a PCE of 2.2% [24]. Since the first reported PCE of 2.2% for solar cell based
on perovskite until nowadays, many improvements were made in the perovskite
structure resulting in a PCE of 23.7% [25], as illustrated in Fig. 5.
In order to improve the efficiency of perovskite-based photovoltaic devices,
researchers have focused their efforts on some strategy, like chemical composi-
tion/structure, morphological evolution [26], and methodology of synthesis. Among
all factors described before, perhaps the chemical composition is the most expressive
concerning efficiency. For example, Deepa et al. [27] have described the importance
of doping of Cs+ into Csx MA1−x PbI3 . For Cs+ content, it was achieved a PCE of
17.1%, which was higher than without Ce+ doping. The insertion of the Cs+ into the
perovskite structure increase V oc , J sc , and FF values, Fig. 6a.
Cho et al. [28] reported the influence of the surface passivation in increase of
both PCE and stability. For passivation of composition (FAPbI3 )0.85 (MAPbBr3 )0.15 ,
a PCE of 21.3% was achieved, as well as better stability was exhibited, Fig. 6b, c.
In this work, the authors described that using the technique of passivation, it was
possible to reduce the amount of the traps and defects which are located more at the
surface of the perovskite film, factors responsible for the recombination of electron–
hole pairs. This observation agrees with observations made by Wang et al. [29] in the
paper reported. For the FA0.83 Cs0.17 Pb(I0.6 Br0.4 ), the composition C60 doped, besides
a better PCE, an improvement to stability was also achieved, Fig. 6d.
As described before, an improvement in the performance of the perovskite-based
photovoltaic device depends on the chemical composition, which can be made

Fig. 5 Efficiency evolution

of perovskite solar cells from
2006 to 2017. Reprinted with
permission from Ref. [8b].
Copyright @ Royal Society
of Chemistry
Recent Advances in Solar Cells 85

Fig. 6 a J–V curves of Csx MA1−x PbI3 with and without Cs+ addition. Reprinted with
permission from Ref. [27]. Copyright @ Royal Society of Chemistry. b J–V curves of
(FAPbI3 )0.85 (MAPbBr3 )0.15 . Reprinted with permission from Ref. [28]. Copyright @ Royal Soci-
ety of Chemistry. c J–V curve hysteresis of the passivated cell for (FAPbI3 )0.85 (MAPbBr3 )0.15 .
Reprinted with permission from Ref. [28]. Copyright @ Royal Society of Chemistry

through doping using different ion metals [30]. Another alternative to it is the employ-
ment of organic cations mix [31]. Zhang et al. [32] showed that to perovskite hybrid
system, to the mix ionic composition of MA and FA cation, a performance over 20%
can be achieved, Fig. 7a. For this structure, the pristine (MAPbI3 ) has presented a
performance of 18.59%. When the guanidinium organic structure is added into per-
ovskite, the PCE value was increased to 20.26%, which is justified by an increase
of all photovoltaic parameters, with highlight to FF, which suggests a reduction of
defects into the interface as well as less hysteresis.
Jodlowski et al. [33] also analyzed the influence of organic cations into the per-
ovskite structure films (MA1−x Guax PbI3 ) but not to the guanidinium (CH6 N3+ , Gua).
For MA1−x Guax PbI3 with x = 0, the PCE observed was 18.00%, when that to x =
5, 10, 14, and 17, it was found 18.81, 19.09, 20.15, 19.29%, respectively. Here, it
was observed that the performance increased only 5 and 10%, which are attributed
to improvements in the photovoltaic parameters J sc , V oc , and FF. Here, it is worth
highlighting to MA1−x Guax PbI3 perovskite with x = 25 that though the PCE values
found were 18.3%, this device presented a better stability when compared with other
86 M. A. P. Almeida

Fig. 7 a J–V curve of FAx MA1−x PbI3 (x = 0, 10, 20, 30%). Reprinted with permission from Ref.
[32]. Copyright 2017 American Chemical Society. b J–V curve of MA1−x Guax PbI3 perovskite
solar cells. Reprinted with permission from Ref. [33]. Copyright 2017 Springer Nature. c Thermal
stability test of MA1−x Guax PbI3 perovskite solar cells. Reprinted with permission from Ref. [33].
Copyright 2017 Springer Nature

devices, Fig. 7b and c, which can be attributed to the hindrance of moisture that
the guanidinium cation proves into the perovskite structure, therefore avoiding the
degradation of film.
Another factor that influences the efficiency of perovskite-based solar cells is the
morphology of the perovskite thin film [26]. The morphology has a direct relation
with the amount of defects which can be present on the film surface, the bulk of the
grain or boundary between neighboring grains. Thus, growth control in thin films
has been attracted many efforts, since this when optimized, reduced defect density
can be obtained and therefore fewer recombination sites, which contributes to the
enhancing of PCE [34].
Wang et al. [35] showed that though different anti-solvents (toluene, chloroform,
diethyl ether, and di-isopropyl ether) used in the deposition process for obtaining
the perovskite-based solar cell, several PCE values have been found, Fig. 8g. The
device obtained with di-isopropyl anti-solvent presented 17.19%, which is superior
to the PCE of the device obtained with the anti-solvent most used in the manufac-
turing of perovskite thin films, chlorobenzene. Indeed, Fig. 8a–f shows clearly as
the anti-solvent influences in the grain and therefore in PCE. The FF value to the
device obtained with di-isopropyl ether was 0.79, which is higher than the FF value
Recent Advances in Solar Cells 87

Fig. 8 Top view SEM images of perovskite films prepared by the anti-solvent deposition method
with different solvent treatments: a without antisolvent. b Toluene. c Chlorobenzene. d Chloroform.
e Diethyl ether. f di-isopropyl ether. h J–V curves of perovskite solar cells fabricated with different
anti-solvent treatment. Reprinted with permission from Ref. [35]. Copyright 2017 Royal Society
of Chemistry

to the device obtained with chlorobenzene, 0.62. For perovskite, a great FF value
indicates fewer defects in the device and therefore a reduction in the recombination
of electron/hole pair rate.
88 M. A. P. Almeida

3.2 Advanced Materials for Charges Transport in Solar Cells

Both inorganic and organic solar cells, being great charge-transfer materials, play
an efficient role in PV systems. These materials, when working efficiently, promote
great charge separation and therefore optimize the PCE. Electron-transporting mate-
rials (ETMs) extract electrons in conduction band from sensitizing and driving to the
photoelectrode (e.g., anode for perovskite solar cell normal) while hole-transporting
materials (HTMs) is responsible for collecting holes of the valence band from sen-
sitizing and transport to the external circuits, cathode, if we have the configuration
glass/FTO/ETM/sensitizing/HTM/Au, Fig. 9. Currently, in the research, there are
several options of inorganic electron transport materials, but TiO2 is the most used
material, which is reported on several reviews [36]. For HTM, although there are
many alternatives to inorganic materials, the organic molecules are most used, with
highlight to spiro-OMeTAD.

3.2.1 Advances in the Development of ETM

It is known to all that three basic criteria are necessary for a great ETM: (1) good
optical transmittance in the visible range, (2) energy level of ETM near the sensitizing,
and (3) presenting a great electron mobility. The second item, the energy level, is
very important because depending on ETM, the configuration of the device can be
normal or an inverted type, for example, for perovskite, Fig. 9b–d. Currently, in the

Fig. 9 Schematic illustration of the most common device architectures of PSCs: a (n–i–p) meso-
porous and planar structures. b Energy diagram of the different components of a conventional PSC.
c Inverted (p–i–n) mesoporous and planar structures. d Energy diagram of the different components
of an inverted PSC. Reprinted with permission from Ref. [37]. Copyright 2018 Royal Society of
Chemistry
Recent Advances in Solar Cells 89

research, TiO2 is the most widely used ETM in the world [38]. However, researchers
all over the world have found new alternatives of ETM, because in order to obtain
ETM (thin films) with great crystallinity high temperature (>450 °C) annealing is
required, which results in the process becoming expensive.
Other alternatives of ETM such as SnO2 [39], WO3 [40], ZnO [41], C60 [39c],
and PCBM [39c] have to arise as options to replace TiO2 . Luo et al. [41d] showed
in a huge review of the potential that ZnO has to act as ETM. They showed that
the efficiency performance of photovoltaic devices with ZnO as HTM depends on
the synthesis method of zinc oxide as well as the device structure, which can be
mesoporous, mesoporous inverted, planar and inverted planar structure, Fig. 9a–c.
For such configurations using ZnO as ETM, it is possible to achieve PCE values
ranging from 2.56 to 17.17%.
Son et al. [42] showed that PCE to ZnO-based photovoltaic devices might be
enhanced through control of the growth using different concentrations of the precur-
sor solution as well as immersion time. In the optimizing process, it was possible to
achieve PCE of 11% when used the concentration 35 mM of solution precursor with
time fixed at 180 min and 90 °C. In 2015, Xu et al. [43] presented the TiO2 /ZnO
bilayer as new propose of ETM, Fig. 10. This new design brings as news, the reduc-
tion of interface recombination, as well as the increase of PCE from 13% (ZnO-based
device) to 17.17%. Li et al. [44] have also made the same observation to ZnO-based
as ETM, and to its device, a PCE of 17.3% was achieved.
Also, in 2015, Chang et al. [45] showed a new approach in the design of solar cells
with ZnO as ETM. Unlike Xu et al. (deposition by spin coating), it was used atomic
layer deposition (ALD) method to deposit ZnO in the design of the inverted perovskite
device, which was achieved a PCE of 16.50%. Comparing both methodologies used
in the building of photovoltaic devices, the device made by the ALD method is better
than the spin coating method since the device made by ALD has a great stability at
the air in 45 days and low hysteresis. Similar to the ZnO, SnO2 has also attracted
much attention of the researchers because of its application as ETM in solar cells.
Thus, SnO2 structure has shown a high potential to replace TiO2 in photovoltaic
devices, and such efficiency depends on the methodology used, data that was well
written by Xiong et al. in their review [39c].
For an improvement of the efficiency in devices containing SnO2 as well as other
materials, it is very important to understand band alignment engineering between
ETM and perovskite. For example, Baena et al. [46] described the importance of
energies level on the conduction band (CB) in ETMs to electrons extraction from
perovskite. Following such criteria, Baena and co-collaborators obtained the device
FTO/SnO2 /Perovskite/Spiro-MeOTAD/Au type, which presented PCE of 18.4%.
Moreover, to this device containing SnO2 , it was observed a low hysteresis as well
as stability at the under air by 30 days. Other authors, such as Song et al. [47],
Chu et al. [48], Huang et al. [49], and Anaraki et al. [50], have reported SnO-based
photovoltaic devices with PCE over 20%. These results are encouraging, since such
efficiency conversion is near to the values found to TiO2 -based devices, and moreover,
these devices presented a reduced hysteresis and good stability.
90 M. A. P. Almeida

Fig. 10 a Schematic diagrams of the device structure. b Energy levels. c Perovskite surface mor-
phology SEM image. d Current–voltage curves of the planar perovskite solar cell. Reprinted with
permission from Ref. [43]. Copyright 2019 Royal Society of Chemistry

3.2.2 Advances in the Development of HTM

As previously described, the 2,2,7,7-tetrakis-(N,N-p-dimethoxyphenylamino)-9-9-

spirobifluorene abbreviated as Spiro-OMeTAD, which was firstly presented in 1998
by Graetzel’s group [51] (Fig. 11a) is the most used HTM in the research on solar cells
[52]. However, the synthesis of this HTM with high purity requires some care, which
makes it very difficult. Furthermore, to its activity, and improve conductivity, some
additives as lithium bis(trifluoromethane)sulfonimide (LiTFSI, doping) and 4-tert-
butylpyridine (TBP) are necessary, which reduce the stability of the PSCs because
of its hygroscopic properties [53]. Thus, the researchers have been concerned to find
out new alternatives to HTM (inorganic or organic) of low cost and high stability
[54], Fig. 11b.
Recent Advances in Solar Cells 91

Fig. 11 a Scheme for the electron transfer processes (inj., injection; reg., regeneration; rec., recap-
ture; hopping) occurring in the dye-sensitized heterojunction. Reprinted with permission from
Ref. [51]. Copyright 1998 Springer Nature. b Energy level diagram of representative inorganic
HTMs (CuI, CuSCN, Cu2 O, CuO, CuS, Cu2 ZnSnS4 , NiOx, MoO3 , V2 O5 , and CuGaO2 ), along
with HOMO level of Spiro-MeOTAD. Reprinted with permission from Ref. [55]. Copyright 2018
American Chemical Society

Due to these many drawbacks, for the use of Spiro-OMeTAD, in 2016,

Graetzel’s group showed again a new option for the HTM, the 2 ,7 -bis(bis(4-
methoxyphenyl)amino)spiro[cyclopenta[2,1-b:3,4-b ]dithiophene-4,9-fluorene],
FDT, which is cheaper (60US$g−1 ) than Spiro-OMeTAD (500US$g−1 , high purity,
Merck).
For perovskite-based photovoltaic devices with FDT, it was obtained a PCE of
20.2%, while that for devices using Spiro-OMeTAD, the PCE was 19.7% [56],
Fig. 12a. Though the increase of efficiency using FDT proved to be slightly higher
than the devices with Spiro-OMeTAD, this result is encouraging, since the obtaining
cost for FDT is cheaper than Spiro-OMeTAD and, furthermore, the FDT is soluble
in more solvent environmental friendly, as toluene instead of chlorobenzene.
Similar to the Graetzel’s group, Xu et al. [57] showed that SFX-based 3D
oligomers called X55 (Fig. 12b, c) have a great potential to replace the Spiro-
OMeTAD. For efficiency of the device with X55 HTM, it was found a PCE of
20.8, while that for the device using Spiro-OMeTAD, the PCE observed was 18.8%.
Another important factor observed for these HTMs was its stability since, for the
device with X55, after six months stored, the PCE exhibited was 19.3% while that
to the device with Spiro-OMeTAD PCE was 16.9%. Wang et al. [58] recently have
proposed two new alternatives of HTM for solar cells, organic molecule, which was
called X61 and X62. For a photovoltaic device with X62 HTM, it was observed PCE
of 15.9 while that to control device (with Spiro-OMeTAD), PCE value was 10%. In
this work, the improvement of PCE is addressed to the shift of the valence band to a
more negative value, which potentiates the hole transfer process from the perovskite
layer to the HTM film.
92 M. A. P. Almeida

Fig. 12 a J–V curves of perovskite solar cells fabricated with FDT, and Spiro-OMeTAD. Reprinted
with permission from Ref. [56]. Copyright 2016 Springer Nature. b J–V curves of perovskite
solar cells fabricated with X55 and Spiro-OMeTAD. Reprinted with permission from Ref. [57].
Copyright 2017 Elsevier. c The chemical structure for X55. Reprinted with permission from Ref.
[57]. Copyright 2017 Elsevier

Bi et al. [59] in its work also showed a new approach of HTM of easy
obtained. In this work, the researcher showed that the N ,N ,N ,N -tetrakis(4-
methoxyphenyl)spiro[fluorene-9,9 -xanthene]-2,7-diamine HTM labeled of X59
exhibit efficiency (19.8%) similar to the photovoltaic device containing Spiro-
OMeTAD, PCE of 20.8%. Although the PCE value for the device with X59 is lower
than the one with Spiro-OMeTAD, the synthesis of X59 HTM was classified as being
a more interesting alternative, a significantly more positive factor in the designing
of new HTMs.
All HTMs described previously are organic molecules. In the last years, inorganic
materials have also attracted much attention to applications as HTMs. These new
materials have shown ability to improve PCE and stability in perovskite-based pho-
tovoltaic devices, as well as reduce the cost of perovskite solar cells. Such materials
are mostly copper oxide-base, which are reported in literature [60].
For example, Rao et al. [61] obtained an inverted perovskite-based solar cell using
CuOx as HTM, Fig. 13a, b. To this device, it was observed a PCE of 19.0%, as well
as the absence of hysteresis, which can be attributed to fewer defects in the interface
Recent Advances in Solar Cells 93

Fig. 13 a Schematic illustration of the energy level diagram to a device containing CuOx as an
HTM. b J–V curve of the perovskite-based device containing CuOx as an HTM. Reprinted with
permission from Ref. [61]. Copyright 2016 Elsevier

perovskite/HTM. This result (PCE) is closer to values found in the literature to PCE
in systems using Spiro-OMeTAD as HTM.
Zhang et al. [62] described the potential that CuGaO2 to the HTM. The synthesis
of CuGaO2 is easier than Spiro-OMeTAD, and moreover, this oxide has better sta-
bility. Thus, when it was made a comparison of PCE to different HTM, the device
with CuGaO2 presented PCE (18.51%) better than the device with Spiro-OMeTAD,
17.14%. The difference between PCE values is slightly small; however the device
with CuGaO2 exhibits excellent stability when stored under humidity, which was
not observed to the device with Spiro-OMeTAD. Liu et al. [63] also showed the
versatility of copper oxides for HMT. It was made Cu2 O-based (modified) device,
which was observed a PCE to 18.9%, while that to the device with Cu2 O (unmod-
ified), the PCE was 11.9%. The device using Spiro-OMeTAD as HTM exhibits a
PCE of 20.0%, which is slightly higher than Cu2 O-based device, but the stability
studies to these devices show that both devices with Cu2 O display better stability
than Spiro-OMeTAD.
Though the results described previously look great, who presented the best pro-
posal of new inorganic HTMs was Chen et al. [64] with Zn: CuGaO2 -based solar
cell, Fig. 14a, b. In this solar cell, besides improving PCE (20.67%), thermal stability
and resistance under a humid environment have been both observed. Herein, though
it has been exhibited an inverted perovskite solar cell, which was used NOx instead
of TiO2 , the improvement of PCE may be addressed to the insertion of Zn2+ ion into
CuGaO2 because Zhang et al. [62] reported a PCE to CuGaO2 -based solar cells with
lower PCE. The insertion of Zn2+ improves the alignment of the valence band of
HTM with the perovskite, which facilitates the hole transport.
94 M. A. P. Almeida

Fig. 14 a Schematic illustration of the device structure and J–V curve between a device with
Zn:CuGaO2 . b Comparison of J–V curve between a device with and without Zn:CuGaO2 . Reprinted
with permission from Ref. [64]. Copyright 2019 Elsevier

3.3 Application of SWCNTs in Perovskite-Based Solar Cells

3.3.1 A Short Approach to Carbon Nanotube

CNT structures, due to their versatility, can become available as the most incred-
ible electronic and optical applications. It depends on their chirality since CNTs
can display different diameters, resulting in different semiconducting or metallic
characteristics [65]. It takes place due to their molecular structure present different
structure band which results in different bandgap, factors acquainted for their con-
ducting properties. General reduction of diameter to CNT is followed by an increase
of bandgap value, which makes it an easy tuning structure.
For electronic applications, the chirality of SWCNT, (n, m) index has to satisfy
n − m = 3j, wherein j is an integer to SWCNT metallic and n − m = 3j + 1
or 3j + 2 to SWCNT semiconducting [66]. This overview previously described
shows us the potentiality to the most diverse type of applications that CNTs display
nowadays. Generally, p-type CNTs are the most used to perovskite-based solar cell,
but CNTs can also present n-type characteristic as well as it can be obtained from p-
type semiconducting. This depends on surface functionalized, and synthesis methods
used [67], which results in a different type of defects created in their structure.
For example, photovoltaic applications of single-chirality SWCNTs have been
shown better than SWCNT chiral mixtures and metallic semiconducting [68]. Here,
the factor crystallinity is very important, since a mixture of CNTs has lower crys-
tallinity and therefore more defects, which are responsible for photoluminescence.
The increase of crystallinity (prove by Raman spectroscopy) in chiral CNTs reduces
the amount of defects, leading to a lower e− /h+ recombination rate, making it ideal
to photovoltaic applications such as solar cells.
The development of new materials toward solar cells is supported in an improve-
ment of p and n-type material, which can be achieved by functionalization technical.
CNTs have been known either p- an n-type material, and it depends on the function-
alized group. For example, SWCNTs exhibit p-type majority charge carriers due to
Recent Advances in Solar Cells 95

oxygen impurity [69]. Therefore, SWCNTs (not functionalized) can act as electron
transfer material (ETM) in solar cells system.
Unlike SWCNTs, when functionalized with organic molecules nitrogen-
containing electrons donors such as polyethyleneimine (PEI) [70] and phosphine
[69c], they can convert SWCNT from p- to n-type. It happens because the doping
molecule transfers partial electrons to conduct band SWCNT (LUMO) and block in
part hole in the valence band [69c]. This versatility to CNTs shows us the poten-
tial to this class of the material in the most diverse applications, thus toward the
development of electronic devices.

3.3.2 SWCNTs into Perovskite-Based Solar Cells

Perovskites are the most commonly studied materials for the application in solar cells,
a fact which has resulted in a large amount of reviews reported [36c, 71]. Though
perovskite structure has presented PCE over 20% [20, 72], three issues of fundamen-
tal importance have to be overcome concerning devices containing such structures:
(1) low stability, (2) high hysteresis, and (3) charges recombination, electron/hole
pair.
The low stability in perovskite structure is a consequence of degradation of per-
ovskite structure under humidity [73], heating, and/or on a long time under irradi-
ation, while the hysteresis can be attributed to charge accumulation either in trap
states of the perovskite/TiO2 interface or in the HTL, for example, Spiro-OMeTAD
involving LiTFSI and TBP as p-dopants [74]. To high recombination rates, they are
results of localized new states created into the structure during synthesis or deposition
process, which are derived from structure defects [75]. Thus, to photovoltaic systems
containing SWCNTs on perovskite working as a p-type semiconductor (Fig. 15a–c),

Fig. 15 a Schematic of a MaPbI3 solar cell, using an s-SWCNT interfacial layer to extract holes.
b Fast PHT is observed from MAPbI3 to s-SWCNTs, while recombination is slow. c J–V curve
of a representative MAPbI3 solar cell with and without an s-SWCNT hole extraction layer, only
showing the fourth quadrant. Reprinted with permission from Ref. [76b]. Copyright 2017 American
Chemical Society. s-SWCNT, semiconductor single wall carbon nanotube
96 M. A. P. Almeida

Fig. 16 SEM images of (a, d) CH3 NH3 PbI3 films with CNTs, (b, e) conventional CH3 NH3 PbI3
films, and (c, f) CH3 NH3 PbI3 films with s-CNTs. g XRD patterns of pristine CNTs, s-CNTs, conven-
tional CH3 NH3 PbI3 film, CH3 NH3 PbI3 films with CNTs and s-CNTs. Reprinted with permission
from Ref. [78]. Copyright 2016 Royal Society of Chemistry

it is possible to achieve an increase of J, V oc , and FF as well as reduction of the

recombination rates and hysteresis, resulting in a gain of PCE [76].
Currently, solar cells containing structure perovskite/CNTs display PCE to values
between 10 and 20% [72a, 77]. Zhang et al. [78] have obtained perovskite solar cells
with functionalized SWCNTs (sulfonic group, s-SWCNT), which has presented great
results. In this work, it was observed an increase (from 12.50 to 15.10%) of PCE
to devices with s-CNTs. The incorporation of s-SWCNTs into perovskite increased
the crystallinity and grain size of perovskite, which was proved by XRD pattern and
SEM images, Fig. 16. The increase of crystallinity and grain size indicates that to
such structure, there is a less amount of structural defects to perovskite as well as a
reduction of the presence of grain boundaries, observations also reported at several
works [34a, 79].
The grain size is directly related to optoelectronic properties of perovskites, since,
films with little grain generally, much grain boundaries (harmful to PCE) have been
found. Such factor takes place because grain boundaries, which are from defect states,
forward to high recombination rate, which has been investigated by photoluminescent
measurement and high-resolution confocal [79b, 80].
Zhang et al. [78] in your work have displayed the importance of synthesis method
in the improvement of PCE in solar cells perovskite-based. In this work, all J–V data
to the device with s-CNTs has been presented better, with highlight to FF which pre-
sented the value of 0.75, suggesting that to such device, there is less interface defect
as well as structural defects in the perovskite, observations that are suggesting the
existence of a smaller amount of hysteresis. Thus, the control of growth to perovskite
single-crystal films is one of the key roles to improve the optoelectronic properties
in photovoltaic devices [34a, 81].
The control of morphology in the preparation of the film is also important to
improvement, which has been described by Zhang et al. [78]. Differently from Wang
et al. [82], concerning building a FTO/TiO2 /CH3 NH3 /PVSK-SWCNTs/SWCNTs-
photovoltaic system, it was described that to SWCNTs when added on the top of
peroveskite a PCE of 15.73% (Fig. 17a, b) can be achieved, which is a better alterna-
tive compared to pristine. Here, similar to the Zang et al. it took place an increase of
Recent Advances in Solar Cells 97

Fig. 17 a J–V curves of various devices. b J–V curves measured in the forward and reverse scanning
directions. Reprinted with permission from Ref. [82]. Copyright 2019 American Chemical Society

J–V data indicating that the method used (CNT bridging) results in superior charge
extraction and transferability.
The hysteresis is another factor that has worried the researcher since its presence
also contributes to the reducing of the PCE. The CNTs have also been able to reduce
hysteresis, an observation made by Wang et al. [82]. The reduction of hysteresis—
like observed here by the author indicating less structural defects and therefore little
recombination rates, which is supported by photoluminescence impedance measure-
ment. The CNT bridging method has shown effectiveness to an improved enhance-
ment of exciton separation and carrier transport as well as the superior conductivity
resulting in great stability during ninety days, results which can be considered very
promising.
As it has been previously described, the papers have shown that preparation
method to perovskite-CNTs films is an important factor to a better PCE. We can
support this affirmation when compare the Aitola’s works [77c] with Tiong’s works
[77a]. Both works have SWCNTs on the top of perovskite. Aitola et al. have added
SWCNTs via simple press transfer from method filter paper (dry method), whereas
Tiong co-works has used spin coating method are quite different, since to Aitola’s
work, a PCE reduction from 18.4% to 15% occurred, while to Tiong’s, an increase
from 9.8 to 10.1% has been observed. The key role to better PCE here is the homo-
geneity of the films. In the dry method, it is possible to obtain a regular film while to
spin coating method this is not possible, which strongly interferes in the separation
of charge process, factor important to efficiency in solar cells. To also methods, the
data to J–V curve is better when compared with control. It was also observed that
to devices with s-CNTs, a smaller hysteresis has been observed as well as a better
stability.
98 M. A. P. Almeida

3.4 Stability Issues in Inorganic Solar Cells

The first application of perovskite structure as an absorbing material was made in

2009 by Kojima et al., which for PCE, 3.8% was achieved [83]. This discovery has
been a milestone in the history of new materials for the development of photovoltaic
devices. From Kojima and co-workers until nowadays, several contributions have
been given, and currently, perovskite solar cells (PSC) have achieved an efficiency
over 22%, [20, 23b].
Although perovskite-based solar cells have been achieved PCE to 22%, stability
issues have been a big obstacle toward their commercialization as a manufactured
product. The PSC is sensitive to moisture, thermal stress, molecular oxygen, and
even long time under ultraviolet light. So, currently, great efforts have been made to
improve the stability of PSC [84].
Among several factors, one that has been influencing the stability for perovskite-
based solar cells is humidity, which makes them one of the biggest challenges to
be overcome. The moisture is very dangerous because it causes degradation of per-
ovskite as illustrated below, proposed mechanism by Walsh and co-workers to form
halide acid and organic base [85]. Therefore, it creates new methodologies that to be
able to obtain perovskite films with more stability, it becomes necessary.
In order to improve the stability of perovskite solar cell, You et al. [86] have
used a new strategy to build the perovskite-based photovoltaic device, Fig. 18a. In
this new approach of the device, metal oxides were used to protect the perovskite
thin film. To this new structure (ITO/NiOx /perovskite/ZnO/Al), which NiOx to work
as p-type (HTML) and ZnO as n-type (ETML), an efficiency of 16.1% has been
achieved and after a 60 day (1440 h) storage in air at room temperature, a loss of
only 10% in PCE took place. In this new design, NiOx and ZnO beyond work as
HTML and ETML also act to prevent the perovskite structure to moisture, which
avoids its degradation, which are encouraging results. Other works reported [87]
also forward to results similar described by You and colleagues. For example, Zang

Fig. 18 a J–V curves for ITO/NiOx (80 nm)/perovskite/ZnO(70 nm)/Al stored in ambient air for
several days. b Stability of the devices in an ambient environment (30–50% humidity, T = 298.15 K).
Reprinted with permission from Ref. [86]. Copyright 2015 Springer Nature
Recent Advances in Solar Cells 99

et al. [88] have described a perovskite structured ZnO-based device. The results are
too clear concerning the effect that the zinc oxide has in both, acting as ETM and
protecting the perovskite structure, which after 90 (2160 h) days it is still possible to
have 88.7% of PCE.
Among metals oxides used to encapsulant perovskite structure, aluminum oxide
also has stood out. Choi et al. [89] using the atomic deposition layer method, obtained
a perovskita-based photovoltaic device encapsulated with Al2 O3 . To this device,
excellent durability (Fig. 19a) to PCE was achieved, which is attributed to the capacity
of Al2 O3 to prevent moisture in the perovskite structure. In this same approach, Wu
et al. [90] have obtained a better result using a bismuth interlayer in their device.
Besides, an improvement to PCE (18.02%) has been achieved and after 500 h stored
at ambient air in the dark 95–97% of their initial PCE. As displayed in Fig. 19b–c, the
bismuth oxide prevents the entrance of water and molecular oxygen in the perovskite
structure resulting in the low rate of degradation of the device.
Another strategy that has shown great results in stability of perovskite-based solar
cells is used to doping of metals ions [91]. Depending on metal ion and oxidation
state, the chemical bonds can be stronger enough and therefore to a more stable
structure. For example, Chan et al. have called attention to the potential that the
alkaline-earth metal cations (Ba2+ , Ca2+ , Sr2+ , and Ba2+ ) can offer in the replacement
of lead in perovskite-based photovoltaic devices [91b]. In this work, it was obtained
a perovskite structure doping with metal cations from two groups of the periodic
with highlight to barium.
To Ba2+ doped (3.0 mol%) perovskite device, it was observed an increase of PCE
from 11.8 to 14.9% when compared with pristine perovskite, which results from
better J–V curve parameter (J sc , V oc , and FF). The best of all is that besides the
improvement, a better stability in control atmosphere (N2 with H2 O, 0.1 ppm) has
been achieved to this device with 3% mol% Ba2+ , Fig. 20a. The Cs+ doping in the
perovskite structure has been another great alternative to improve stability. Zhang
et al. [91d] have observed that the replacement of organic cations by Cs+ (5%)
improved the stability of the device, observations also made by Saliba et al. [92].
These results suggest in the perovskite structure to form a stronger bond justifying a
better stability under humidity.
Although it has been reported some inorganic materials with the potential to pre-
vent moisture in the perovskite structure, organic materials are also related to such
proposal, which are greatly described by Yang et al. [93]. Yang and co-works have
described the importance that organic polymers can act to functionalization of per-
ovskite thin films and thus prevent the moisture. With this new approach to build
perovskite thin films to solar cells, they also have achieved successful functional-
izing ammonium salts (tetra-methyl ammonium, hexadecyl trimethyl ammonium,
tetra-ethyl ammonium, tetra-butyl ammonium, and tetra-hexyl ammonium) on top
of perovskite film, which after stored in 55% relative humidity (in the dark) shown
to be stable for 500 when compared with the unfunctionalized. This ammonium
salts are low soluble in water, justifying its action to prevent water, with highlight to
tetra-ethyl ammonium (Fig. 21).
100 M. A. P. Almeida

Fig. 19 a PCE’s of full mesoporous (FAPbI3 )0.85 (MAPbBr3 )0.15 /HTM/Au/50 nm Al2 O3 PSCs
during storage at room temperature (dark) in 50% RH for 7500 h (~10 months).
Reprinted with permission from Ref. [89]. Copyright 2018 Elsevier. b Stability tests
to FTO/NiMgLiO/PVK/PCBM/BCP/Bi/Ag devices. Reprinted with permission from Ref.
[90]. Copyright 2019 Springer Nature. c Schematic diagram to: the device structure type
FTO/NiMgLiO/PVK/PCBM/BCP/Bi/Ag; energy level diagram; SEM cross-sectional image of the
device (scale bar: 500 nm); J–V curves of a typical large-area. Reprinted with permission from Ref.
[90]. Copyright 2019 Springer Nature

Using the same previous methodology, Meng et al. [94] also have obtained great
results of the stability of perovskite-based devices. In this work, Meng and colleagues
have shown the potential that the 1-dodecyl mercaptan (NDM) has to modify the
interface between perovskite and hole transport layer (HTML) and prevent water into
perovskite. For such device (with NDM), it was possible to achieve an improvement
to PCE (15.04%) when compared with the pristine (without NDM, PCE 12.75%) and
a better stability after stored in air at room temperature over 2400 h. Several other
Recent Advances in Solar Cells 101

Fig. 20 a Stability of PSCs with the pristine and 3.0 mol% Ba2+ -doped perovskite films when
stored the glovebox system with the integrated gas purification system. Reprinted with permission
from Ref. [91b]. Copyright 2017 Royal Society Chemistry. b Long-term stability measurements of
both solar cell without any encapsulation under ambient conditions where the relative humidity is
30% RH. Reprinted with permission from Ref. [91d]. Copyright 2017 Royal Society Chemistry

Fig. 21 a J–V curves with reverse and forward scans for typical PSC devices based on MA, TMA,
and TEA films. b Evolution of the normalized photovoltaic parameters of unsealed devices which
were stored in 55 5% relative humidity and dark conditions. Reprinted with permission from Ref.
[93]. Copyright 2016 Springer Nature

works have also called attention to the potential that organic molecules have to prevent
water when they are supported on top of perovskite films. Such assumption suggests
that the size [93, 95] (Fig. 23) of the organic molecule, as well as low solubility
in water, are pre-requisites for a great design of a structure moisture-tolerant and
therefore provide an improvement of stability (Fig. 22).
102 M. A. P. Almeida

Fig. 22 a Schematic structure of a PSC, modified by NDM molecules on the interface of MAPbI3
and an HTL. Schematic structure for the surface of pristine MAPbI3 and MAPbI3 anchored with
NDM. b Current-voltage curves of the best PSCs using pristine MAPbI3 (orange curve) and NDM-
anchored MAPbI3 (blue curve). c Time evolution of the efficiency for the two different devices stored
in air at room temperature out of the sun. Reprinted with permission from Ref. [94]. Copyright 2019
American Chemical Society

4 Organic Solar Cells

It is well known that OSC is a junction between two-organic molecular structure, one
electron donor and another electron acceptor (Fig. 24) so-called n–p heterojunction
as illustrated in Fig. 25a–c. Though inorganic-based materials, photovoltaic devices
have exhibited great results (PCE > 22% [25]), organic solar cells (OSCs) since their
discovery in 1986 by Tang [96] with PCE of ~1%, great efforts [97] have been made
by researchers in the last decades, and currently, a record PCE of 14% has been
achieved by Zhang et al. [97a]. For organic molecules used in OSCs, depending on
the molecular weight, they can be classified into conjugated polymers (high molec-
ular weight compound with repeating units in the polymer chain), oligomer (low
molecular weight compound with repeating units), and small molecules, which are
considered low molecular compounds without repeating units.
For the first proposal of OSC (by Tang), it was presented a donor–acceptor bilayer
structure wherein the electron acceptor material was coated on donor material. In
this photovoltaic device, donor material is responsible for absorbing the light and
exciting the electrons from highest occupied molecular orbital (HOMO) to lowest
unoccupied molecular orbital (LUMO) of the donor material, and such electrons
Recent Advances in Solar Cells 103

Fig. 23 a Molecular structure of β-cyclodextrin. b Schematic diagram to show the interactions

between the perovskite and β-cyclodextrin molecules. c Schematic diagram to show the mechanisms
of the degradation process of the pristine perovskite. d The water-resistant property of the perovskite
with β-CD. Reprinted with permission from Ref. [95a]. Copyright 2019 Royal Society Chemistry

follow LUMO of the accept material as illustrated in Fig. 25d. Moreover, there are
other two configurations to OSC, one which the donor and acceptor materials are
mixed to form a junction in a single layer, which is known as the bulk-heterojunction
(BHJ) configuration, and another wherein the position of the electrodes are inverted,
a concept this introduced by Glatthar et al. [99]. In this last configuration, there is a
change in the position of the electrodes (e.g., ITO or the FTO), so these act as the
cathode and the high work function metal acts as the anode, as well as the polarity
of charge collection also is inverted.
104 M. A. P. Almeida

Fig. 24 a Chemical structures of the fullerenes. b Chemical structure of some conjugated polymers
used in OSCs. Reprinted with permission from Ref. [98]

Fig. 25 a Conventional device structure to BHJ OSCs. b Inverted structure device to BHJ OSCs.
Reprinted with permission from Ref. [100]. Copyright 2017 Elsevier. c Structure bilayer to OSCs
proposes by Tag. d Principle of working to conventional OSCs. c BHJ OSCs

4.1 Main Electron Donor/Acceptor Molecules Used in OSCs

Among OSCs, BHJ is one of the most studied configurations in the last years
[101]. For this model, which consists of electron donor/acceptor blend system,
π -conjugated polymers are used as electron donor materials, which can highlight
poly(3-hexylthiophene), so-called P3HT, among others [102]. A typical structure
scheme of the bilayer OSCs is P3HT (or analogous) as donor mater and [6,6]-phenyl-
C61 -butyric acid methyl ester (PC70 MB) or analogous as the electron acceptor. For
this structure of the OSCs, PCE over 5% [103] has been achieved, but many efforts
aiming at improving the performance of BHJ solar cell devices have been made. For
Recent Advances in Solar Cells 105

polymers act as an electron donor, it is necessary that it presents absorption in the

visible range, since this ensures a better absorption of photons in the visible range.
Currently, the challenge for improving in OSCs is to develop donor materials
(polymers) with high absorption on the visible range, which implicates in obtaining
low bandgap π -conjugated polymers with reasonable energy levels able to harvest
more photons from solar light [104]. For these materials besides having a low bandgap
(between 1.2 and 1.9 eV), it is also required that the energy level HOMO to be −
5.2 and −5.8 eV while for LUMO energy level −3.7 and −4.0 eV is required [105].
This last condition is directly related to the alignment between HOMO and LUMO
of electron acceptor, which improves the carrier charges and so enhances the PCE
value.
Although P3HT is ordinarily used as donor material, other polymers like
PCPDTBT [106], PCDTBT [106a, 107], PTB7 [108], and DPPTT [109], which
present absorption in visible, have been presented as an alternative of electron donor
exhibiting PCE similar or better than P3HT when combined with electron acceptor
(fullerene or no-fullerene). Bin et al. [110] knowing the importance of absorption of
visible spectral to organic molecules to the improvement of PCE in OSCs studied the
influence of the replacements of thiophene conjugated side chain of the benzodithio-
phene (BDT) for different branched alkyl (Fig. 26) in the photovoltaic performance
of OSCs. For simple replacement of the 2-iso-octyl (J52) by alkylthio ramification
(J60), alkylthio linear (J61), and tri-N-proprylsilane (J71), it was observed a change
in the profile in the absorption spectra, which resulted in a narrowing of the bandgap.
As illustrated in Fig. 27, the absorption spectrum to J60 and J61 is similar, but
a red-shift was exhibited when compared with J52. This suggests that the groups
added are strong electron donors favoring the electronic transitions in low energy.
Thus, the improvement of the absorption in the visible range to these molecules and
its use as an electron donor in OSCs resulted in an increase of PCE (from 5.51 to
11.20%, Table 1). The work of the Bin and collaborators shows the following to the
engineering of donor molecules able to obtain of OSCs of high performance: Here,
it is important to highlight that although the absorption of the donor is improved, the
HOMO and LUMO of donor/acceptor must have the max of alignment, a condition
necessary to charge carrier.
Xu et al. [111] use the concept of the composite to prepare new donor materials
to solar cells. Herein, we see the importance of synergism as well as the visible light
absorption of the composite to improve the performance of the OSC. With an adding
of PTB7-Th weight ratios, it rises a new band at 750 nm. For device optimized
(ratio 0.7), it was found a PCE of 12.27%, while that to content 0.0 and 1.0, the
PCE was 9.39 and 10.10%. Fei et al. [112] found PCE value slowly higher than it
was found by Xu et al., but to a different donor/acceptor system. In this system, it
was used the PFBDB-T/C8-ITIC-based cell, which presented PCE of 13.2%. For this
great performance, the authors attributed the replacement of hydrogen in PBDB-T by
fluorine. This substitution is responsible for the shift of the absorption band to more
wavelength, which results in a narrowing of the bandgap, and thus more absorption
in the visible range.
106 M. A. P. Almeida

Fig. 26 Chemical structure of the copolymer. Reprinted with permission from [110a]. Copyright
2016 American Chemical Society

Fig. 27 a Absorption
spectra of the donor
polymers in film states.
Reprinted with permission
from Ref. [110a]. Copyright
2016 American Chemical
Society
Recent Advances in Solar Cells 107

Table 1 Properties of the copolymers

Copolymers λmax λedge Eg V oc J sc FF (%) PCE
(nm) (nm) (eV) (V) (mA/cm2 ) (%)
J52 538, 630 1.96 0.73 13.11 0.57 5.51
590
J60 550, 642 1.93 0.91 16.33 0.60 8.97
598
J61 552, 642 1.93 0.89 17.43 0.61 9.53
600
J71 528, 632 1.59 0.94 17.40 0.68 11.20
573

Although the results presented above are good, recently, Zhang et al. [97a] have
presented a new design of OSCs using PBDB-T-2Cl as a donor material. Unlike
Xu and collaborators, the hydrogen was replaced by chloride instead of fluorine.
For the device containing PBDB-T-2Cl, it was found a PCE of 14.4%, which was
addressed to lower HOMO and LUMO levels of the chlorinated polymer when com-
pared with a fluorinated polymer. Furthermore, when it was made a comparison
of stability between two donor polymers, the device with PBDB-T-2Cl presented a
better stability.
So far, we have described only to electron donor, but it is known that the electron
acceptor also has its importance in the process of manufacturing of OSCs. Although
in order to be building an ideal organic donor material, the choice of the acceptor
pair to the flow of the hole is important, and this is only possible if its HOMO
and LUMO present a good alignment with donor material, since these conditions
toward to increase the V oc and therefore improve PCE, Fig. 28a. Following this
pathway, in the literature, there are a huge number of options to acceptor material in
OSCs, which generally are classified into two big groups, fullerene and non-fullerene
acceptor groups [98, 113]. Furthermore, non-fullerene acceptors can be divided into
two categories: (1) small molecules [113d, 114] and (2) polymer acceptors [115].
In the last decades, fullerene-based acceptors have been widely used in OSCs,
which PCE values found to these solar cells are from 1 to 10% [116]. For
example, Kim et al. [117] obtained fullerene-based OSCs PPDT2FBT/PC71 BM
(donor/acceptor), which presented PCE of 8.16%. However, concerning the same
device, it was added another donor material (mix PPDT2FBT:IDT2BR), and the PCE
value was increased to 9.02%. Herein, the improvement of PCE can be addressed
to a better alignment of the HOMO/LUMO of donor material with HOMO/LUMO
of the acceptor, PC71 BM. Zhao et al. [118] showed that to fullerene-based OSCs,
the choice of solvent influences the improvement of PCE. In this work, the authors
addressed the improvement of PCE (11.7%) to the synergistic effect of solvents 1,2,4-
trimethylbenzene (TMB) and 1-phenylnaphthalene (PN) in the solar cell, which acted
directly in the morphology control. When making the comparison between the two
devices without (TMB) and with a solvent mix (TMB-PIN), it was observed an
increase to all photovoltaic parameters with highlight to V oc . The increase of V oc
108 M. A. P. Almeida

Fig. 28 a Simple energy diagram of a donor/acceptor interface showing the HOMO and LUMO
energy offsets (HOMOs and LUMOs ). b Example of a device configuration, with a depiction of
idealized morphology of the donor/acceptor active layer. c Most commonly used electron acceptors
in solution processable bulk heterojunctions: [6,6]-phenyl-C61 -butyric acid methyl ester (PC61 BM)
and [6,6]-phenyl-C71 -butyric acid methyl ester (PC71 BM). Reprinted with permission from Ref.
[114a]. Copyright 2015 American Chemical Society

and J sc in the device indicates a better alignment between HOMO and LUMO of
donor/acceptor blend and more absorption of the visible spectrum, resulting in great
PCE.
Currently, it is known that to fullerene-based OSCs, poor light absorp-
tion, limited chemical, energetic tunability, high cost, and instability morpho-
logic are issues that hinder practical applications of fullerenes acceptors in
OSCs. Thus, the researchers have been devoted to developing non-fullerene
electron acceptors, which the PCE values are from 1 to 16% [113a, 113d,
114c, 116b, 119]. For example, in 2016, Zhao et al. [119a] showed that
it is possible to obtain non-fullerene OSCs of high performance. For this
device, it was used the 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-
5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2 ,3 -d ]-s-indaceno[1,2-b:5,6 b ]
dithiophene) (ITIC) as acceptor, which presented a PCE of 11.21%. The results
exhibited by Zhao and co-work agree with article reported by Li et al. [114c], which
used an analogous acceptor (IT-M) in their device, resulting in a performance of
12.05%.
Currently, the best results of non-fullerene-based OSCs were reported by Li et al.
[120b] and Cui et al. [116b], which displayed PCE of 13.9 and 15.08%, respectively,
Fig. 29. The new PCE values found are very positive in scientific communities, since
such values were recently achieved only in inorganic-based solar cells.
Recent Advances in Solar Cells 109

Fig. 29 a Chemical structure of the IT-4F acceptor. b J–V of the P2:IT-4F-based blend cell.
Reprinted with permission from Ref. [119b]. Copyright 2018 American Chemical Society. c Chem-
ical structure of the acceptor BTP-4Cl used in OSCs. d J–V curve of the PBDB-TF:BTP-4F blend
cell. Reprinted with permission from Ref. [116b]. Copyright 2019 Springer Nature

Among the wide number of electron acceptors used in OSCs, the 2,2 -
[[6,6,12,12-Tetrakis(4-hexylphenyl)-6,12-dihydrodithieno [2,3-d:2 ,3 -d ]-s-

indaceno[1,2-b:5,6-b ]dithiophene-2,8-diyl]bis[methylidyne(3-oxo-1H-indene-
2,1(3H)diylidene)]] bis[propanedinitrile] (so-called ITIC) and its derivates have
been widely used in organic-based photovoltaic blends [120]. Its potential as an
acceptor to the improvement of PCE depends on the substituted groups in structure
(Fig. 30), as it showed by Yang et al. [121]. With a great optimization in the ITIC
structure, the charge carrier can be improved, which is observed by an increase of
V oc and J sc resulting in high performance of the OSCs.
For example, Zhao et al. [122] showed that to ITIC when four hydrogen atoms
are substituted by fluorine atoms (IT-4F), the performance in the device increases
from 11.05 to 13.1%. Comparing the photovoltaic parameters of two devices (PBDB-
T:ITIC vs. PBDB-T-SF:IT-4F), though after adding of fluorine in both, donor polymer
and acceptor material, it has taken a reduction of V oc (from 0.90 to 0.88 eV), J sc
increased from 17.02 to 20.88 eV, which means a better absorption of visible spec-
trum, data which is supported by the absorption spectra, since the PBDB-T-SF:IT-4F
110 M. A. P. Almeida

Fig. 30 a Nonfullerene structure acceptor materials. Reprinted with permission from Ref. [121].
Copyright 2019 Royal Society of Chemical. b Molecular structure of the fluorinated donor and
acceptor. c J–V curve of PBDB-T-SF:IT-4F blend used at the photovoltaic device. Reprinted with
permission from Ref. [122]. Copyright 2017 American Chemical Society

blend presents a shift-red. As shown above, IT-4F depending on substituents in both,

donor and acceptor, an improvement of PCE can be achieved. Li et al. [119b] using
different polymer (PDTB-EF-T) obtained PCE of 14.2%. However, though the results
presented above are great, it was Cui et al. [116b] who has presented BJH OSCs with
excellent performance to PBDB-TF:BTP-4Cl blend with PCE of 16.5%. Cui and
co-worker showed that the replacing of the fluorine atoms by chlorine in the accep-
tor could increase photovoltaic parameters (V oc , J sc , and FF), resulting in higher
PCE. Such replacement is responsible to exhibit an extended optical absorption and
meanwhile displays a higher voltage when compared with PBDB-TF:BTP-4F.

5 Tandem Solar Cells

Both inorganic and organic solar cells have achieved excellent PCE values, as pre-
viously described. The efficiency of a solar cell depends on the bandgap energy of
the semiconductor since the spectrum of sunlight has a wide variety of wavelength
(Fig. 31), from infrared (lower energy) to ultraviolet, higher energy. Thus, for single-
junction solar cells (a particular bandgap), only a little wavelength range of solar
spectrum can be used, which limits the performance of the photovoltaic device.
According to Shockley and Queisser, for inorganic single-junction solar cells,
PCE value under non-concentrated air mass 1.5 global (AM1.5G) sunlight can reach a
Recent Advances in Solar Cells 111

Fig. 31 Schematic structure

of the tandem organic solar
cell. Reprinted with
permission from Ref. [123].
Copyright 2009 Royal
Society of Chemistry

maximum value of ∼33% with the bandgap between 1.1 and 1.4 eV [124]. Shockley–
Queisser limitation can be overcome when the concept of multi-junction solar cells
are employed. Solar cells tandem are known as a photovoltaic systems composed
by stacking of the solar cells with different bandgaps. This configurates a better
absorption of energy in the visible spectrum Fig. 32 and therefore improves the
performance. Theoretical calculus made by De Vos et al. [125] described that for

Fig. 32 Standard solar spectra for space and terrestrial use. Reprinted from Ref. [126]. Copyright
@ PVeducation
112 M. A. P. Almeida

two inorganic subcells, the performance of the photovoltaic device could rise up to
42% with bandgap of 1.9 and 1.0 eV, respectively, while to three inorganic subcells
having a bandgap of 2.3, 1.4, and 0.8 eV, a PCE of 49% can be achieved.
The use of the concept of a tandem for the organic system requires solving two
well-known problems in the designer of organic photovoltaic devices: (1) poor charge
carrier mobility and (2) low light absorption in the visible spectrum, which can be
overcome by using a combination of different materials, donor–acceptor composite,
which can increase the absorption of visible range as described by Xue et al. [127] and
Ameri et al. [123]. Thus, through the tandem system, the performance is improved
because thermalization losses of high-energy photons are reduced by conversion in
the subcell with a wide bandgap and transmission losses are lowered by absorption
of the low energy photons in the subcell with a small bandgap [128].
Currently, silicon-based solar cells, which are widely used around the world,
present PCE between 25 and 26% [129]. As already described, the best PCE values
for inorganic and organic single-solar cells are reported to 14.3% [98a] and 23.7%
[25, 130], respectively. For multi-junctions, both inorganic and organic, performance
values have already been overcome. For example, Werner et al. [131] already obtained
in 2016 a perovskite-based tandem solar cell with PCE of 21.2%. This PCE value is
the same photovoltaic which has been overcome by Bush et al. [132] and Jost et al.
[129], which achieved PCE values of 23.6% and 25.5%, respectively.
By comparing single and multi-junction of perovskite-based solar cells, there
was an increase in PCE of 1.8% when compared with the value found by Li and co-
workers [25]. Although the increase is small, in this model of multi-junction, there
is a stability gain about the other perovskite-based photovoltaic devices. Besides,
when compared with silicon-based solar cells, it looks that perovskite-based solar
cells will achieve the max of performance within a few years, and solving the issues
of stability, such technologies (cheaper than silicon technologies) will be able to
manufacture in large scale and therefore commercialized.
For organic-based multi-junctions, Meng et al. [133] have exhibited a new model
of multi-junction for a two-terminal monolithic solution-processed tandem. In this
design of solar cell, a PCE value of 17.3% was achieved, which is currently a record
value with 2.9% more than the PCE found by Zhang and co-workers [97a], 14.4%.
Making a comparison of multi-junction made by Meng and co-workers with single-
junction made by Zang and co-workers took place a reduction of J sc (14.21 V) and
FF (0.72%), but V oc was increased to 1.63 V, which means that took place an increase
in charge carries, therefore improving the performance of device.
The results above described to tandem solar cells are great, but there are better
results to GaInP/GaAs//Si-based tandem solar cells with values from 27.9% (over
silicon-based) to 35.9% reported by Yamaguchi et al. [15a]. For example, Cariou
et al. [134] in 2017 related a triple-junction tandem solar cell with 30.2% under 1-sun
AM1.5g. Although these results are promising, Essig et al. [135] have shown some
improvement for monolithic two-terminal III–V//Si tandem solar cell, which reached
an excellent PCE of 35.8%. As it previously showed, the PCE values for tandem solar
cells are much higher than other photovoltaic systems, but due to issues of growth
Recent Advances in Solar Cells 113

Fig. 33 a Design of the four-terminal GaInP/GaAs//Si triple-junction solar cell. b NREL-certified

J–V characteristics of the GaInP/GaAs top cell and the Si bottom cell when illuminated under
AM1.5g spectral conditions at 25 C. The bottom-cell J–V curve was measured while the top III–V
tandem cell was biased at its maximum power point. Reprinted with permission from Ref. [135].
Copyright 2017 Springer Nature

techniques, such photovoltaic systems are more expensive than silicon-based solar
cells and therefore they are valid for large-scale production (Fig. 33).

6 Conclusion

In summary, here we showed that photovoltaic technologies, which already are used
all over the world, have a big grown potential, which depends on research advance.
The OSCs in a short time have presented an expressive increase in PCE. The OSC
devices have attracted attention due to being lighter, more flexible, and present a
low manufacturing cost. The limitation for OSCs is directly related to issues of poor
charge mobility and low absorption in the visible range. Another option to reduce the
cost of producing solar cells is that an option to replace silicon-based technologies
is perovskite-based solar cells. The PCE for these solar cells is almost ready at the
silicon technologies, but issues of stability (also for OSCs) are still challenging to
be overcome and so make them available for large-scale production. Finally, tandem
solar cells are currently photovoltaic technologies that present a better performance,
but the high cost in the manufacturing process makes it more expensive than silicon
technologies, which makes it currently impracticable for commercial applications.
Thus, we have tried to show the last advances in inorganic and organic solar cells
aiming to improve performance.
114 M. A. P. Almeida

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Photovoltaic Materials Design
by Computational Studies: Metal Sulfides

Edan Bainglass, Sajib K. Barman and Muhammad N. Huda

Abstract Materials design for the next generation of solar cell technologies requires
an efficient and cost-effective research approach to supplement experimental efforts.
Computational research offers a theoretical guide by applying cutting edge method-
ologies to the study of electronic structures of newly predicted materials. In this
chapter, we present our recent research efforts on sulfides. First, we will also pro-
vide a brief overview of oxide-based photovoltaic materials. We have conducted a
density functional theory (DFT) study of two sulfide systems: acanthite Cu2 S and
S-doped triclinic CuBiW2 O8 . With these two systems, we will demonstrate both the
cation and anion doping mechanisms. In Cu2 S, we investigate the effects of various
cation doping in Cu sites, namely Zn, Sn, Bi, Nb, and Ta and contrast their electronic
structures with that of a previously studied Ag-doped Cu2 S system. A subsequent
charge analysis provides a correlation between dopant charge states and detrimental
mid-gap trap state concentrations. We then present our best dopant choice for Cu2 S-
based photovoltaic systems. Finally, for CuBiW2 O8 , a new experimentally verified
DFT-predicted quaternary oxide, the effects of S-anion-doping in O sites are studied,
and results indicate favorable photovoltaic properties. This highlights the potential
of S-anion-doping as a mechanism for engineering suitable band gaps for solar cell
applications.

Keywords DFT · Doping · Alloying · Cu2 S · CuBiW2 O8

1 Introduction

Highly efficient, yet cost-effective, materials suitable for solar-to-electric energy con-
version applications remain both elusive and in great demand, as continued depen-
dence on fossil fuel risks the health of both the environment and the global population
[1–3], and hence, the energy independence becomes a necessity beyond the economic
aspect. Photovoltaic technology is well-established as one of the most viable can-
didates for tackling future energy demands. However, the challenge of designing

E. Bainglass · S. K. Barman · M. N. Huda (B)

Department of Physics, The University of Texas at Arlington, Arlington, TX 76019, USA
e-mail: [email protected]
© Springer Nature Switzerland AG 2020 123
S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_5
124 E. Bainglass et al.

new materials that can meet the host of properties required for efficient solar power
conversion is a formidable one. Extensive research has been conducted over the
decades in this pursuit, and though advances have been made, photovoltaic technol-
ogy contributes less than 5% of the electric grid [4]. In part, this is due to the balance
required between high efficiency and cost-effectiveness. New materials must be sta-
ble and reliable, earth-abundant, environmentally safe, and inexpensively scalable to
meet global demands. To achieve the cost requirement, device efficiencies must be
improved beyond the current state. Power conversion efficiencies of commercially
available Si-based solar cells, for example, range from 18 to 22% [5]. Devices that
surpass this efficiency tend to rely either on novel designs [6, 7], rare components,
isolated conditions, or all of the above, and exist outside of any commercial markets.
Other designs utilize inexpensive and abundant components but suffer from efficien-
cies too low for global scalability. Hence, additional research must be conducted
to obtain a better understanding of material properties in hopes of increasing the
utilization of solar energy.
Traditionally, scientific breakthroughs in material science and engineering have
been achieved primarily through experimental efforts. However, as computational
resources became increasingly available, a significant theoretical effort has pushed
for deeper investigations of the physical and chemical inner workings of materials [8,
9]. Today, computational studies are a common and often essential component of new
materials research. They offer a cost-effective and efficient method for large-scale
materials design and study and have produced many new materials, as evident in
crystallographic databases such as the Inorganic Crystal Structure Database (ICSD)
or the Materials Project [10]. In the following sections, we briefly give an overview
of oxides and sulfides, two promising material groups at the frontier of photovoltaic
materials research. We highlight the inherent difficulties and challenges of metal
oxides in solar energy conversion applications and introduce sulfides as a promis-
ing alternative. Lastly, we present a computational investigation of the electronic
properties of Cu2 S, a pure metal sulfide, and a study of the effects of S-doping in
CuBiW2 O8 , a recently discovered novel quaternary oxide.

2 Metal Oxides

Many aspects of PV devices incorporate metal oxide compounds, from transparent

conductive layers, to transport barrier layers and photoactive light-harvesting layers.
Oxides have been utilized in solar cells as insulators, semiconductors, and conductors
due to their large range of conductivities [11]. They are non-toxic and abundant
in nature due to their ability to form stable chemical bonds with most elements
[12]. Many structural flavors of oxides exist including non-crystalline amorphous
forms. This overall flexibility is highlighted in the emerging all-oxide solar cell field
[13]. Of the various oxide materials, transition metal oxides are especially suited
for PV applications. Their partially filled d-orbital character yields properties both
unique and complex. Many binary transition metal oxides exhibit band gap energies
Photovoltaic Materials Design by Computational Studies … 125

larger than that of silicon (1.12 eV) and have thus been considered for transparent
conducting layers (TCO) [14–16]. However, the requirement of both a wide gap and
high conductivity is often at odds due to the band gap property.
Much research has gone into the effects of dopants on the properties of transition
metal oxides in attempt to tailor suitable band gaps. Most doped oxides in solar cells
are n-type materials, especially for TCOs [17], due to intrinsic oxygen vacancies, and
exhibit high electron mobilities due to strong metal–oxygen orbital overlap [18]. In
contrast, highly electronegative O 2p states mixed with localized 3d states at oxide
valence band maxima (VBM) hinder shallow acceptor states required for p-type
doping and tend to instead result in large hole effective masses [19–21]. In some cases,
such as Cu2 O, this challenge is resolved due to the proximity of Cu 3d and O 2p energy
levels and intrinsic Cu1+ vacancies. Additionally, the ns2 electronic configuration,
e.g., Bi3+ , has shown the presence of anti-bonding states at the VBM, which, through
hybridization with O 2p states, can lead to reduced effective masses and higher
hole mobilities [22]. This is analogous to the chemical modulation technique [23]
of O 2p—Cu 3d VBM hybridization, which has yielded dispersive valence bands
in Cu(I) ternary oxides. The technique has since been extended to the chalcogen
group, as Cu 3d orbitals hybridize better with S, Se, and Te p orbitals [24, 25].
Cu2 O has also been utilized as a light-absorbing layer due to its 1.4–2.2 eV band
gap [26] resulting in power conversion efficiencies of ~8% [27]. According to the
Shockley–Queisser detailed balance limit [28], the band gap of Cu2 O can, at best,
reach a ~22% theoretical conversion efficiency. On the other hand, cuprous oxide
(CuO) has a theoretical efficiency limit of ~31% owing to its 1.4 eV band gap [29].
However, CuO has yielded poor efficiency thus far, which has been attributed to
high defect concentration or interface recombination [30, 31]. Some improvements
to CuO efficiencies were found in the nanoscale, reaching an efficiency of 2.88%
[32].
To enhance the efficiencies of Cu-based oxides, we must pay careful attention to
the challenges inherent in the oxide group. Oxides tend to be wide-gap semiconduc-
tors due to the high electronegativity of oxygen. Furthermore, 3d transition metal
oxides suffer from greater localization at the band edges which generally results
in large carrier effective masses. Thus, a study of different anion species may be
required. Several of these have been studied in the scope of solar fuel generation,
including the nitride and sulfide groups, as well as Se (CIG(S, Se)) and Te (CdTe).
Theoretically, the reduced electronegativity of these species with respect to oxygen
is expected to upshift the VBM, thus providing a mechanism for band gap engineer-
ing. And, as previously mentioned, Cu 3d tends to hybridize more strongly with the
chalcogen group, which may lead to lower effective masses at the band edges. These
are desirable properties for efficient solar energy conversion.
126 E. Bainglass et al.

3 Sulfides

Cu-chalcogenides are well-known energy harvesting materials, especially in photo-

voltaic applications. These materials are composed of Cu1+ cations and chalcogen
anions such as S, Se, and Te. Chalcogenides may also include other cations along with
Cu from groups IIB, IIIA, IVA, and VA. Such compounds include Cu (In, Ga) (S, Se)2
and Cu2 ZnSn(S, Se)4 or CIG (S, Se) and CZT(S, Se), respectively, both regarded as
prominent solar cell absorbers. Apart from these complex multinary compounds, the
binary Cu-chalcogenide Cu2 S has also been found to be a promising solar absorber
due to its suitable band gap of 1.2 eV. Of these, a CIGS-based solar cell was found
to be superior due to its high solar conversion efficiency of nearly 20%, which was
first reported by NREL [33]. Several other materials have shown similar efficien-
cies, including Si, GaAs, CdTe, and the perovskite group. However, Ga, In, Cd, and
Te are relatively scarce and very expensive. Even though Si-based technologies are
widespread around the globe, pure grade Si is not cost-effective nowadays and thus
unsuitable to meet the global solar energy demand. In contrast, CZTS- and Cu2 S-
based solar cells, with reported solar-to-light conversion efficiencies of 12.6% [34]
and nearly 10% [35], respectively, can be cost-effective alternatives in this respect due
to the abundance of Cu, Zn, and Sn in Earth’s crust and their eco-friendly, non-toxic
nature.
To meet future energy demands and replace fossil fuel with cost-effective alter-
natives, thin film-based solar cells are so far the best candidate since they require
less material and provide a pathway to go beyond the established Si-based solar
cell technology [36, 37]. However, both CZTS and Cu2 S suffer from some intrinsic
drawbacks which require careful attention and proper study to develop the nec-
essary solutions. Defect-free synthesis of CZTS is rather challenging. Due to the
similar ionic radii and tetrahedral coordination of Cu and Zn, the cations may swap
their lattice sites with relative ease. In addition, annealing multinary compounds at
high temperatures during synthesis results in defects to the crystal and electronic
structures, which would eventually impact device activity [38]. In an earlier study,
we have shown from thermodynamic considerations that defects would destabilize
single-phase stability of CZTS [39]. Although Ba-substitution in Zn sites, leading to
the chalcogenide family BaCu2 SnSex S4−x (BCT (S, Se)), provides a mechanism for
controlling the coordination environment, the resulting conversion efficiency is well
below expectation [40]. As a counterpart to multinary complex chalcogens, Cu2 S
suffers from intrinsic p-type defects due to spontaneous Cu vacancy formations in
the crystal. Hence, the performance of Cu2 S-based thin-film solar cells degrades in
air over time. Careful crystal stability and electronic structure studies, along with
possible doping effects on this material, may shine light on the prospect of their
photovoltaic uses in the near future.
Photovoltaic Materials Design by Computational Studies … 127

4 Case Studies

The density functional theory (DFT) is the state-of-the art tool for calculating elec-
tronic structures of materials. DFT methodology shifts the quantity of interest in
electronic calculations from the complex wave function to the electronic density
scalar. It establishes a one-to-one correlation between the two quantities and defines
an energy functional of the latter. The energy functional can then be variationally
minimized under constraint leading to the ground-state density of the system. With
this quantity in hand, and via the one-to-one correlation with the wave function, all
ground-state properties of the system are now obtainable. The mathematical rigor of
the theory is encapsulated in the Hohenberg–Kohn theorems [41]. Applications of it
involve iterative solutions of the so-called Kohn–Sham equations [42], a set of one-
electron Schrödinger-like equations describing a fictitious non-interacting system
that, by construction, leads to the same ground-state density as the real, interacting
system of interest. The theory has seen tremendous growth over the past 50 years and
has since become a staple in the study of electronic structures of materials [43–47].
One of its many successes is the reproducibility of experimental results [48].
In the following subsections, we discuss results from two separate DFT studies
of Cu(I) systems with a focus on photovoltaic properties. First, we address the prop-
erties of sulfides by studying the effects of doping on the relatively new acanthite
phase of Cu2 S. Then, we present a study of the effects of S-doping on the novel
CuBiW2 O8 quaternary oxide, dubbed CBTO. In both studies, the generalized gra-
dient approximation of Perdew–Burke–Ernzerhof (GGA-PBE) [49, 50] was used
to model exchange-correlation effects. The Kohn–Sham equations were solved in
plane wave form, as implements in the Vienna ab initio Simulation Package (VASP
5.4.4) [51, 52], under the pseudo potential frozen-core approximation of the pro-
jector augmented wave (PAW) [53, 54] method. Plane-wave kinetic energy cutoff
values of 520 and 600 eV were used for Cu2 S and CBTO, respectively. Reasonable
convergence criteria were used for ionic relaxations (≤0.01 eV/Å in ionic forces)
and electronic densities (≤10−6 eV in total energy). Brillouin Zone (BZ) integrations
were performed on a 7 × 3 × 3 -centered k-point mesh for Cu2 S and a 7 × 7 ×
7 Monkhorst-Pack [55] mesh for CBTO. A smaller 5 × 5 × 5 mesh was deemed
sufficient for S-doped CBTO via convergence testing. Due to the well-known under-
estimation of band gap energies by pure DFT calculations, further exacerbated in
localized d-electron systems [56–58], the Hubbard U parameter was applied (DFT
+ U) on Cu 3d to enhance on-site Coulomb interactions following the methodology
of Dudarev [59]. An effective U value of 7 eV was used in the case of Cu2 S, while a
value of 6 eV was used for CBTO, both adopted from previous studies [60, 61]. The
different values are due to the unique chemical environments of the two systems. We
note that the Bader charge analysis [62–66] conducted on doped Cu2 S was derived
from a pure GGA-DFT calculation.
128 E. Bainglass et al.

4.1 Cu2 S

Of the many experimentally known phases of Cu2 S [67–71], only the monoclinic
low chalcocite structure forms below 104 °C (Fig. 1a). Cu2 S-based thin-film solar
cells have previously shown efficiencies near 10% [35, 72]. However, the tendency to
spontaneously form Cu vacancies in all phases and the consequent excessive p-type
doping in the crystal make Cu2 S behave as a degenerate semiconductor [73, 74].
Hence, the efficiency of Cu2 S-based solar cells degrades over relatively short time
periods [75, 76]. Recently, a new phase of Cu2 S known as acanthite [77] (Fig. 1b) was
computationally derived from a materials database search and found to be thermody-
namically more favorable than its naturally occurring counterpart (low chalcocite).
Despite the new phase not showing any indication that its tendency for Cu vacancy
formation is any less than that of low chalcocite, a theoretical study did show that
Ag alloying in the acanthite phase can reduce this tendency, as well as control the
diffusion of Cu ions inside the crystal structure [60]. The study also found that the
electronic band gap of the acanthite phase can be increased with Ag alloying without
introducing any intermediate or defect states to its band structure. This suggests the
potential for tailoring a suitable band gap for photovoltaic applications via Ag alloy-
ing in Cu2 S. Experimentally reported band gaps for Cux S (1 ≤ x ≤ 2) are all within
1.1–1.2 eV. A recent study of silver copper sulfides comprising both experimen-
tal and theoretical efforts demonstrated promising electronic structures for AgCuS
(stromeyorite) and Ag3 CuS2 (jalpaite), both suitable for high-efficiency solar cells
[78]. Hybrid density functional theory was implemented in band gap calculation
yielding 1.27 and 1.05 eV, respectively, for AgCuS and Ag3 CuS2 . Hence, Ag doping
of Cu sites, or Ag alloying in the crystal structure, offers an opportunity to tune the
band gap of Cux S-based materials for photovoltaic applications.
It was also reported in a separate study that favorable growth of Cu2 S thin-film
interfaces with suitable metal oxide thin films such as TiO2 and Al2 O3 could help
stabilize the intrinsic Cu vacancy formation and minimize the Cu diffusion in the

Fig. 1 Crystal structures of a low chalcocite and b acanthite phases of Cu2 S. The low chalcocite
has 96 Cu and 48 S atoms. The acanthite phase is presented as a 3 × 2 × 2 supercell for comparison.
The unit cell of acanthite has 8 Cu and 4 S atoms
Photovoltaic Materials Design by Computational Studies … 129

system [79]. As an earth-abundant, non-toxic, and relatively cost-effective alterna-

tive, this material may provide the best outcomes compared to other ternary and
quaternary materials currently available. However, understanding the fundamental
characteristics of the electronic structures of the different phases of Cux S and the
effects of various doping schemes requires more attention. For example, it is known
that the low chalcocite phase of Cu2 S has a very complex crystal structure consisting
of 96 Cu and 48 S atoms per unit cell. The Cu atoms are distributed in 24 sym-
metrically inequivalent sites within the crystal structure. This renders computational
studies highly expensive and inefficient. On the other hand, the acanthite phase has
only two inequivalent Cu sites. Hence, defect-related studies in this phase are far
easier and become computationally feasible. Our recent investigation [80] shows
that doping Cu sites in the acanthite phase reproduces the effects of doping on the
low chalcocite phase. Thus, the simpler acanthite phase presents a computationally
feasible alternative for defect-related electronic structure studies. Furthermore, the
established structural correspondence allows results to be extrapolated to the more
complex low chalcocite phase. We next present band structures and corresponding
density of states for Ag, Zn, Sn, Bi, Nb, and Ta doping of Cu sites in the acanthite
phase of Cu2 S.
Results show that Ag doping does not introduce any intermediate or defect mid-
gap states, as was previously mentioned [60] (Fig. 2). The DOS plot shows that the
compositions of both the valence band maximum (VBM) and the conduction band
minimum (CBM) are similar to those found in pristine acanthite and low chalcocite
phases (Fig. 2). Added Ag 4d states are found deep in the valence band and do
not contribute to the band edges. Under Zn doping, the Fermi level shifts up in
energy, as the higher charge state of Zn with respect to Cu causes Zn 4s electrons
to partially occupy the CBM. This adds extra charge carriers to the system, making
it an n-type semiconductor. For Sn doping, a defect-related or intermediate mid-
gap state is observed about the Fermi level. The DOS plot shows that the band is
primarily composed of Sn 5p and Cu 3d. This kind of band is known to affect the
photo-absorption of the system. A similar effect occurs in Bi doping, where Bi 6p
shows significant contributions to both band edges. These phenomena become more
pronounced in Nb and Ta doping, which suggests that the higher the charge states of
the dopant, the more defect bands it introduces to the system, causing the material
to tend toward a metallic character. We note that these effects appear to be limited
to the CBM, and apart from the defect bands, the overall shape of the Cu2 S VBM is
retained in all doping scenarios.
A Bader charge analysis of Cu2 S (Table 1) shows that Ag and Cu have near
identical charge states which is expected as they are isovalent, while Sn is almost
twice that value. It is now evident that the coordination of a dopant in the system
correlating to its charge state will have a direct effect on the electronic structure
of the system. Thus, due to the proximity of the charge states of Ag and Cu, we
conclude that the defect-free band gap and favorable crystal structure of Ag-doped
acanthite Cu2 S make it the best candidate to tailor for a suitable band gap and optical
absorption.
130 E. Bainglass et al.

Fig. 2 GGA + U calculated band structures (top) and density of states plots (bottom) for Ag, Zn,
Sn, Bi, Nb, and Ta doping (separately) of a single Cu site, denoted as M Cu , in 2 × 2 × 2 supercells
(64 Cu and 32 S atoms) of Cu2 S acanthite. The Fermi level is set to 0 eV. The density of states
(DOS) is given in arbitrary unit. Ag plots are included for comparison. AgCu and ZnCu introduce
no intermediate or defect mid-gap states. However, the CBM in ZnCu shifts to a lower energy and
intercepts the Fermi level. For SnCu , an intermediate band is introduced at the Fermi level, which
is composed of both occupied and unoccupied states. Meanwhile, BiCu occupies a band from the
CBM and moves it below the Fermi level. For NbCu and TaCu , the system shows near-metallic
characteristics

Table 1 Calculated average Bader charge states of different species in doped Cu2 S
Average Bader charge states
Cu Ag Zn Sn Bi Nb Ta S
+0.37 +0.30 +0.71 +0.66 +0.52 +1.23 +1.28 −0.74
Photovoltaic Materials Design by Computational Studies … 131

4.2 CuBiW2 O8 :S

A recent computational materials prediction study by Sarker et al. suggested a triclinic

ground-state structure for the quaternary Cu(I)-oxide CuBiW2 O8 [61], or CBTO, for
potential photovoltaic application. For this DFT-predicted structure, an indirect band
gap was calculated at 1.43 eV, well suited for absorptions in the visible range. Calcu-
lated optical absorption spectra showed a slightly higher optical band gap of ~1.49 eV,
which was attributed to O 2p—W 5d transitions with O 2p situated slightly below
the VBM. This is because the Cu 3d (VBM)—W 5d (CBM) transitions are not so
favored by quantum selection rules, and Bi 6p contributions at the CBM are relatively
small. Analysis of the band structure of CBTO found no mid-gap Cu 3d states, as
compared to those found in CuWO4 thought to cause its high resistivity. Furthermore,
dispersive bands were found at the CBM indicating low electron effective mass and
high mobility. However, the top of the valence band was quite flat, indicating less
favorable hole mobilities. The ns2 md0 electronic configuration, exhibited by Bi–W–
O systems, has been suggested as a mechanism for reducing hole effective masses
via the introduction of dispersive anti-bonding s orbitals at the top of the valence
band [81, 82]. The contrary result in CBTO may then be due to occupied and highly
localized Cu 3d states at the VBM, which are slightly higher in energy than Bi 6 s
states.
CBTO was previously synthesized over 27 years ago [83] though no data regarding
its structural, optical, and electronic properties was provided in that report. However, a
recent collaborative study [84] of the quaternary compound successfully confirmed
the computationally predicted triclinic structure via solid-state synthesis methods
performed in a Cu-rich environment. Moreover, the study provided the first mea-
surements of the optical, electrical, and photoelectrical properties of CBTO. Light
absorption measurements yielded an indirect band gap of 1.46 eV, as compared to
the 1.43 eV gap produced from photoluminescence spectroscopy—both in excellent
agreement with the theoretical value. Hall effect measurements determined CBTO to
be a p-type semiconductor, as expected for Cu(I) oxides, with hole majority carrier
mobility of 0.32 cm2 V−1 s−1 and carrier lifetime of 2.12 ns. The diffusion length was
calculated at ~42 nm, a value comparable to that of BiVO4 [85], an ns2 md0 material
well known for its good light absorption and transport properties.
To improve hole carrier mobility, as well as the band gap energy, we look toward
S-doping in CBTO. These improved outcomes are expected from the lower elec-
tronegativity and ionization potential of sulfur with respect to oxygen. Thus, as a
dopant, S is expected to upshift the VBM and narrow the band gap. Additionally,
due to the proximity of their energy states, S 3p is expected to hybridize with Cu
3d at the VBM. Therefore, the localized Cu 3d character of the VBM should give
way in part to the more dispersive S 3p states, consequently reducing hole effective
mass. The electronic properties of CBTO: S was investigated within the framework
of DFT under similar conditions considered in the original CBTO study, as outlined
earlier. However, since the publication of the original computational work, a lower
ground-state structure of CBTO was derived from CuBi2 O4 (see acknowledgement).
132 E. Bainglass et al.

Calculated XRD peaks for the new triclinic structure were found to be a better match
with the experimental diffraction patterns. For this reason, the new CuBi2 O4 -derived
CBTO structure was used in the current study (Fig. 3).
The affinity of S to Cu becomes apparent at the single S-in-O site doping level,
with S pulling Cu toward it, hybridizing its 3p orbitals with Cu 3d states at the VBM.
This is due to the proximity of Cu 3d and S 3p electron energies, as mentioned above.
Moreover, as S distorts the Bi octahedron, the now closer Cu 4s orbitals hybridize
with Bi 6p and significantly decrease in density at the VBM. The linear O–Cu–O bond
found in the pristine cell bends toward angles reminiscent of the S-Cu-S network of
the low chalcocite Cu2 S phase, which leads to sharper, more localized Cu 3d and W
5d densities. The top of the valence flattens, with a calculated hole effective mass of
7.19 m0 , as compared to 2.16 m0 in pristine CBTO. Electron effective mass increases
slightly from 0.68 m0 to 0.87 m0 . The band gap is reduced to 1.534 eV, compared
to the 1.618 eV calculated for the new CBTO structure. The narrowing of the gap is
not due to an increase in the VBM, as expected, but rather a decrease of both band
edges. This may be due to asymmetric distortions caused by the 1:3 ratio of S-to-O
coordination about Cu atoms. The gap remains direct about the high symmetry Z
point. The CBM character exhibits similar localization, with a slight increase in Cu
4s and Bi 6s contributions, though far less than the primary contributions from empty
Bi 6p, O 2p, and W 5d states.
The localization effect is not limited to Cu and W orbitals and is observed through-
out the electronic landscape. This effect intensifies with additional S-doping as the
cell is transitioned to a 50/50 S-in-O doping/alloying level, where the lowest energy
configuration is obtained with Cu fully bonded to the 4 S sites (Fig. 3). More pro-
nounced effects are observed at this level of doping. All cation–cation distances are
increased as the larger S pushes atoms away from previously O-occupied sites. This
is true for all but neighboring Cu and W atoms, where the distance decreases with
respect to the pristine structure. This is caused by the increased attraction of the Cu–
S environment. With the now fully coordinated CuS4 cluster, the Cu–S–W network
becomes the primary photoactive site. This is highlighted in the density of states,
in which, and as expected, the VBM sees a primary S 3p contribution over that of
Cu 3d. At the conduction band, Bi 6p and O 2p hybridize more strongly than at the
single S-doping level. More importantly, as the S 3p density of states increases about
the Cu–S–W network, the W–S bond length decreases by ~0.2 Å leading to greater
W 5d-S 3p hybridization at the CBM. As a result, the CBM detaches from the rest of
the conduction band and shifts down below 1 eV, reducing the band gap to 0.766 eV.
Here, the narrow gap is indeed caused by a VBM upshift of 0.461 eV, as expected,
in addition to a CBM downshift of 0.391 eV. Despite the increased localization, both
electron and hole effective masses are reduced with respect to the pristine cell, with
1.99 m0 for holes and 0.43 m0 for electrons, suggesting an overall increase in car-
rier mobility for CBTO:S4 . Hence, S-anion-doping in CBTO may lead to improved
electronic properties suitable for photovoltaic applications.
Photovoltaic Materials Design by Computational Studies … 133

Fig. 3 Unit cells, band structures, and density of states plots for pristine CBTO (top), single S-in-O
doped CBTO (center), and 50% S-doped CBTO (bottom). Symmetry points were obtained from
AFLOW [86]. Densities are plotted in arbitrary units. Pristine CBTO contains 1 Cu, 1 Bi, 2 W, and
8 O atoms. Doping was applied to the unit cell to model high S concentrations. Band gap energy
decreases from 1.618 eV (pristine) to 0.766 eV (50% doping) due to increasing interactions along
the Cu–S–W network. S 3p hybridization at both VBM and CBM reduces effective masses of both
charge carriers
134 E. Bainglass et al.

5 Summary and Conclusions

In this chapter, we have outlined the benefits and effectiveness of computational

studies applied to new materials research for photovoltaic applications. An overview
of oxides was provided including the success of the material group, as well as the
difficulties it faces. As a viable alternative, sulfur-based solar absorbers were dis-
cussed in detail, with emphasis on their potential for suitable photovoltaic material
properties. Two case studies were presented, discussing first the electronic properties
of the pure sulfide compound Cu2 S and second the effects of S-doping in the novel
newly predicted quaternary oxide CBTO. In Cu2 S, we showed that Zn doping leads
to partial occupation of conduction band minima by 4s electrons, increasing charge
carrier concentrations resulting in an n-type material, while the remaining dopants
introduce intermediate defect states leading to metal-like characteristics. A corre-
lation between dopant charge states and mid-gap defect state concentrations was
suggested, with lower charge state dopants, which are isovalent to the host cation,
deemed favorable for photovoltaic applications. By comparing these results to Ag,
which has previously been shown to minimize intrinsic Cu vacancies and diffusion,
as well as increase the band gap without introducing detrimental mid-gap trap states,
we conclude that Ag alloying is the best candidate for band gap engineering in Cu2 S
systems. For S-doped CBTO, S-in-O anion doping was shown to cause distortions
in the pristine unit cell forming a photoactive Cu–S–W network through Cu 3d-S
3p and W 5d-S 3p hybridizations at the VBM and CBM, respectively. These inter-
actions lead to widespread localization of electron densities in the material. Despite
the localization, S 3p hybridizations reduce overall charge carrier effective masses
and narrow the band gap below 1 eV. This suggests that anion doping may provide
an additional mechanism for tailoring suitable photovoltaic material properties.

Acknowledgements All computations were performed on Texas Advanced Computing Center

(TACC) servers. We acknowledge Dr. Pranab Sarker for the discovery of the new triclinic ground
state of CBTO. This work was partially funded by NSF grant# 1609811.

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Photovoltaic-Based Nanomaterials:
Synthesis and Characterization

Kanwal Akhtar, Naveed Akhtar Shad, M. Munir Sajid, Yasir Javed,

Muhammad Asif, Khuram Ali, Hafeez Anwar, Yasir Jamil and S. K. Sharma

Abstract Improving the conversion efficiency and reducing cost are the major tasks
to make more energy competitive-based photovoltaics and able to replace the tradi-
tional fossil energies. In organic/inorganic-based solar cell development, nanotech-
nology seems to be the most promising branch. Nanostructure materials with large
band gap synthesized from III–V and II–VI elements are gaining more attention
because of their potential use in emerging energy applications. Nanostructures with
different morphologies including nanowires, nanosprings, nanobelts and nanocombs
can be prepared. Variations in atomic arrangements to minimize the effect of elec-
trostatic energies produces from different ionic charges on the polar surfaces are the
major reason of diversified range of nanostructures. In this book chapter, we will
focus on the contribution of different nanomaterials in the advancement of solar cell
technology.

Keywords Nanomaterials based solar cells · Photovoltaic devices · Inorganic

nanomaterials · Photovoltaic cell efficiency · Characterization parameters

1 Introduction

The fast-growing rate of world population demands new sources to sustain and
improve the amenity of life. The depletion of fossil fuels and declining its reserves

K. Akhtar · Y. Javed (B) · M. Asif · K. Ali · H. Anwar · Y. Jamil

Department of Physics, University of Agriculture, Faisalabad, Pakistan
M. Asif
e-mail: [email protected]
N. A. Shad · M. Munir Sajid
Department of Physics, Government College University, Faisalabad, Pakistan
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago

© Springer Nature Switzerland AG 2020 139

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_6
140 K. Akhtar et al.

subsequently is influencing environmental degradation, health, global warming

issues and creating alarming situation for humanity. The renewable future might
be guaranteed through contraction of greenhouse gas emissions and engendering
new resources to meet energy demands. So, clean and renewable energy sources
are best alternate to meet the world sustainability energy demands with zero quan-
tity of carbon emission. Solar, hydro, wind, biomass and geothermal are considered
the clean energy sources in which solar energy is main and excessive source for
renewable [1].
The sun is the main source of solar energy, excessively available and inexhaustible
rather than other renewable energy resources. Moreover, the captured power on earth
from sun is roughly equal to 1.8 × 1011 MW, which is generally larger energy rate than
all the present sources. There are diverse solar-based technologies, which are involved
in cooking, heating, drying, refrigeration, thermal power and photovoltaic [2, 3].
Photovoltaic (PV) is the finest source to fill the gap of world energy crises by direct
conversion of sun light into electricity, based on simple design that necessitating
low maintenance and high output. Therefore, PV has applications in numerous fields
such as communication, refrigeration, street light, disaster relief, water pumping,
charging vehicle batteries, satellites and space vehicles [4–6].
Solar cell based on photovoltaic effect was first presented by a French scientist
Edmond Becquerel [7], who observed the deflection of electrical voltage as sun light
fall on material. Few years later in 1883, a solar cell composed of selenium(Se) mate-
rial was manufactured by Charles Fritts based on photovoltaic effect [8]. Afterward,
it was discovered that silicon possessed more efficacy than selenium. Therefore, in
1953, first silicon-based solar cell was fabricated. First cell was silicon-based wafers
which convert solar energy into electrical power. Advanced PV technology was estab-
lished on electron-hole formation in two layers (p-type and n-type) semiconductor
material when photon falls on p–n junction [9].
The photovoltaic technology broadly categorized into four generations based on
their characteristics that are abridged in Table 1.
Using solid-state physics, solar cells attained its maximum possible efficiency
by employing different materials such as cadmium telluride (CdTe), silicon (Si)
and copper indium diselenide (CuInSe2 ), whereas efficiency was further improved
by triple-junction compounds based on indium gallium phosphide, indium gallium
arsenide and gallium arsenide [15]. Later on, chemistry seems to be an alternate

Table 1 Classification of different solar generations

Photovoltaic cells Characteristics based on efficiency
Wafer-based silicon cell (1-G) Attaining high efficiency and cost [10]
Thin film-based cells (2-G) Copper indium gallium selenide (CIGS),cadmium
telluride and amorphous silicon [11, 12]
Organic cells (3-G) Nano crystalline-based cells [13]
Inorganic in organic-based cells (4-G) Polymers-based and most advanced cells [14]
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 141

option that may boost photovoltaic cell conversion efficiency; therefore, these days
polymer-based and hybrid solar cells become area of interest for researchers.
Nanomaterials prepared through chemical routes offer enough chances in effi-
ciency improvement by accumulating light trapping and photo-carrier collection.
Nanomaterials have attained completely altered chemical and physical properties
from bulk materials owing to its high surface-to-volume ratio. This factor is further
diversified by architecture of the nanomaterials such as nanowires [15, 16], nanopil-
lars [17–19], nanocones [20], quantum dots [21], nanotubes, nanofibres, nanorods,
nanosheets and nanopores. It is also observed that light trapping is due to wide photon
path in nanostructures [22–24] that boost the electron–hole pair formation possibility.
Photovoltaic related properties of nanomaterials are (i) energy band-gap flexibility
and inter-changeability which relies on size (ii) improved optical path owing to mul-
tiple reflections and (iii) substantial decrease in the probability of recombination of
charge carriers [25]. Moreover, nanomaterials offer flexibility in photovoltaic assem-
blies having capability to alter solar energy conversion via novel approaches [26, 27].
Quantum dots (QDs), on the other hand, have size-dependent band gap [28–30] that
is useful to capture maximum solar spectrum depicted in following Fig. 1.

Fig. 1 Size dependency of quantum dot on band gap. Band gap of semiconductor material increases
with the decrease in size. Adapted from [31]
142 K. Akhtar et al.

2 Classical Review of Photovoltaic (PV) Cell

PV is considered an electronic device, attaining semiconducting properties composed

of P-N junction that made it a feasible device to convert solar energy into electricity
based on photovoltaic principle [32]. When a semiconductor material exposes to light,
photons of light are immersed by the semiconductor crystal and removes substantial
free electrons in the crystal that cause the electricity. Not all materials have properties
for solar cell except have capable to trap sun light and the visible spectrum conversion
into electricity. This occurred thanks to the creation of e− -hole pairs during photons
absorption with energies greater/equal to band gap [33].
The air mass (AM) is a level, where atmosphere diminishes the light to reach
the Earth’s surface. Broadly it is categorized into two levels; one is AM0 and other
AM1.5. AM0 is a level of light spectrum outside the atmosphere while AM1.5 for
terrestrial solar cell is standard solar spectrum at solar zenith angle of 48.2°. Graph
of sun light spectrum, elaborated that temperature of blackbody radiations increases
from 1000 to 2000 K and its highest values can attained by using Wien’s displacement
law [12]. Graph is showing blackbody maxima shifted toward greater wavelengths
conferring to Wien’s displacement law with temperature (Fig. 2). It indicates that
photovoltaic cell having greater-energy band gaps corresponding to greater radiator
temperature. Estimated band gap value of silicon-based solar cells is hv = 1.12 eV
(it usually goes up to 1.11 mm) as a result shows the matching with blackbody at
temperature range of 2610 K [34, 35]. In the visible region, major portion of the solar
spectrum varies from 0.38 to 0.76 mm.

Fig. 2 Comparison of blackbody spectra and solar spectra taken at earth-sun distance in semi-
logarithmic scale. Reprinted with permission from [34]
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 143

So, first assortment standard of PV absorbent is energy band gap which is around
1 eV and several materials lies in this energy gap such as silicon, gallium arsenide
(GaAs), copper indium diselenide (CIS), cadmium telluride (CdTe), Cu2 ZnSnS4
(CZTS) and other materials [36–38]. Secondly, the e− -hole creation by holding elec-
tric voltages and migration of electron from one terminal to other until equilibrium.
Conversion efficiency (η) and fill factor (FF) are basic defining terms for the behavior
of PV cell, where fill factor is defined as the ratio of maximum power (Pmax ) with
respect to theoretical power and conversion efficiency is ratio of output power to
input. The fill factor and conversion efficiency are described below [39].

Pmax IMP · VMP

FF = =
PT Isc · Voc
Pout
η=
Pin
Pmax FF × Voc × Isc
η= =
Pin Pin

Pout is maximum output power, Pin is input power, V oc is open circuit voltage and
I sc short circuit current density.
Each parameter has particular effect on the performance of solar cell. The typical
FF value is 0.70 for commercial use. The classical photovoltaic-based cell demands
thicker materials to show efficiency in optical absorption, but carrier collection
efficacy of particles can diminish due to wider length [40, 41].

3 Architecture-Based Classification of Nanomaterial

The light absorption and carrier collection properties of different architectures of

nanomaterials can enhance the efficiency of solar cell. Therefore, different forms of
nanomaterial are reviewed to explore their technological relevant properties. These
architectures include nanowires, nanotubes, nanopillars, nanobelts, nanofiber etc.
[42, 43].

3.1 Nanowires

The geometry of nanowires offers potential benefits against wafer-based or thin film-
based technology and improves light trapping, band-gap, and defect tolerance, for-
example, Si nano-wires improved path length of the incident solar radiation varies up
to 73 cm−2 [44]. Within sheet resistance, silver nanowires mesh electrodes exhibited
small transparency that is why its flexible substrates coincides with organic solar cell
and 19% improved values of photocurrent are reported [45]. The deposition of silver
144 K. Akhtar et al.

Fig. 3 Schematic diagram of core-shell nanowires. a Core ZnO nanowires array first grown in ITO
substrate by CVD, b ZnS growth on the ZnO nanowires by pulsed laser ablation, c PMMA layer
coating by spin coater, d then final prepared cell for measurements. Reprinted with permission from
[53]. Copyright (2015) American Chemical Society

nanowires is carried out via very low-cost protocol i.e., simple brush painting and
attained efficiency of 3.231% [46]. Diverse deposition ways are used for nanowires,
most simple is colloidal lithography. It takes less time and appropriate for large scale
deposition [25]. Vapor liquid solid technique is also very efficient to fabricate core
shell nanowires [26, 27].
Nanowires are fabricated via different protocol which can be top-down and
bottom-up approaches. With different deposition tools, nanowires can directly grow
on substrate e.g., chemical vapor deposition (CVD) [47, 48] and molecular beam
epitaxy (MBE) [49–52]. Nanowires epitaxial growth is organized at moderate tem-
perature by employing catalyst droplet. Following schematic is showing different
steps involved in the synthesis of NW (Fig. 3). This can be clearer in SEM images of
the grown nanowires (Fig. 4). Figure 5 provides cross-sectional view of the Si-based
nanowires grown by metal assisted chemical etching.

3.2 Nanotubes

Nanotubes are also considered important architecture of solar cell applications. Dif-
ferent material-based nanotubes have been fabricated for the applicability in solar
cell. To develop Schottky junction of Carbon nanotubes conducting layers when
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 145

Fig. 4 Structural characterization of the nanowires shown schematically in Fig. 3: a, b top view
of the core-shell grown nanowires. c High resolution image of nanowires showing ZnO and ZnS
structures. d Line profile of the nanowires by energy dispersive spectroscopy indicating presence
of Zn, O and S materials present in the nanowires. Reprinted with permission from [53]. Copyright
(2015) American Chemical Society

placed on n-type silicon, photovoltaic cell having efficiency up to 1.9% under expo-
sure of AM1.5 boosted up to 8.6% by doping of trifluoramethanesulfanyl amide [55].
For the optimization of solar cell efficiency, graphene can be used as compared to the
silicon (ITO/Si) under indium tin oxide (ITO)-based Schottky solar cells. Nanotubes
based on titanium dioxide can be used tremendously for dye-sensitized solar cells
as transparent photoanodes. Nanotubes of titanium oxide widely used in diversified
fields due to their electronic properties such as greater surface-to-volume ratio, high
electron mobility and low carrier recombination ability. For active charge transfer,
direct pathways tremendously increase the electron transport capacity [56, 57].

3.3 Nanopillars

Nanopillar photovoltaics possessed many promising features which can substitute

classical photovoltaics because of cost effectiveness. These are listed below:
1. Increase the collection carrier efficiency
2. Without use of expensive methods, growth of crystallized nanomaterials
146 K. Akhtar et al.

Fig. 5 Cross-sectional view Si nanowires arrays taken by SEM: a conventional metal assisted
chemical etching process using b nonconductive tape, c one-layer and d three-layer conductive
carbon tapes. Sample configurations are presented in the insert figures [54]

3. Decrease in the optical losses.

Nanopillars fabrication process is demonstrated in the Figs. 6 and 7 given below
[58].

Fig. 6 In the fabrication process, four main steps have been involved: anodization, electropolishing,
wet etching and anodization step. Modified with permission from [58]
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 147

Fig. 7 Schematic figure for nanopillar solar cell. Large part of a-SiH-nanopillar structure describe
the transport and photogeneration mechanism [59]

3.4 Nanorods

ZnO acceptor and conjugated polymer donor have been used as hybrid polymer-
based solar cells. ZnO nanorods in poly [1-methoxy-4-(2-ethylhexyloxy-2,5-
phenylenevinylene)] actively formed the heterojunction hybrid bulk-based solar
cells. Up to 0.045% efficiency can be obtained. This exposes the decrease in high
interior resistance of photovoltaic cells [60–62]. Figure 8 presenting the SEM micro-
graphs for different zinc (Zn2+ ) concentrations. With the increase in the zinc concen-
tration, bigger diameter of ZnO nanorods can be obtained. Electron mobility for zinc
oxide nanoparticles and bulk zinc oxide has been found up to 1–1000 cm2 V−1 s−1 .
Significant difference explains the high quality of ZnO nanoparticles in comparison
with bulk ZnO. Polymer donors having energy difference up to 0.3 eV leads toward
the effective separation of excitons to form free carriers [61].

4 Inorganic-Based Nanomaterials for Solar Cells

Inorganic nanoparticles exhibit promising physical properties due to their size in

nanometric dimensions. These particles possessed unique optical and physical prop-
erties of nanocrystalline quantum dots might lead toward their tremendous use in dif-
ferent biomedical and electrooptic applications. Core/shell inorganic nanoparticles
with hierarchical multicomponent assemblies exhibit many functional and enhanced
properties.
148 K. Akhtar et al.

Fig. 8 Scanning electron microscope top view micrographs of zinc oxide nanoparticles with dif-
ferent zinc concentrations a 0.0125M, b 0.025M, c 0.05M and d 0.1M. Reprinted with permission
from [61]

CdSe: Cadmium selenide is considered as primarily ionic compound having cova-

lent character. It is present in three crystalline forms but wurtzite hexagonal struc-
ture is most common among all. It is n-type semiconductor. Nanoparticles of cad-
mium selenide are useful photocatalysts. Core/shell structures having combination of
CdTe/CdSe showed the emission of near infrared radiations which does not exist for
the CdTe nanoparticles individually. Core/shell structure unswervingly dependent on
the lowermost lattice mismatch among the used nanomaterials [63, 64]. Polymeric
solar cells based on the CdTe quantum dots having single wall carbon nanotubes
containing composites of poly (3-octylthiophene)-(P3OT) revealed carrier transport
and good exciton dissociation. Current density of the short circuit and voltage of
open circuit were estimated in the range of 0.16 mA/cm2 and 0.75 V, respectively
[65, 66].
Silicon-based nanomaterials: High performance of silicon-based solar cell can
be attained through silver screen printed contacts. Silver nanoparticles can be intro-
duced in the paste to enhance the contact compactness, conversion factor and fill
factor. Silicon-based nanowires tremendously used in solar cells. Diameters of sili-
con nanowires vary from 200 to 1.5 mm. Diffusion length of minority carriers has
been found around 2 mm, minimum lifetime of the carrier is 15 ns, whereas the
velocity of maximum ability of surface recombination is 1350 cm s−1 (Fig. 9) [67].
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 149

Fig. 9 Micrograph taken through field emission scanning electron microscopy of the as-synthesized
silver NPs prepared by using solvothermal method. Reprinted with permission from [67]

For the silicon bulk materials, minimum lifetime of carrier is around 30 ms, diffu-
sion length is about 200 mm and surface recombination velocity is about 8600 cm/s.
For improving the efficiency of solar cells, effect of solar cells seems more obvious
when compared with the data available previously [68, 69]. Recombination velocity
seems to be reduced with the different structures of nanomaterials, which revealed
the increased photon collection [70].

5 Organic-Based Nanomaterials for Solar Cells

Organic-based nanomaterials gained tremendous attention from the last few

years. Key phenomenon in the manufacturing of photovoltaic cells was accord-
ingly mastered such as light trapping, exciton generation effect and one-
dimensional (1D) nanomaterials for Schottky barrier arrays [71]. Organic
solar cells/photoelectrochemical solar cells consist on counter electrode
(metal/semiconductor) and photoactive(semiconductor) electrode. In an electrolyte,
both are immersed which composed of redox couples. e− h pairs are formed when
light having greater energy as compared to semiconducting material is absorbed [72].
Figure 10 is showing schematic of the organic-based solar cell.
150 K. Akhtar et al.

Fig. 10 Schematic diagram for FTO/PEDOT:PSS/P3HT:PCBM(PSCs-2) and

FTO/TiO2 /dye/PEDOT:PSS/P3HT:PCBM (PSCs-1) heterojunction solar cells [73]

Table 2 Photoelectric performances of the perovskite solar cell (PSC-I) [73]

P3HT:PCBM (2:1) J sc (mAcm−2 ) V oc (V) FF Z (%)
Atm. annealed 3.96 0.83 0.67 2.19
Barrier 3.63 0.82 0.68 2.04
Vacuum annealed 4.3 0.83 0.67 2.37

Table 3 Photoelectric performances of the perovskite solar cell (PSC-II) [73]

Poly(3-hexylthiophene)(P3HT):[6]-phynyl-C61-butyric J sc (mAcm−2 ) V oc FF Z
acid methyl ester(PCBM) (2:1) (V) (%)
Atm. annealed 3.27 0.78 0.62 1.58
Barrier 2.83 0.80 0.65 1.48
Vacuum annealed 3.59 0.80 0.66 1.90

6 Nanomaterials for Dye-Sensitized Solar Cells

Titanium oxide(TiO2 ): TiO2 nanomaterials can be synthesized by combining the

chemical methods with the dealloying processes. Solar cell performances based on
TiO2 nanoparticles are listed in the Tables 2 and 3.

7 Nanomaterials for Perovskite Solar Cells

Achieving high short circuit current density and high open circuit voltage simulta-
neously is great challenge in the field of enhanced efficiency-based perovskite solar
cells. It is because of complex nature of excitonic hybrid-based inorganic-organic
semiconducting nanomaterials. Zhang et al., developed an effective and facile method
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 151

to fabricate the high-efficiency-based plasmonic devices. They prepared the solar

cells based on incorporation of gold nanoparticles into TiO2 mesoporous films and
depositing passivating MgO films in the modified silver NPs with mesoporous titania
through pyrolysis and wet spinning of magnesium salt. Plasmonic solar cells based
on MgO and silver NPs result in high conversion power efficiency about 16.1%, high
current density of short circuit of 21.76 mA cm−2 and high voltage of open circuit
up to 1.09% [74].
Perovskites are excitonic-based photovoltaic materials like quantum dots and
organic dyes. These materials also revealed the noticeable conductance for holes
and electrons. Because of the broad spectrum of p–p direct optical transitions, these
materials possessed greater optical absorption. Hence, perovskite layer is squeezed
between electron conducting and hole conducting materials matched with current
collecting electrodes in highly efficient perovskite solar cells. Zhang et al., used
poly(3-hexylthiophene) and stable CH3 NH3 PbI2 Br as hole transporting layer and
light absorbing layer to fabricate mesoscopic perovskite solar cells with high con-
version power efficiency up to 6.64% was reported. With bromine, partial substitution
of iodine in the perovskite results in prolonged lifetime of the charge carriers [75].

8 Nanomaterials-Based Photovoltaic Cells Efficiency

Perovskite organometal halide-based solar cells have been considered as important

photovoltaic technology because of their promising power conversion efficiency
(PCE) and low-cost materials. In 2012, PCE for solid-state perovskite-based solar
cell was 9.7% and it was reported high as 19.3% in 2014. In the Table 4, efficiency
of photovoltaic cells has been listed.

Table 4 Photovoltaic performance depending on cell configurations and material types of

perovskite solar cell [76]
Material (cell configuration) V oc PCE J sc FF Reference
(V) (mA/cm2 )
MAPbl3 (ZnO 1.02 8.9 16.98 0.51 [77]
nanorod/MAPbl3 /spiro-MeOTAD)
MAPbl3 (MAPbl3 /PCBM) 0.60 3.9 10.32 0.63 [77]
MAPbl3−x ClX 0.921 10.4 20.8 0.542 [78]
(MAPbl3−x ClX /P3HT)
MAPbBr3 1.30 0.56 1.08 0.4 [79]
(mp-Al2 O3 /MAPbBr3 /PDI)
MASn0.5 Pb0.5 I3 0.42 4.18 20.04 0.50 [80]
(mp-TiO2 /MASnx Pb(1−x) I3 /P3HT
152 K. Akhtar et al.

9 Solar Cell Characterization

In this section, we have discussed solar cell characterization considering the capa-
bilities of electrical power generation mechanism. These characteristics are related
to the working of cell structure including charge carrier life time. Key cell charac-
terization includes current versus voltage (I–V ) curve (Fig. 11) performance under
solar simulator and measurements of spectral irradiance. From I–V curves, open
circuit voltage, short circuit current and maximum power output can be identified.
Many additional solar cell parameters with different relationships are used for the
characterization of solar cell efficiency [81, 82].

• Current Versus Voltage (I–V) Curves:

Measurement of (I–V ) module of a solar cell provides information about solar cell
parameters such as open circuit voltage (V OC ), short circuit current (I SC ), power effi-
ciency, fill factor, maximum voltage (V max ) and maximum current (I max ) at maximum
power (Pmax ). For single junction generic cell, parameters at specific solar illumina-
tion level are mentioned in the figure given below. Internal loss is represented by fill
factor (FF) which is communicated by I–V curve in 4th quadrant of current voltage
in rectangular shape [84, 85]. As shown in I–V curve obtained through photovoltaic
cell, electrical generation depends on many factors including operating temperature,
solar radiation spectrum, applied electrical load and orientation of cell related to
solar beam input cells. To compare different cells, current and voltages are measured
based on common operating conditions. Standard test conditions (STC) are the set
of primary operating conditions which is also called standard reporting conditions
(SRC) [86, 87]. For SRC, standard reference spectrum is 100 W/m2 total irradiance
and 1.5 global air mass. This spectrum typically corresponds for mid latitudes at
earth surface. Operating temperature condition for SRC in specified device is 25 °C.
In outdoor setting, it is difficult to get SRC conditions according to practical point

Fig. 11 Representative I–V

curve of the solar cell.
Reprinted with permission
from [83]
Photovoltaic-Based Nanomaterials: Synthesis and Characterization 153

of view, whereas in indoor environment, electrical measurements usually performed

in laboratories under simulated sunlight [88, 89].
• Solar Simulator Performance:

Solar simulator is optical light source having broad band output comparable to sun
over wide response range of solar cell technologies. For the characterization of solar
cells, solar simulator is widely used for irradiance exposure to devices and materials.
Solar simulator is widely used in pulsed mode or steady state mode [90, 91]. Light
emitting diodes, xenon arc lamps, quartz tungsten halogen lamps and metal halide
arc lamps are being widely used in solar simulators. Xenon-based solar lamps are
most common among them. Currently, solar simulator is evaluated on three basic
unique criteria: (1) nonuniform irradiance within test measurement plane, (2) over
certain range of wavelength, spectral match with reference spectrum, (3) temporal
irradiance instability during measurement. Irradiance shows power of radiations per
unit area. It is expressed in watts/meter2 . Irradiance measurement is usually expressed
as wavelength function called spectral irradiance in W/m3 [92, 93].

• Measurements of Spectral Irradiance:

Spectral output of any light source or solar simulator is measured through spec-
troradiometer calibrations. These instruments are typically equipped spectrographs
with silicon-based charge coupled devices or fast photodiode arrays which provides
reliable and sensible information about intensity of light and spectrum [94]. Two
or more types of detector such as InGaAs-and Si-based arrays are used. For spec-
troradiometer calibration, light source should be calibrated at 1000 W for correct
irradiance measurements. Set of operational conditions are important for the calibra-
tion of reference lamp: (1) from bulb filament center, proper placement and alignment
of spectroradiometer optics at some definitive distance (2) use of high accuracy and
stable power supply with proper feedback mechanism for the precise control over
lamp current [28]. So, 0.1% better output accuracy is required typically. Input current
of the lamp maintained 0.01% better during calibration. For low uncertainty bud-
get, periodic calibration of spectroradiometer is needed. On regular basis, irradiance
characteristics of the simulator should be measured due to shape of spectral out and
age of lamps [95, 96].

• I–V Curve Measurement:

For I–V measurements, correct setup of solar cell is a network based on 4 wire
connection which is also known as Kelvin configuration (Fig. 12). These connections
are usually referred as sense leads and source leads. Current flow is measured through
source leads while voltage is measured through sense leads [97]. Source current will
stop flowing due to high input impedance. Hence, voltage can be measured only.
To take I–V data, setup based on 2 wire connection is usually used. Voltage drop
is observed with the flow of current through leads. In the cell, large photocurrent is
produced under comparable illumination/SRC that is why this effect is significant
for the solar cells with larger area [98, 99].
154 K. Akhtar et al.

Fig. 12 Circuit diagram for the I–V measurements. Reprinted with permission from [83]

10 Conclusion

To make use of photovoltaic energy in our daily life, improvement in the performance
of solar cell is considered as the major challenge. For low-cost fabrication and high
performance of solar cells, processes based on nano-electrochemistry seem to be
essential. These processes can be carried out at ambient temperature or low temper-
ature ranges, which minimizes sensibly the energy bills related to the manufacturing
of photovoltaic cells. Conversion efficiency is relatively high when obtained through
conventional solar cells in comparison to the solar cells based on nanomaterials.
But nanomaterials-based photovoltaic solar cells gained much attention because of
their potential applications in everyday life and low manufacturing cost. To over-
come the limitations encountered through solid-state physics leads the shift toward
nano-electrochemistry. Great opportunities are available to enhance the photo-carrier
collection and light trapping abilities. Enhanced efficiency of inorganic-based solar
cells is observed as compared to organic-based solar cell. Most promising next gener-
ation solar cell is based on organic materials which can be much better than inorganic
materials. Conversion efficiency of solar cells is small and difficult to implement on
the large scale. More efforts are needed to make high conversion efficiency-based
solar cells.

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Carbon Nanotubes: Synthesis
and Application in Solar Cells

Shazia Shukrullah, Muhammad Yasin Naz, Khuram Ali and S. K. Sharma

Abstract Unique structures and outstanding properties of carbon nanotubes (CNTs)

have drawn significant attention of scientific community working in materials science
and engineering. Researchers are taking interest in dealing with certain constraints
of solar power systems and harnessing maximum energy from the sun. Construction,
working life, manufacturing cost and efficiency of the solar cells are the key factors in
defining their widespread use. Different strategies are being adopted to develop stable
materials for manufacturing the low cost but highly efficient solar cells. Owing to
high thermal stability, mechanical strength, surface area to volume ratio and electrical
conductivity, CNTs can be a good choice as a solar cell material. CNT-based solar
cells are fascinating the world due to their reduced manufacturing cost and high
efficiency. Also, the future CNT-based hybrid solar cells would be much cheaper
than the traditional energy source cells. This chapter discusses the carbon-based
nanoscience and nanotechnology, structures and properties of CNTs, methods of
synthesis of CNTs and use of CNTs in manufacturing the efficient solar cells.

Keywords Carbon nanotube · Chemical vapor deposition (CVD) ·

Photovoltaicscells · Heterojunction solar cell

1 Carbon-Based Nanoscience and Nanotechnology

Nanoscience and nanotechnology are the study of engineering of matter, manipu-

lation of structures and particles of nanometer scale (about 1–100 nm), which are
the forefront of modern research. The properties of nanometer-sized objects can be
qualitatively different from those of ordinary matter because they result from a more
direct expression of the laws of quantum mechanics [1]. In the last twenty years,
carbon plays a leading role in materials science due to nanometer-sized systems and

S. Shukrullah (B) · M. Y. Naz · K. Ali

Department of Physics, University of Agriculture, Faisalabad 38040, Pakistan
e-mail: [email protected]
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies, St.
Augustine, Trinidad and Tobago
© Springer Nature Switzerland AG 2020 159
S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_7
160 S. Shukrullah et al.

Fig. 1 Different carbon nanostructures: single-walled carbon nanotubes (SWCNTs), multi-walled

carbon nanotubes (MWCNTs), fullerenes (C60, C240 and C540) and a carbon nano-onion

unique ability to form long chains to create new materials, that’s why it is known
to be versatile element on the earth. Diamond and graphite are considered as the
classical allotropes of carbon, whereas discovery of fullerenes was referred to as the
third allotropic. Soon afterward, new and intriguing forms of carbon were discov-
ered, named as carbon nanotubes (CNTs). CNT is one of the allotropes of carbon
which includes fullerenes, diamonds and graphite, as shown in Fig. 1.
CNTs have extraordinary interest and promising applications in the field of
nanoscience and nanotechnology due to their exceptional and highly desirable mul-
tiple chirality, fascinating electrical, thermal, magnetic and mechanical properties.
Recently, CNTs have been used in many types of solar cells applications due to
incredible structured arrangement of carbon atoms, large surface to volume ratio,
multiple chirality nature and absorbing power [2].

2 Structures and Properties of Carbon Nanotubes

The search was given new impetus when CNTs was first reported by Radushkevich
and Lukyanovich in a Russian language journal and largely unknown to scientific
world due to language barrier and heightened Cold War tension at that time [3].
One-dimensional material research started with the discovery of CNTs in 1991 by
Japanese scientist “Sumio Iijima” [4]. Iijima synthesized nanotubes by using arc
discharge technique and was first explored by using transmission electron microscopy
Carbon Nanotubes: Synthesis and Application in Solar Cells 161

(TEM). Subsequently, the floodgates have been opened to better understanding of

this marvelous material. CNTs captivate the great attention in scientific field due to
outstanding properties. The carbon atoms are strongly attached with each other by
covalently bound, approximate distance between the carbon–carbon atoms is nearly
about 0.14 nm. Whereas, the layers between them are in weak long-range of weakly
van der Walls-type interaction and inter-layer distance is about 0.34 nm. The weak
inter-layer coupling gives graphite the property of a seemingly very soft material,
the property which allows using graphite in a pen to write with. The C–C bonding
structure of nanotubes makes them more incomparable to diamond and graphene.
The structure of CNT is graphitic sheet rolled in cylindrical shape of diameter in the
order of a nanometer with both open ends. Hollow cylindrical structure is formed
due to bonding mechanism of carbon atoms. Carbon atomic structure is 1s2 2s2 2p2 ,
two electrons fill in 1s, while the other electrons fill the sp and when carbon atoms
combine to form graphite, then hybridization of sp2 occurred as shown in Fig. 2
[5]. In this hybrid sp2 -orbitals, sigma-bond (σ-bond) appeared at 120°, while π-bond
(pi-bond) is found at 90°. The chemical bonding of CNTs is composed entirely of sp2
bonds, like those of graphite. This bonding structure, which is stronger than the sp3
bonds found in diamond, provides the molecules with their unique strength. CNTs
naturally align themselves into ropes held together by van der Waals forces. Under
high pressure, CNTs can merge together, trading some sp2 bonds for sp3 bonds,
giving great possibility for producing strong, unlimited length wires through high
pressure CNT linking [6]. Due to delocalization of π-bond, it acts as thermally and
electrically conductive. This ability of nanotubes exhibit much more extraordinary
properties than graphite in term of electrical, chemical, mechanical, thermal and
biological due to rolling of graphite [7].
Rolling of graphite sheets in seamless manner by linear combination of base
vectors a and b can be written as

r = na + mb

where n and m as integers that defines the structure of nanotube. Based on values of n
and m, nanotubes can be divided into three categories. For n = m, resultant nanotube
will be armchair, m = 0 results in zig-zag and for other non-zero values of n and m,
result will be chiral nanotube (Fig. 3).

Fig. 2 Hexagonal bonding

structure for the graphite
sheet [5]
162 S. Shukrullah et al.

Fig. 3 Roll up vector as combinations of base vectors a and b [8]

Rolled axis of graphene sheet at corresponding θ of each structure of nanotubes

such as zig-zag (10, 0), armchair (6, 6) and chiral (8, 4) nanotubes are shown in
Fig. 4. The diameter d and chiral angle θ of the nanotubes can be given as,

d = 0.783 n 2 + nm + m 2 A0
√
−1 3m
θ = sin
2(n + nm + m 2 )
2

Theoretically nanotubes deliberated perfect structures where as in reality defect-

free structures will almost seem impossible. Defects were such as discontinuity,
bamboo like structure, capped, cone-shaped walls, bent tubes, toroidal, helical and
branched.
The extraordinary chemical, physical, mechanical and electrical properties of
CNTs have made them useful in many areas and still new industrial applications are
being reported frequently. For example, CNTs show a tensile strength of almost 50
times higher than steel, thermal conductivity greater than the diamond and one of the
lowest resistivities among the nonmetals. A summary of most important properties
of CNTs is given in Table 1. Based on such exceptional properties, vast applicability
of CNTs has been demonstrated in optical materials and electronics [10], structural
materials and polymeric additives [11] and biosensor [12] and energy-storage devices
[13]. In terms of commercial applications, CNTs are being effectively used as paint
additives and the electrical conductivity enhancers for composite materials [14].

2.1 Types of Carbon Nanotubes

CNTs are considered as nearly one-dimensional structures (1D buckytube shape)

according to their high length to diameter ratio. Most important structures are SWC-
NTs and MWCNTs. A SWCNT is considered as a cylinder with only one wrapped
Carbon Nanotubes: Synthesis and Application in Solar Cells 163

Fig. 4 Schematic illustration of SWCNT rolling vectors (n, m), and the corresponding armchair,
zig-zag and chiral structures. Adopted from Zhang and Zhao [9]

Table 1 Details of some common properties of CNTs

Property SWCNTs MWCNTs References
Tensile strength (GPa) 75 150 [15]
Young’s modulus (GPa) 900–1700 690–1870 [16]
Resistivity ( m) 10−6 – [17]
Maximum current density (A m2 ) 107 –109 – [18]
Quantized conductance (k )−1 6.5 – [19]
Theoretical quantized conductance (k )−1 12.9 – [20]
Thermal conductivity (W m−1 K−1 ) 1750–5800 3000 [21]
164 S. Shukrullah et al.

graphene sheet, while MWCNTs are like a collection of concentric SWCNTs. The
length and diameter of these structures differ a lot from those of SWCNTs and of
course, their properties are also very different. The bonding in CNTs is sp2 and
consists of honeycomb lattices and is seamless structure, with each atom joined to
three neighbors, as in graphite. The tubes can, therefore, be considered as rolled up
graphene sheets. The type of CNT depends on how the graphene sheet is oriented on
rolling. This can be specified by a vector (called chiral vector), which defines how
the graphene sheet is rolled up.
• At θ = 30◦ , m = 0 for all zig-zag tubes
• At θ = 0◦ , n = m for all armchair tubes
• At 0 < θ < 30◦ they are called chiral tube.
The value of (n, m) determines the chirality of CNT and affects the optical,
mechanical and electronic properties. CNTs with |n _ m| = 3i are metallic like as in
(10, 10) tube, and those with |n _ m| = 3i ± 1 are semiconducting like as in (10, 0)
tube, whereas i is an integer. The armchair and zig-zag tubes structures have high
degree of symmetry. These terms refer to the arrangement of hexagons around the
circumference [2].

2.2 Single-Wall Nanotubes

A single-walled carbon nanotubes (SWCNTs) can be formed by the rolling of a single

layer of graphite into a seamless cylinder. SWCNT consists of two separate regions
with different physical and chemical properties. Generally, CNTs have a length to
diameter ratio of about 1000, that’s why it was considered as nearly one-dimensional
structure. Most SWCNTs have a diameter of <1 nm along with important feature
of electric properties. The most basic building block of these systems is the electric
wire, and SWCNTs can be excellent conductors. Despite of that, SWCNTs are still
very expensive to produce. The SWCNT growth mechanism can be explained by
solid–liquid–solid graphitization of amorphous carbon or other imperfect carbon
forms catalyzed by molten super-saturated carbon-metal nanoparticles [22] (Fig. 5).
These atoms arrange in a graphene sheet with any local defect of this graphene
sheet results in its buckling and formation of SWCNT nucleus. Further precipitating
carbons incorporate in edges of growing nanotubes which are anchored to the catalyst
nanoparticles by overlapping its unsaturated sp2 orbitals with the metal orbitals of the
catalyst nanoparticles. Catalytic decomposition of hydrocarbon gases releases heat
which leads to rise in temperature of nanoparticles explaining the existence of molten
catalyst particles at low temperature but Krivoruchko and Zaikovskii suggest that the
additional heat is negligibly small and cannot explain the apparent low-temperature
catalyst melting [23, 24]. Chirality and diameter of the nanotubes influenced the
characteristics of SWCNT becoming either semiconducting or metallic.
Carbon Nanotubes: Synthesis and Application in Solar Cells 165

Fig. 5 Rolling of a single layer of graphite sheet into SWCNT

2.3 Multiwall Nanotubes

MWCNTs are the widely explored nanomaterials since its discovery is about two
decades ago. MWCNTs can be considered as a collection of concentric multiple lay-
ers of graphite rolled in on themselves to form a tube shape with different diameters.
The length and diameter of these structures differ a lot from those of SWCNTs and, of
course, their properties are also very different [4]. The inter-layer spacing of MWC-
NTs equals to approximately 3.3 Å which is the distance between graphene layers in
graphite as shown in Fig. 6 [25]. In transmission electron microscopy (TEM) analy-
sis, an inter-layer spacing of MWCNTs is also an important parameter for the study
of imperfections in carbon-layer stacking and the crystallinity of MWCNTs. The

Fig. 6 TEM analysis of MWCNTs and tubes with inter-layer spacing of 0.33 nm [26]
166 S. Shukrullah et al.

tubes with inter-layer spacing of 0.33 nm are regarded as the best graphite structures.
This value is specified for the graphite, which is a crystalline form of the carbon [26].
MWCNTs provide great opportunities in various applications due to unique prop-
erties such as high sensitivity to large specific area, chemically stability and good
biocompatibility although it is much more defective than SWCNT [8]. Chiral and
rolling vectors resolve the structure of nanotube which may be either in armchair zig-
zag or chiral form. The chemical, physical and optical properties of carbon nanotubes
are controlled by the synthesis process.

3 Mechanism of Synthesis of Carbon Nanotubes

3.1 Growth Mechanism

The fundamentally accepted growth mechanism of MWCNTs is when hydrocarbon

source is exposed to the metal catalysts, it decomposes into carbon atoms, which
dissolve and diffuse with the metal catalyst particles. The dissolved carbon then
precipitates out and crystallizes in the form of energetically stable tubular structures
with no dangling bonds. Dissociation of hydrocarbon is an exothermic process which
releases heat to the catalyst surface, while carbon crystallization is an endothermic
process and absorbs heat from the metal’s precipitation zone. This process keeps
the metal catalyst active for nucleation of CNTs. After a certain period, the catalyst
particles terminate the further growth of the nanotubes due to end capping, as shown
in Fig. 7.
Normally, it happens when passivation layer, such as amorphous carbon or car-
bide, poisons the catalyst thus stopping the growth of nanotubes [27]. In thermal
CVD process, there could be two possible modes of MWCNTs growth, namely the
tip growth and base growth. The tip growth mechanism is based on the weak inter-
actions between the catalyst particles, as illustrated in Fig. 7a. The carbon atoms
produced by the dissociation of hydrocarbon diffuse with the metal and the nan-
otubes precipitate out by lifting the metal catalyst up [28]. The nanotubes continue
to grow until excess carbon covers the catalyst particle rendering it inactive and halt-
ing the further tube growth. Unlike to tip growth, the base growth model is driven by
the strong interactions between the catalyst particles. The carbon precipitation fails
to lift the metal up, as shown in Fig. 7b.

3.2 Reaction Mechanism

CNTs can be formed by reaction mechanism in which hydrocarbon molecules decom-

poses on free metal surfaces such as cobalt or nickel. Commonly used carbon sources
Carbon Nanotubes: Synthesis and Application in Solar Cells 167

Fig. 7 a Tip growth and b base growth models for MWCNTs [27]

were ethylene, carbon monoxide, methane, ethanol and acetylene. During this pro-
cess, the carbon contained in the negative electrode sublimates because of the high
temperatures caused by the discharge. Because CNTs were initially discovered using
this technique, it has been the most widely used mechanism of CNT synthesis which
producing carbon atom with the simultaneous evolution of molecular hydrogen. This
is due to the reason that high electrons as carriers are generated at high temperature
which creates nucleation point for the growth of nanotube. Carbon atoms are decom-
posed from carbon gas and primarily deposited on the metal surface to form carbide.
At this stage of carbide phase, graphite layers are started to form outside the metallic
particles. This metal particle is then started to squeeze out by a strong pressure. Con-
sequently, it buildup the formation of graphite layer at the internal surface of graphite
envelope and continues the growth of carbon nanotube. This is possible only due to
liquid-like behavior of the metal. Kataura et al. [29] illustrated the growth of SWCNT
in three steps. Carbon clusters formed during first step and it was fullerene-shaped
structures which dissolved in metal particles. During Step 2, metal particle surfaces
started to cover due to saturation with carbon fragments. Lastly, nanotubes grow out
from the particles in Step 3 as shown in Fig. 8.
168 S. Shukrullah et al.

Fig. 8 Illustration of a model for SWCNT growth [29]

3.3 Catalyst-Free Growth

Rare examples of catalyst-free carbon growth are seen in literature. In catalyst-free

growth, CNTs are deposited on the cathode plate by an electric arc technique, which
is merely a chemical vapor infiltration mechanism for carbon growth. The driving
force is obviously related to the electric field; in other words, to charge transfer from
one electrode to the other via the particles contained in the plasma. It is not clear how
the MWNT nucleus is formed, but once it has, it may include the direct incorporation
of carbon species into the primary graphene structure. It revealed that growing CNTs
on the cathode is by increasing carbon concentration from the anode which indicates
C2 as secondary species and actively participate in MWCNTs growth.

4 Synthesis Techniques of Carbon Nanotubes

Since their discovery [4], CNTs continued to draw tremendous attention of the scien-
tific community due to their countless applications and properties. Based on specific
nature of each application, CNTs are being produced through a range of growth
processes including electric arc discharges, laser ablation and chemical vapor depo-
sition [30–32]. The other published techniques for CNTs production include flame
synthesis [33], plastic pyrolysis [34] and liquid hydrocarbon synthesis [35]. The later
techniques will not be discussed further since these are not developed yet to the extent
required for bulk production of CNTs. A detailed comparison of the established CNTs
production techniques is provided in Table 2.

4.1 Arc Discharge Method

It is one of the oldest techniques for production of CNTs. First utilized by Iijima [4]
in 1991 at NEC’s Fundamental Research Laboratory to produce new type of finite
Carbon Nanotubes: Synthesis and Application in Solar Cells 169

Table 2 A comparison of the major CNT production techniques

Technique Arc discharge Laser ablation CVD
Inventor Ebbesen and Ajayan, Smalley, Rice Endo, Shinshu Uni.,
NEC, Japan 1992, [2] University, 1995, [2] Nagano, Japan, [2]
Description Arc evaporation of Vaporization of the Catalytic
the graphite in the graphite targeted by a decomposition of the
presence of an inert laser beam hydrocarbons over
gas CNTs are formed on transition metals or
CNTs are normally a receiver during the their mixture to form
formed on an quenching process CNTs
electrode during the
quenching process
Process temperature >3000 °C >3000 °C <1200 °C
Typical yield 30–90% Up to 70% 20–100%
Process pressure 50-7600 Torr, 200–750 Torr, 760-7600 Torr
generally under generally under
vacuum vacuum
SWCNTs Shorter tubes with Long bundles of Longer tubes with
average diameter CNTs (5–20 μm) average diameter
range of 0.6–1.4 nm with individual range of 0.6–4 nm
diameter range of
1–2 nm
MWCNTs Shorter tubes with It is not very Longer tubes with
average inner interesting technique average diameter
diameter range of for MWCNTs, since range of 10–240 nm
1–3 nm and outer it too expensive. But
diameter range of production of
10 nm MWCNTs is possible
using this technique
Advantage Suitable for both Primarily used for This technique is easy
SWCNTs and SWCNTs with good to scale-up to
MWCNTs diameter control but industrial production
SWCNTs may have few structural defects Long tube length
few structural defects High selectivity and
Open-air synthesis is purity is possible
possible High product yield at
relatively low cost
Disadvantages Difficult to scale-up Difficult to scale-up. The product is usually
Expensive, Expensive, it requires MWCNTs and often
high-temperature expensive lasers, high riddled with defects
process temperature and
high-power
requirements
References [2, 30, 36–38] [2, 39–43] [2, 44–46]
170 S. Shukrullah et al.

carbon structures consisting of needle-like tubes. CNTs were produced using an arc
discharge evaporation method, which is similar to the fullerene synthesis. Working
principle of an arc discharge technique is to generate an electric arc between two
closely spaced electrodes (<1 mm apart) of graphite under an inert atmosphere of
argon or helium [47] The gas pressure is usually set between 50 and 700 mbar. A
direct current of 50 to 120 A, carried by a driving potential of ∼ 30 V, is used to
create high-temperature plasma between two conducting electrodes at temperature of
>3000 °C [36]. The carbon electrodes sublime in the inter-electrode plasma region
and condense rapidly to form CNTs along with other carbonaceous by-products.
The carbon needles with 4–30 nm diameter and up to 1 mm in length are possible to
grow on the negative end of the carbon electrode. Iijima used a pressurized discharge
chamber filled with a mixture of methane and argon at 10 Torr and 40 Torr, respec-
tively. A direct current (DC) source was used for arc discharge evaporation of the
carbon. Two vertically aligned thin electrodes were closely separated and installed
in the middle of the chamber, as shown in Fig. 9. The negative electrode (cathode)
contained a small piece of iron in a shallow dip, purposefully made to hold iron [48].
After an arc application time, discharge stopped and final deposit (CNTs) was
collected from the walls of cathodic and chamber. Final product further purified and
characterized to investigate their morphology.

Fig. 9 Geometric illustration of an electric arc discharge reactor

Carbon Nanotubes: Synthesis and Application in Solar Cells 171

Fig. 10 Geometric illustration of a laser ablation reactor

4.2 Laser Ablation Method

The working principle of the laser ablation technique is similar to the arc discharge
technique [46]. This technique was first used by Smally et al. [49] at the Rice Uni-
versity in 1995. At the time of this discovery, they were investigating the effect of
laser impingement on the metal surface. For production of CNTs, a carbon target is
subjected to the high intensity laser beam. With the rise of the temperature, the car-
bon rapidly vaporizes and cools down in the presence of a stream of an inert carrier
gas. CNTs grow on the cooler side surface of the reactor, as the vaporized carbon
condenses [49]. In the most practical laser ablation systems, a water-cooled jacket is
also added to control the system temperature and to collect the nanotubes, as shown
in Fig. 10.
In their two-step laser ablation experiments, initially a laser vaporizing pulse was
impinged on the graphite target followed by a second laser pulse to vaporize the
target more rapidly. The two-step ablation process is used to minimize the amount
of the carbon deposition as soot. SWCNTs produced by this technique grow in the
form of mat of ropes with 10–20 nm diameter and up to 100 μm length. However, by
having control over process temperature, catalyst composition and other parameters,
the average tube diameter and length can be varied and limited to the desired range
[44, 45].

4.3 Chemical Vapor Deposition Method

Chemical vapor deposition (CVD) technique involves decomposition of hydrocarbon

source over transition metals such cobalt, nickel, or iron to diffuse and precipitate
nanotubes under specific temperatures for MWCNT. CVD is a flexible and multi-
functional technique, which allows continuous growth of the nanotubes in a fluidized
bed operation [1–3]. It is also regarded as one of the most promising techniques,
available so far, for large-scale production of CNTs in an economical way [42, 43].
Different types of CVD are used such as plasma-enhanced (PECVD), thermal CVD,
172 S. Shukrullah et al.

Fig. 11 Schematic of a CVD setup in its simplest form

radiofrequency (RFCVD), catalytic chemical vapor deposition (CCVD), microwave

plasma (MPECVD), water-assisted CVD and hot-filament (HFCVD) [50]. As com-
pared with laser ablation, CCVD is an economically practical method for large-scale
and quite pure CNT production. The two main advantages of CVD are easy to handle
and controlled reaction process [51]. CCVD considered as standard technique for
the synthesis of carbon nanotubes which involves the chemical breakdown exciting
carbon atoms of a hydrocarbon on a substrate or with metallic catalyst particles. An
example of CVD setup is shown in Fig. 11.
Nanotubes obtained using CVD method is generally have much larger diameter
as compared to arc discharge due to this interrupted graphitic wall.

5 Applications and Functionalization of CNTs

The functionalization of CNTs makes them useful in a range of different applica-

tions. Their structure means that the tubes have an inner and an outer core which can
both be modified by different functional groups. The chemically stable surface of
CNTs restricts the functional groups to attach on. CNTs are usually functionalized
with organic functional groups to improve their solubility and dispersion [52]. Gen-
erally, covalent and non-covalent functionalization of CNTs are carried out to over-
come their hydrophobicity and to chemically tailor the surface properties. Oxygen-
containing groups, such as phenol, ketone, carboxyl group, ether, lactone and acid
anhydride are introduced on CNT surface via controlled oxidation. These oxygen-
containing groups can improve the wettability of CNTs in water and other polar.
Because of their exceptional and anisotropic properties, CNTs can be designed for
very specific purposes and have been widely investigated for electrical, mechanical
and thermal applications such as hybrid solar cells, biomedical imaging biosensors
and solar cell. In case of solar cell, CNTs are considered as import element because of
Carbon Nanotubes: Synthesis and Application in Solar Cells 173

Fig. 12 Applications of CNTs at different fields, a epoxy resin and security boats, b data cables
and electromagnetic (EM) shielding material [54]

high carrier mobilities (~120,000 cm2 V−1 s−1 ), independent of the channel length,
large surface areas (~1600 m2 g−1 ), absorption in the IR range (E g : 0.48–1.37 eV)
and enormous current carrying capability—109 A cm−2 [53] (Fig. 12).

6 World Power Demand and CNT Solar Cells

Growing global energy demands motivated search for alternative energy sources
such as accessible fossil fuels, particularly renewable solar energy. In comparison
to conventional energy resources, the adoption of solar cells is considered as cost-
effective due to simple manufacturing processes. Since 1991, dye-sensitized solar
cells (DSSCs), photovoltaic (PV) cells have received wide spread research atten-
tion over the 20 years with their advantageous attributes (e.g., good performance,
lightweight, low toxic, flexible and in diverse light conditions) [55]. Suzuki et al.
integrated CNTs into DSSCs as a counter electrode material where nanotubes were
deposited onto filter cells of Teflon membrane, consequential photovoltaic conver-
sion efficiency (PCE) device with a promising of 4.5%. Moreover, CNTs fused into
photoelectrochemical cells as additives where it behaves like donor–acceptor pairs
in conjunction with fullerenes, quantum dots and many other photoactive polymers
174 S. Shukrullah et al.

Fig. 13 Schematics of
perovskite structure
illustrating the ABX3
formation. A—Organic
cation, B—Metal cation,
X—Anion [58]

[56]. Among the developing renewable energy sources, solar energy is the most
promising due to sunlight covering almost all the earth’s surface. In harvesting solar
energy, silicon solar cells have been dominated up to 90% share of the PV cells
market. Though great improvements, solar cells classified into three generations, the
first-generation design called PV cells, whereas second-generation cells represented
as cost-effective thin film PV cells. Due to poor performance in efficiency of both
previous-generation cells, improving technology introduced third-generation solar
cells (organic solar cells, DSSC and perovskite solar cells PSCs) [57]. These cells
have the potential to cut cost to US$0.2/Watt with from US$0.8–1.0/Watt of thin film
solar cells. Among researchers, PSCs have become popular due to high efficiency of
about 22.1% in 2016 which is the record efficiency of previous-generation PV cells.
Organic–inorganic metal halide semiconductors known as perovskite used as basic
elements in PSCs with active layer of high absorption coefficient and high charge
carrier mobility ABX3 structures as shown in Fig. 13.

7 CNT-Based Perovskite Solar Cells

The carbon-based hole-transporter-free form is probably the most promising

for applications due to its low manufacturing cost, high efficiency and maxi-
mum long-term stability among the various perovskite solar cells. Wei et al.
[59] made a systematic comparison of efficiency between multiwall carbon nan-
otube (MWCNT) and two other carbon products, carbon black and graphite.
MWCNT electrode was used as shown in, the chemical embedding technique
was used to create a seamless interface between the MWCNTs and the per-
ovskite. Seamless interface ensured that it is an efficient interface for hole-
extraction process as shown in Fig. 14c. The MWCNT electrode turns out
to be superior to the other carbon electrodes as shown in Fig. 14b, d. What
is unique here with other carbon elements is that, the MWCNT network can function
Carbon Nanotubes: Synthesis and Application in Solar Cells 175

Fig. 14 a Energy-level diagram of the hole-transporter-free perovskite solar cells. Hole-extraction

process of three carbon-based perovskite solar cells fabricated with different carbon materials:
b Carbon black, c MWCNT and d Graphite flake [59]

as a transfer road for holes and should benefit the photovoltaic efficiency. Here in,
carbon material was also connected seamlessly to the perovskite film by chemical
reaction embedment strategy, forming carbon/perovskite interface that allows the
fluent extraction of hole from perovskite to carbon as shown in Fig. 14b, where black
particles indicated the carbon black. Nevertheless, due to unavailability of binding
force, the carbon black film can be easily and quickly cracked. In this way, it was
expected to be slow to transport the extracted holes from one particle to the sur-
rounding particle through the carbon black film which was not such an efficient way.
Wei et al. [59] believed that the cracks on thin carbon film damaged the photovoltaic
efficiency. Poor charge transfer was also observed in case of graphite flake film.
Figure 14d indicated that the hole extraction from the perovskite to the graphite
flakes loaded simply because the graphite flakes were too large and inflexible to fold.
Even after chemical embedment, many gaps were found which was due to weak
contact with the perovskite crystalline film. Although, these gaps caused serious
issues and problems in the transfer of charges and result in low photovoltaic effi-
ciency. On the other hand, MWCNTs were strongly attached on the perovskite thin
film. The reason behind was the long chain-like structure of MWCNTs which made
them to easily pack and cross together to form a continuous and crack-free thin film.
MWCNT works as a medium of transfer of charges from one place to another. Con-
sequently, the output efficiency of solar cells of MWCNT systems is considerably
greater than black carbon and graphite devices. Figure 14a showed the energy-level
176 S. Shukrullah et al.

diagram of the hole-transporter-free perovskite solar cells. In such perovskite solar

cells, electrons were injected from perovskite to TiO2 and finally collected by FTO.
Meanwhile, holes are extracted from perovskite to carbon electrode directly, elim-
inating both noble metal electrode and HTM. The solid green arrows indicated the
effective and fast transport of the charges, while the dashed green lines indicated the
poor and ineffective transport.

8 Photoactive Side of Predominantly Semiconducting

Nanotubes

Solar energy is eco-friendly and cost-effectives. Solar cells convert the solar energy
into the electrical energy. Operation of a solar cell depends on following factors:
• Absorption of light to create electron–hole pairs.
• Diffusion of charge carriers.
• Separation of electron and hole.
• Collection of charge carriers.
The functioning of solar cells is based on the transformation of free electrons by
additional energy, gained by the photons when it is incident on the surface of the film.
Bu Jong et al. discovered that cells gain energy from photons which generate free
electrons, these free electrons started to recombine and produce some photovoltaic
current to reduce the film’s binding energy, indicating that the highest number of
electrons is obtained. Bu Jong et al. manufactured new solar cells using CNTs, twice
as effective as the prior one to convert sunlight into electricity [61]. Utkarsh et al.
found that the solar cells efficiency can be increased by using CNTs and silica as a
p-type and n-type semiconductors, respectively [60]. This heterojunction is shown
in Fig. 15. After the formation of heterojunction, the transition of electrons and holes
started and band-gap between them formed. When light fall on the CNTs solar cell,
holes and electrons gained the energy and electrons transferred from silica to CNT
to generate photovoltaic current which further can be stored in the battery.
Aspitarte et al. demonstrated a p–n junction device with thin diameter of CNTs,
yield a photocurrent about 20–40% [62]. They have also found increasing trend
in photocurrent quantum efficiency by increasing nanotubes diameter. Lee et al.
demonstrated the photovoltaic efficiency increased by using a CNTs p–n junction
diode [63]. Freitag et al. investigated the interesting property and mechanism of
photoconductivity along with photocurrent generation [10, 64]. Schematic diagram
of photo carrier generation in CNTs is shown in Fig. 16.
A mechanism of the photovoltaic process is electrons and holes as the carriers are
extracted, separated, excited, transported, collected, and then finally extracted to an
external circuit. Charge carrier separation is required for this process which can be
obtained by intrinsic asymmetry potential between holes and electron to drive charges
away from their point of origin of the solar cell which generate the photocurrent to
Carbon Nanotubes: Synthesis and Application in Solar Cells 177

Fig. 15 Fabrication of solar cell using CNTs [60]

Fig. 16 Variation of band structure of CNT-based solar cell [60]

an external circuit as shown in Fig. 17. The photocurrent density of the device is
described as

JSC = q QE(E)bs (E)d E

where JSC is photocurrent density, energy E, electronic charge is q, incident spectral

photon flux density bs (E) and QE(E) is the probability of incident photon. This also
depends on the two main factors of photoactive material, one is absorption coefficient
178 S. Shukrullah et al.

Fig. 17 Schematic of photocarrier generation in CNTs [64]

and second is efficiency of charge collection and separation [65]. The current which
flows in the opposite direction of the photocurrent is named as dark current denoted by
Jdark and is generated by the potential difference between the cell terminals. Mostly,
cell behaved like a diode under dark conditions. The current flowing through this
diode under an applied voltage is given by
 qV 
Jdark = JO e n KB T − 1

where Jdark (V) is dark current, J 0 is constant, n is an ideality factor, k B is Boltzmann’s

constant and T is the absolute temperature. Thus, net current–voltage obtained by
summing up both short-circuit and dark currents. Net photocurrent density in the cell
is given by

Jm = JSC + Jdark

The efficiency (η) of a solar cell at operating condition is given by

Jm Vm
η=
Pin

whereas V m is the voltage, J m is the current density, Pin is the incident light power den-
sity of solar cell, respectively. These parameters are much important to characterize
the performance of solar cells.
Carbon Nanotubes: Synthesis and Application in Solar Cells 179

9 CNT Dispersion and Thin Film Formation

Performance of solar cells depends on the basic properties of photovoltaic such as

CNT films, film thickness and sheet resistance; sequentially, it is also correlated
with the structure, morphology and nanotube loading. CNT films properties changed
with different types of nanotubes morphology. Self-assembled CNT films with high
transmittance (80–90%) have intensively studied as transparent electrodes in CNT-
silicon heterojunction solar cells [66–68]. Jia et al. [70] prepared CNT films loaded
with nanotube by using vacuum filtration. They found the correlation between cell
efficiency and merit of the films. This study illustrated the future improvement of
photovoltaic performance based on the optical transmittance of the films and sheet
resistance [69]. The schematic of nanotube–silicon junction solar cells is shown in
Fig. 18.

Fig. 18 a, b Schematic diagrams for nanotube film preparation and c configuration of nanotube-
on-silicon heterojunction solar cell [69]
180 S. Shukrullah et al.

10 Heterojunction and Environmental Stability

of CNT-Based Solar Cells

Heterojunction photovoltaics CNT-based advanced material has gained a tremen-

dous interest in developing next generation due to its high carrier mobility and
two-dimensional networks. Recently, researchers reported that high performance
of heterojunction Si-CNT solar cell achieved as compared to simple p–n junction Si
modules [55, 60]. Jia et al. [70] established Si-CNT solar cells by glazing CNT film
on n-type Si which results increase in efficiencies up to 7%–13.8%. This photoelec-
trochemical unit in addition to Si-CNT with infiltration of nitric acid steps is shown
schematically in Fig. 19.
CNTs are good light absorber and have been used in solar cells as photo carrier
generation materials. Kozawa et al. [71] invented Si-SWCNT-based solar cells and
fabricated with the solution of CoMoCAT. It was observed that efficiency strongly
dependent on the thickness of the film. Whereas, performance increased up to approx-
imately 70% by balancing the effective p–n junction area and the light intensity based
on an equivalent circuit model. This model suggested that the fabrication of a high-
density semiconducting SWNT network at the interface of Si is the key to improving
the conversion efficiency of the SWNT/n-Si heterojunction solar cell [71]. Hybrid
heterojunction and photo electrochemistry solar cells based on silicon nanowires
found to enhance the light absorption. Muramoto et al. [72] fabricated heterojunc-
tion solar cells by combining surface-textured of CNTs and Si substrates synthesized
by solution-based process. It was found that Si surface formed pyramidal texture by
adding the dilute alkaline solution which support the capacity of the light absorption
[72]. It has been revealed that the morphology also plays a main role in photo-
voltaic applications beyond the donor–acceptor system’s electronic characteristics
where functionalized CNTs are involved. Addition of functionalized CNTs with a
polyethylenedioxythiophene (PEDOT) reduced the general output but increase the
current. These modifications have been ascribed to the system’s nano morphology.

Fig. 19 Structure of
Si-CNT-based solar cell with
acid infiltration [64]
Carbon Nanotubes: Synthesis and Application in Solar Cells 181

Carbon materials considered as a great candidate for solar photovoltaic cells, ele-
vated optical absorption, superior thermal, and photostability. Carbon-based solar
cells with active layers made them exclusively of same benefits as of polymer-based
solar cells, i.e., processable, possibly flexible and chemically tunable solutions [73].

11 Conclusions

The sun has huge potential for serving the growing demand for global energy. Nev-
ertheless, as compared with traditional energy sources, gigantic barrier is found
between the cost and efficiency of solar energy. Due to the demand to produce green
energy sources, researchers have been taking a keen interest to overcome the cer-
tain limitations of the power generated from solar source. Noteworthy, strategies
have been developed to find the solutions of use of expensive materials, installation
cost, low conversion efficiency, proper integration in the grid, diluted energy den-
sity of solar radiation and fabrication process. These challenges are conquered by
introducing the nanostructure architectures such as CNTs with incredible proper-
ties, structure, large surface to volume ratio, multiple chirality nature and absorbing
power. Therefore, in progress of manufacturing the solar cells, CNTs are considered
as most potential and stable material. Nanotechnology has launched new ways to
design efficient CNTs solar cells. Additionally, ballistic pathways are found to boost
the performance and efficiency of the solar cells by blending CNTs in the active layer.
CNTs have the ability to separate electrons–holes carriers as they can form hetero-
junction with conducting polymers and exhibit good PV properties for absorption to
generate current. In addition, CNTs can transfer electrons or holes efficiently. Con-
cerning the cost, CNT-based hybrid solar cells would be much cheaper as compared
to traditional energy source cells. Due to highly efficient with more ecologically and
environmentally stability, CNTs will play vital role in fulfilling the world’s future
energy demand.

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Basic Concepts, Engineering,
and Advances in Dye-Sensitized Solar
Cells

Mohan Chandra Mathpal, Promod Kumar, F. H. Aragón, Maria A. G. Soler

and H. C. Swart

Abstract The day–by-day increasing need for light energy has reduced the nec-
essary supply of energy for mankind usage and hiked the prices of natural energy
resources. To avoid energy tragedy in future, one needs to use the non-degrading
sources of energy for energy harvesting. The advancement in solar cell technology
allows us to convert the sunlight more efficiently into electrical energy, though the low
cost with highly stable and efficient solar cells is still desirable. The dye-sensitized
solar cells (DSSCs), a class of third-generation photovoltaic cell, have emerged out
as economic, eco-friendly, and much easier fabrication process over other existing
technologies such as single-crystal Si solar cells, polycrystalline Si solar cells, thin-
film solar cells, and other semiconductor (GaAs, CdTe, CuInSe2, etc.) thin films. The
main challenge and limiting factor with DSSC’s fabrication are their efficiency and
durability in the environment. In the last decade, enormous efforts have been made
to improve the efficiency and stability of DSSCs. One of the possible ways is the
manipulation of light at nanoscale on some metal–dielectric interface and integrating
it on some cheaper electronic devices for highly efficient solar cell applications. On
the other hand, the research on modifying the design and fabrication of photoanode,
dyes materials, and counter electrode materials have paid huge attention in architect-
ing DSSCs. This chapter provides an insight into the fabrication of DSSCs and the
challenges associated with its fabrication, stability, and efficiency.

Keywords TiO2 · Semiconductor · Dye · Nanoparticles · Plasmonic · Solar cell ·

Photoanode · Counter electrode · DSSC

M. C. Mathpal (B) · F. H. Aragón · M. A. G. Soler

Institute of Physics, Universidade de Brasília, Brasilia 70910-900, DF, Brazil
e-mail: [email protected]
P. Kumar (B) · H. C. Swart
Department of Physics, University of the Free State, Bloemfontein, ZA 9300, South Africa
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 185

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_8
186 M. C. Mathpal et al.

1 Introduction

Increasing consumption of energy sources from fossil fuels compels researchers

to think about the substitutes for everlasting renewable energy sources. Solar cells
as an alternative of renewable energy sources have got high consideration for the
conversion of solar energy into electrical energy. The high-cost and sophisticated
fabrication process of conventional solar cells, such as Si solar cells and many other
semiconductors (GaAs, CdTe, CuInSe2, etc.), limits its practical usage for domestic
and industrial applications. Since the discovery of dye-sensitized solar cells (DSSCs)
in 1991 by Michael Gratzel research group [1], the DSSCs are considered to be one
of the promising future candidates in replacement of high-cost conventional solar
cells. Gratzel and their coworkers have put great efforts for the last two decades to
further improve the several factors involved in DSSC’s device technology in various
aspects to make it suitable for commercialization [2–15]. So far their group achieved
one of the best power conversion efficiencies (PCE) of DSSCs up to 12–13% [9, 15].
The advances in nanoscience technology open new horizons to use various nanocrys-
talline materials for the application of DSSCs. The basic concept of a DSSC system
was hypothesized based on photosynthesis (sunlight is being used by plants to con-
vert water and carbon dioxide into oxygen and sugar) in nature, where the optical
absorption of light takes place by a wide bandgap nanocrystalline semiconductor
material and the charge carriers are separated by the molecules of a sensitizing dye
with the association of an electrolyte solution [1, 16]. The main components consist
of a photoanode (an n-type semiconducting material), dyes for sensitization, elec-
trolyte solution for conduction, and a counter electrode (a p-type semiconducting
material), which create a liquid–solid interface in the DSSC to form a p–n junction.
Overall PCE of a DSSC system depends on several factors such as the transport
of charge carriers, specific surface area, and light-scattering properties of photoan-
ode materials, absorption broadband of dyes, recombination losses, and collection
of photo-generated electron and holes at the electrodes [2–15]. The main advantage
of DSSCs is that it is eco-friendly in nature with an easy and low-cost fabrication
process, whereas the main limitations for its commercial application are due to the
poor long-term stability, narrow absorption spectrum, choice of suitable electrode
materials, charge carrier transportation, and collection losses and poor charge transfer
mechanism for regeneration of dye molecules [17]. There are lot of efforts to increase
the PCE by means of several techniques such as increasing the surface area of the
semiconducting materials with the use of 1D nanostructures (nanotubes, nanowires,
nanotrees, and nanofibers), [1, 18–20], fabrication of composite electrodes [20, 21],
preparation of new dyes and mixing of dyes [22, 23], introducing plasmonic structure
and photonic crystal [23–34], and the inclusion of a light-scattering layer [20]. There
are many excellent review articles, which are focused on various challenges and dif-
ferent perspectives of DSSCs [5, 8, 14, 35–61]. Nonetheless, the literature providing
an insight with a brief overview of DSSCs from the beginning to the recent devel-
opments is today’s demands in this rapidly growing research theme. This chapter is
Basic Concepts, Engineering, and Advances … 187

focused on the basic concept and the main component of the DSSCs; design and fab-
rication scheme of DSSCs; charge separation and collection process; new concepts
in ongoing research with recent advances and future perspectives in the field which
are important to standardize and commercialize the development of stable DSSC
devices of high efficiency. This chapter will surely help in boosting the understand-
ing of DSSCs for the beginner and especially to those who are interested to accept
the challenges in DSSCs as an alternate for renewable energy sources.

2 Basic Concept of DSSC

DSSCs are categorized as a third generation of thin-film solar cells, which are based
on the concept of artificial photosynthesis with the use of dyes or natural pigments
to harvest the solar energy [62]. These devices are cost-effective due to a simple
fabrication procedure. The main used components in dye-sensitized solar cells are
a cheaper substrate, photoanode materials, a photosensitizing dye, an electrolyte
solution, and a counter electrode (CE or photocathode). The solar light conversion
efficiency depends on several parameters such as surface area and the bandgap of
photoanode materials; absorption spectrum of dye molecules; quality of electrolyte
solution (which is responsible for the oxidation and reduction process); collection
and separation process of the charge carriers at electrodes [61].
In a traditional DSSC, a porous titanium dioxide (titania) thin film coated with a
dye is exposed to light, which excites the electrons in dye molecules and generates
negative and positive charges. The nanoporous n-type TiO2 semiconductor not only
supports the adsorption of the dye sensitizer at its surface but also works as an
electron acceptor and electronic conductor [43]. The photoexcited electrons (negative
charges) of dye sensitizer flow out of the cell through the conduction band (CB) of the
titania, while the holes (positive charges) flow into a liquid electrolyte inside the cell.
This transfer of photoexcited electron (from dye to CB of TiO2 ) results in the flow of
current through the nanocrystalline TiO2 film to the charge collecting electrode (such
as ITO, FTO, TCO-based photoanode) and then passes to the external circuit. The
conversion of solar light energy into the current is sustained by the use of a reversible
redox couple (O/R), which is often an electrolyte solution of triiodide/iodide (I− −
3 /I )
for the continuous generation of the reduced dye sensitizer. A schematic for the
operating mechanism is depicted in Fig. 1a, b. All the main processes are highlighted
in Fig. 1 by numbering the process from (1) to (7) and explained in Eqs. (1)–(7),
respectively. Figure 1a illustrates the basic operation mechanism of a traditional
wet-type DSSC, which contains an I− −
3 /I redox couples in an electrolyte solution.
In photoexcitation process, the electron is absorbed by the dye and then transferred
to the photoanode, which consists of an n-type TiO2 semiconductor; therefore, the
neutral dye molecules (S) get oxidized (S+ ). This oxidized (S+ ) dye can be neutralized
to natural dye (S) by the oxidation reaction (R → O) of the redox species present in
the I− −
3 /I electrolyte solution.
188 M. C. Mathpal et al.

Fig. 1 Basic operation mechanism in DSSC. a Wet-type DSSC with liquid electrolyte to act as a
redox couple in the cell. b Solid-state DSSC with a p-type semiconductor by replacing the liquid
electrolyte. Here the symbols are represented as: S—dye as sensitizer, S* —dye in electronically
excited state after absorbing the photon from sunlight, S+ —oxidized state of the dye sensitizer,
O/R—redox couple as oxidizing and reducing agent (here, e.g., I− −
3 /I in electrolyte solution),
CB—conduction band level, and VB: valence band level for semiconductors (here TiO2 ). Green
arrows represent the transition and migration of the electrons inside the solar cell, whereas red
arrows represent the possible recombination losses inside the solar cell

The process is completed by the electrons circulating through the external circuit
after regenerating the mediator R at the cathode (O → R) by reduction. Thus, the
continuous oxidation and reduction process of the dye molecules by photoexcita-
tion and reduction at the cathode, respectively, allow the conversion of light energy
Basic Concepts, Engineering, and Advances … 189

to electric energy without any chemical transformation [43]. Additionally, the elec-
tron recombination usually takes place by either donating electrons to oxidized dye
molecules or to the oxidized redox couple in the electrolyte solution, which are the
main limiting factor to improve the efficiency of DSSCs (shown by red-dotted arrows
in Fig. 1). The main steps involved in the conversion process are described as follows
[36, 58, 63]:

Dye molecules(S) + TiO2 surface → No absorption (1)

Now, the neutral dye molecules (S) on the TiO2 surface absorb the incident light
energy:

S + hν(light energy) → S∗ (photo - excited dye molecule after absorption) (2)

S∗ → S+ (oxidized dye) + e− (electron injection to CB of TiO2 ) (3)

e− (injected electron) + circuit(through back electrode) → e− (at counter electrode)

(4)

3I− (in electrolyte) → I− −

3 (oxidized to triiodide) + 2e (this electron is donated to dye)
(5)
 
S+ (oxidized dye) + e− accepts from I− redox of electrolyte → S(ground state)
(6)

I− − −
3 (triiodide mediator of electrolyte) + 2e (at counter electrode) → 3I (reduction)
(7)

In normal working condition for the mesoporous TiO2 system, the ratios and
concentrations of the different species for a general DSSC are as follows [49]:
(i) Under solar cell operating conditions, there are about 10 electrons per TiO2
particle of 18 nm diameter.
(ii) Almost 90% of electrons are trapped in TiO2 lattice while <10% are injected
into the conduction band.
(iii) There are approximately 10,000 adsorption sites for H+ on a TiO2 particle.
(iv) A TiO2 particle of 18 nm diameter can interact with approximately 600 dye
molecules sitting on its surface.
(v) Each dye molecule in the cell usually absorbs a photon once per second.
(vi) The flux of the injected electron into the TiO2 particle is ~600 s−1 .
(vii) Under light irradiation, about 1 dye molecules per 150 TiO2 particles is in its
oxidized state.
(viii) The total volume fraction of the solutes (iodine ions) in the electrolyte solution
is ~10–20%.
190 M. C. Mathpal et al.

(ix) There are approximately ~1000 I− and 200 I− 3 ions in the pore volume near
the TiO2 particle.
(x) The I2 concentration is <1 μM, which is about one free iodine per 10,000
TiO2 nanoparticles.
(xi) Ruthenium dye complexes are a good choice to offer a turnover number (num-
ber of cycles to reduce the oxidized dye) of 108 for a DSSC, which can be
durable for more than 15 years outdoors. The main drawback of practical
usage of this rare metal-based dye complex is their high cost.
The main problem associated with traditional wet-type DSSCs is their integration
to encapsulate the device owing to the presence of a liquid electrolyte solution.
To avoid solvent-free electrolytes, many researchers are focusing on all solid-state
DSSCs in order to have the stable performances [43, 63, 64]. This can be done by
carefully choosing the redox levels of the dye and a solid p-type conductor (or a hole
transporting layer like spiro MeOTAD, CuSCN, polypyrrole, and CuI) instead of
liquid electrolyte solution as illustrated in Fig. 1b [63, 64]. It results in an electron in
the CB of the photoanode materials (n-type semiconductors, e.g., TiO2 ) while a hole
is localized on the p-type conductor. Murakoshi et al. [65] reported the first TiO2 and
conducting polymer-based heterojunctions as a solid-state DSSC. Bach et al. [64]
used the spin-coating technique to deposit a hole-rich conducting amorphous organic
solid layer on a TiO2 electrode. The mechanism for transport of charge carriers is
via hole hopping in hole conductors which is different than ionic migration in liquid
(I− −
3 /I ) electrolytes.

3 Components of DSSC

In this section, the main components to fabricate a DSSC device are briefly discussed.
Recent improvements for the selection of different components are also highlighted.
Substrates: To reduce the cost of the solar cells, the substrate choice is very
important. In general, soda lime glass substrates are often used after the coating
of a conducting oxide material. The substrates with high transparency, low sheet
resistance which can sustain at high temperature are highly desirable for good per-
formances of the DSSCs. Mostly, indium tin oxide (ITO) and fluorine-doped tin oxide
(FTO)-coated glass among various TCOs (e.g., aluminum-doped zinc oxide (AZO),
antimony-doped tin oxide (ATO)) with a uniform sheet resistance of 5–20 O/square
are frequently used for DSSC applications. These substrates are also commercially
available, though these conducting oxide materials can be directly deposited on glass
substrates via various techniques such as spin coating, spray coatings, direct current
(DC) magnetron sputtering of metal alloys, radio frequency (RF) magnetron sputter-
ing of metal oxide targets, reactive sputtering, pulse laser deposition (PLD), thermal
evaporation, and atomic layer deposition (ALD) [66–74]. The sintering of the pho-
toanode material (TiO2 electrode) is usually carried out in the range of 450–550 °C;
therefore, the sheet resistance of the conducting substrates should be independent
Basic Concepts, Engineering, and Advances … 191

of the sintering temperature [63]. FTO-coated glass substrates are preferred over
ITO-coated glass substrates owing to their low-cost fabrication and high stability at
a higher temperature (in 350–650 °C) for DSSC applications. Nowadays, researchers
are exploring metal substrates (W, Ti, Co, Ni, Pt, etc.) and the plastic substrates such
as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) and using
them as conductive polymer substrates made of ITO coating on PET film (ITO/PET)
and PEN film (ITO/PEN) for DSSC applications [35, 75–78].
Photoanode: Traditionally, anatase TiO2 particles in the nanometer-sized range
are used as photoanode materials due to its high porosity and high surface roughness
and high specific surface area. TiO2 is an n-type semiconducting nontoxic oxide
material with a high refractive index (n) of 2.4–2.5 which is widely used for various
applications such as a white pigment in paint, self-cleaning materials, photocatalyst,
toothpaste, sunscreen. The rutile phase of TiO2 is the most thermodynamically sta-
ble form out of its several popular polymorphs such as rutile, anatase, and brookite.
Anatase phase is commonly preferred for DSSC application because of its larger
bandgap (3.2 vs. 3.0 eV for rutile), large specific surface area, and a higher con-
duction band edge energy (E c ) [49, 79]. TiO2 nanoparticles work as chloroplast in
leaves (that is why called artificial photosynthesis), which allows more dyes to inter-
act with the photoanode surface, thus increasing the light absorbance in the cell. The
doctor blade technique for a colloidal solution of TiO2 NPs, screen printing tech-
niques, chemical methods, and physical vapor deposition techniques is very common
to deposit nanocrystalline n-type TiO2 thin films on glass substrates. The choice of
photoelectrode materials is subjected to its cost, toxicity, and chemical stability under
light irradiation in solution so that it does not decompose due to photocorrosion. That
is why the expensive substrates such as Ge, InP, Si, GaAs, and CdS are not suitable
for DSSC device applications. It is important to have nanopores to increase the sur-
face roughness in TiO2 (photoanode) material so that more dyes can be adsorbed (on
the order of 10−7 mol/cm−2 ) to improve the device performance [63]. In the current
scenario, various photoanode nanomaterials of different shapes and sizes (e.g., ZnO,
ZnO/TiO2 , mixture of anatase and rutile phase TiO2 ) with high porosity are of great
interest to further improve the performance of DSSC [29, 41, 63, 75, 80–83]. The
efficiency of DSSC strongly depends on the physical and chemical properties of
photoanode materials such as morphology (nanorods, nanowires, nanospheres, nan-
otubes, nanocubes, etc.), nature of dopants, light scattering, porosity, and fabrication
techniques [58, 84].
Dyes: The choice of dye is also an important parameter. Dyes are the heart of
DSSCs which stimulate the photon absorption and electron injection to the pho-
toanode materials. A dye must have attachment groups such as phosphonate or car-
boxylate to firmly bind itself to the TiO2 surface by the chemisorption process to
ensure the spontaneous assembling of dye molecules. Ru-based complex photosen-
sitizer such as cis-bis(4,4 - dicarboxy-2,2 -bipyridine)dithiocyanato ruthenium(II)
(RuL2 (NCS)2 complex) also named as N3 dye (or red dye) with an absorption
range of 400–800 nm and trithiocyanato 4,4 ,4 -tricarboxy-2,2 :6 ,2 -terpyridine
ruthenium(II) (black dye) (RuL’(NCS)3 complex), with an absorption range up
to the near-IR region, have been widely used in traditional DSSCs [43, 63]. The
192 M. C. Mathpal et al.

absorption process in dyes is assisted by metal-to-ligand charge-transfer (MLCT)

transition between the highest occupied molecular orbital (HOMO) and the low-
est unoccupied molecular orbital (LUMO). The HOMO and LUMO are originated
from the d-orbitals of the Ru metal and the π ∗ orbital of the ligand, respectively.
Many scientists prefer to use natural pigments, like anthocyanins and betanin,
which are found in many berries and other plants [43, 50, 85–87]. Anthocyanins
strongly bind to TiO2, and its color varies with the pH ranging from red, blue,
to purple [43]. Nowadays, di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2 -
bipyridyl-4,4 -dicarboxylato) ruthenium(II) popularly named as N719 standard dye
(C58 H86 N8 O8 RuS2 ) is frequently used for high performance of DSSC [88]. This
dye has high stability, amphiphilic nature, deeper HOMO energy levels (increased
oxidation potential) and even higher electrostatic binding onto the TiO2 surface at
low pH values. Many other dyes such as metal-free organic dyes, metal complexes,
porphyrins, phthalocyanines with large molar extinction coefficients, whose LUMO
levels are more negative with the CB level of the photoanode materials and the
HOMO is more positive than the energy level of redox couple of the electrolytes can
also be utilized as photosensitizers for DSSCs [2, 49, 61, 63, 89–93]. Besides using
these dyes, a mixed solution of different dyes (called co-sensitization) for photosen-
sitization can be used in order to improve the spectral response of the DSSC onto
the surface of mesoporous TiO2 [49, 57, 61, 89].
Electrolytes: The main role of the electrolyte solution is the propagation and
separation of charge carriers in the DSSC. In the traditional DSSC triiodide/iodide
(I− −
3 /I ), electrolyte solution has been frequently used to mediate electrons between
the TiO2 photoanode and the counter electrode (photocathode). Once a dye molecule
absorbs the sunlight, then it transfers an electron to the TiO2 surface leaving behind
a positive charge on dye molecules [1, 36, 63, 94]. To neutralize this positive charge
on dye, it again requires an electron in order to continue the light absorption process
in the solar cell. The I− −
3 /I electrolyte solution serves as a source of electron to make
dye molecules neutral and generally referred as “ferry” electrons between the counter
electrode and the dye molecules. The triiodide (I− 3 ) works as an electron acceptor,
while iodide (I− ) works as an electron donor in the electrolyte solution. To reduce the
oxidized dye (S+ ) rapidly to its neutral state (ground state S), the electrolyte solution
must contain enough iodide ions. This is accompanied only by the fast migration of
triiodide to the counter electrode (CE) where it accepts the missing electron to regen-
erate the iodide (electron donor) ions, which is donated to the oxidized dye to bring it
back in chemically stable ground state [35, 63, 94]. Thus, a circuit is being completed
via donating an electron by iodide to dye while accepting the electrons by triiodide
at CE through an external circuit. The basic necessity of an electrolyte solution for
DSSC applications is its chemical stability, full reversibility, low viscosity for good
dispersion and rapid diffusion of charge carriers, no absorption in the UV-visible light
range, no desorption of dye, no degradation of TiO2 (or anther semiconductor) at
photoanode, and most importantly, it should be compatible with the sealing materials
[35, 36]. The electrolytes based on the bromide/tribromide (Br− /Br− 3 ) redox couple
has a more positive redox potential (about 1.1 V vs. NHE); therefore, it can also
improve the photocurrent in the DSSCs with the use of suitable dyes [36]. Another
Basic Concepts, Engineering, and Advances … 193

primary choice of an electrolyte solution is based on [Co(bpy)3 ]2+/3+ redox couple,

which was recently used by Prof. Gratzel group and other researchers to achieve a
DSSC of highest power conversion efficiency so far (12.3 and 13%) by molecular
engineering of porphyrin sensitizers [4, 9, 15, 42].
Photocathode (counter electrode): The counter electrode (CE) plays an impor-
tant role to collect the electron passing through the external circuit so that the circuit
is complete to flow the current across the device. This is usually the same substrate
as used for photoanode materials with a difference of platinum (Pt) coating of about
150–200 nm thickness (or roughly 5–10 μg cm−2 ) on ITO/FTO (or any other TCO)
substrates [11, 63]. The CE is placed over the top of the photoanode materials to com-
plete the device formation. The Pt is widely used due to its high electrical conductivity
and high electro-catalytic activity so that it can easily reduce triiodide (I−3 ) to iodide
(I− ) for the regeneration of dye sensitizer. There are a few other choices such as
carbon, graphitic carbon, and carbon nanotubes (CNTs) to avoid the rarely available
and expansive Pt for counter electrode [95]. Currently, a wide class of materials such
as 2D materials (graphene, WS2 , MoS2 , MoSe2, etc.) and 1D nanostructures are stud-
ied by various research groups as an alternate for Pt-free counter electrodes [16, 35,
54, 96–100]. The important parameters to select a CE material are its environment-
friendly nature, availability, cost of preparation and chemical non-toxicity, etc. There
are many ways such as thermal evaporation, thermal decomposition, chemical vapor
deposition, and hydrothermal reactions to grow CE on ITO/FTO substrates [58].
Cobalt sulfide and poly(3,4-ethylenedioxythiophene) (PEDOT) doped with toluene-
sulfonate anions have also shown good catalytic properties for CE applications in
DSSC for the reduction of triiodide ions [49].
Device packing: It is necessary to encapsulate the device at the end, which
required a sealing material to prevent the leakage of the liquid electrolyte solu-
tion and the evaporation of the solvent used in this solution. The sealing materials
should be compatible with dyes and electrolyte solutions and exhibit a good chemical
and photochemical stability. In this regard, Surlyn 1702 (DuPont), a copolymer of
ethylene and acrylic acid, is commonly used for this purpose [11, 63]. Surlyn has
low melting point; so for the longer stability, a resin (e.g., ethylene vinyl acetate,
EVA) can be used for packaging before sealing of the solar cell. An unsealed device
can also be used for measuring I–V characteristics. In this case, a polyethylene (15–
30 μm thickness) film (called as spacer film) is placed over the dye-coated TiO2
surface and then by using the pipette, one or two drops of electrolyte solution are
dropped on the top of the TiO2 photoanode. After placing the counter electrode on
top of the TiO2 photoanode, two binder clips are commonly used to fasten these two
electrodes (photoanode and CE). Water glass solution or a long-term hermetic seal
(also known as solder glass) is also very effective for sealing [95]. The water glass
solution technique is usually applied after pouring an electrolyte solution, where
both electrodes are adhered and hardened well to each other by drying and reaction
with atmospheric carbon dioxide without any external heating. Sometimes, it shrinks
after natural drying and creates cracks, which may results in leakage through sealing.
However, this leaking may be reduced to some extent by the addition of glycerol or
some hygroscopic plasticizer.
194 M. C. Mathpal et al.

4 Device Construction of DSSC

DSSC preparation: In general, the pure anatase TiO2 (many researchers use com-
mercial powder P25) or doped TiO2 nanoparticles can be either spin/spray coated
onto ITO/FTO substrate or deposited by the doctor blade techniques [1, 58, 63, 79,
101]. TiO2 nanoparticles can be synthesized by various techniques such as sol–gel,
co-precipitation, and hydrothermal methods [49, 102–106]. The one simplest and
oldest is the doctor blade technique where TiO2 powder after grinding is usually
dispersed with water, ethanol, or nitric acid, etc., and particle stabilizer (e.g., acety-
lacetone) along with a nonionic surfactant (e.g., Triton X) are added [63]. This forms
a colloidal TiO2 paste solution, which is then spread with a glass rod on the top of a
ITO/FTO (or any TCO) substrate and then further calcined in between 400–500 °C
for 2–4 h in the atmospheric condition resulting into a transparent film. Before coat-
ing on the substrate, its top conducting surface should be covered from all four sides
with a scotch tape so that after completing the device, this area can be used to collect
the charge carriers and seal the device. Nowadays, researchers are modifying the
architecture of DSSC, where they use a TiO2 blocking layer (approximately thick-
ness of ~50 nm) on FTO, then a mesoporous TiO2 light absorption film (~10 μm
thickness with average particle size of ~20 nm diameter), then a light-scattering
layer of TiO2 NPs (~3 μm porous layer with 400 nm size) on the top of the meso-
porous film, and finally followed by TiCl4 treatment and heat treatment to improve
the performance of impure Degussa P25 TiO2 nanoparticles [11, 49]. The TiO2 thin
film (after calcination) can be immersed for 14–24 h in ethanolic solution (or for a
different time in different solutions) of ruthenium dye N945 (many other different
dyes with a different solution in various concentrations can be used to improve and
optimize the best efficiency in DSSC). Once the dye is completely adsorbed on the
TiO2 surface, the substrate can be cleaned with deionized water first and then by
isopropanol to remove water content around the surface. Now another Pt or carbon-
coated ITO/FTO glass substrate surface (of similar exposure area as of photoanode
made of TiO2 semiconductor) is placed on the top of dye-adsorbed TiO2 surface in
such a way that the device can be connected to an external load in the circuit. Now,
the device should be sealed (or closely packed) from two/or three sides so that the
few drops of an electrolyte solution can be uniformly immersed inside the cell to
reduce the oxidized dye molecules to its ground state to flow the current through
the circuit. Finally, the DSSC is ready to expose to the solar energy (the photoan-
ode side should face the irradiation of white light) where one can measure the dark
current and photocurrent by recording the I–V characteristics of the device. There is
much advancement in the fabrication of traditional DSSC [54, 63, 95]. A schematic
fabrication of a simple DSSC with various possibilities is shown in Fig. 2, whereas
a specific design that is widely adopted for DSSC designing as suggested by Prof.
Gratzel group and their coworkers is represented in Fig. 3 [11, 38].
Gratzel et al. [11] performed TiCl4 treatments for two times while preparing
the TiO2 photoanodes for DSSC. The TiCl4 treatments were applied before and
after the screen printing of the mesoporous TiO2 films (Fig. 3). This treatment not
Basic Concepts, Engineering, and Advances … 195

Fig. 2 Simple design for fabrication of a dye-sensitized solar cell. Reproduced with permission
from journal Ref. [38], Copyright 2018, The Royal Society of Chemistry

only enhances the bonding between the FTO substrate and the porous-TiO2 film
but also helps in blocking the charge recombination between electrons coming out
from the FTO and the I− − −
3 ions of the (I3 /I ) electrolyte solution. The influence of
TiCl4 treatments in current conversion efficiency is clearly evident from Fig. 4. In
specific DSSC designs, the inclusion of “double-layer TiO2, ” which consists out of
a transparent TiO2 film of 14 μm thickness and a microcrystalline light-scattering
layer of 5 μm thickness of TiO2 nanoparticles (400 nm size), is used to enhance the
photocurrent of DSSC (Fig. 4). The light conversion efficiency was increased to η
= 10.1% from 9.12% with the use of light-scattering layer [11]. This layer helps
in trapping more photons and in active photovoltaic generation. The thickness of
the double-layer TiO2 is crucial, which plays an important role to optimize the best
photovoltaic performances of DSSC. Figure 5 shows the effect of the TiO2 layer
thickness on the power conversion efficiency of DSSC [11]. The best-optimized film
thickness is about 12–14 μm (with the adherence of an extra anti-reflecting coating
layer) to produce a highly efficient DSSC [11].
196 M. C. Mathpal et al.

Fig. 3 Specific configuration for designing a TiO2 -based dye-sensitized solar cell of high efficiency
as suggested by Prof. Gratzel group. Reproduced with permission from journal Ref. [11]. Copyright
2007, Elsevier B. V.

Fig. 4 Influence of TiCl4

treatments on PCE of
TiO2 -based DSSC.
Reproduced with permission
from journal Ref. [11].
Copyright 2007, Elsevier B.
V
Basic Concepts, Engineering, and Advances … 197

Fig. 5 Influence of total

TiO2 thin film (double layer
+ anti-reflecting coating
layer) thickness on PCE of
DSSC. Reproduced with
permission from journal Ref.
[11]. Copyright 2007,
Elsevier B. V

5 Basic Characterizations for DSSC

It is important to understand the material characteristic before its applications. There-

fore, in this section, a few necessary characterizations techniques are discussed. X-
ray diffraction (XRD) is one primary tool to confirm the structural behavior of the
materials. For example, the commonly used anatase TiO2 or a mixed phase of TiO2
(anatase 70%—rutile phase 30% like as P25 commercial sample) and phase purity
of any photoanode materials can be easily optimized by recording its XRD pat-
tern. Raman spectroscopy is further helpful to differentiate among different phases
of various semiconducting materials. Scanning electron microscope (SEM), trans-
mission electron microscopy (TEM), and atomic force microscopy (AFM) are very
important to realize the microstructure behavior (particles shape, size, distribution
and surface roughness, etc.) and cross section (for growth orientation and thickness,
etc.) of the photoanode materials. Energy dispersive X-ray spectroscopy (EDX) and
X-ray photoelectron spectroscopy (XPS) are very useful to confirm the presence of
elements and detect any impurities that can unintentionally persist in the samples.
The film thickness of photoanode layers can be determined by using a surface pro-
filer (Tencor P-10). UV-visible absorption spectra is very crucial to record to see the
absorption profile of the dye molecules and photoanode materials, whereas photo-
luminescence (PL) spectroscopy can be very helpful to understand the defect states,
which are responsible for influencing the efficiency of DSSCs. Electrical transport
measurements are required to measure the conductivity of the photoanode materials
and conducting substrates, etc [53]. Brunauer–Emmett–Teller (BET) surface ana-
lyzer is useful to get information about pore size distribution and specific surface
area, which provides an idea about the physical adsorption of gas molecules on a
solid surface. Time-correlated single photon counting (TCSPC) and transient absorp-
tion spectroscopy are useful to measure the fluorescence lifetime and to understand
the charge carrier dynamics in the DSSC. Similarly, the electrochemical impedance
198 M. C. Mathpal et al.

spectroscopy (EIS) can be used to analyze the relationship between V OC and the inter-
facial charge transfer kinetics. EIS can be used to determine charge transfer resistance
of the counter electrode, series resistance, diffusion resistance of the electrolyte, the
resistance of electron transport and recombination in the TiO2 , and the chemical
capacitance of the porous TiO2 electrode [22, 49, 53]. Cyclic voltammetry (CV) is
one of most popular electrochemical techniques which is useful to determine the for-
mal potentials of redox processes and obtains the information about the reversibility
of the electron transfer process in the cell. It is also helpful to understand whether
the electrolyte solution is adsorbed on the electrodes or the redox-active species are
free to move in the solution. The energetic distribution of the traps at the surface of a
TiO2 electrode can be deduced from the cyclic voltammograms [49, 107]. Finally, the
prepared devices should be irradiated by solar spectrum simulator in order to obtain
photovoltaic (I–V) characteristics and record the efficiency of the solar cell. The total
electrons concentrations in the TiO2 film under working conditions of the solar cell
can be determined by charge extraction methods, where first light is switched off and
then all remaining charge in the film is extracted as a current during a certain period
and integrated to obtain the charge [49]. In another method, the capacity of the TiO2
film can be measured instead of measuring the charge. To measure this, light pulse
is added at a fixed open-circuit potential, which is obtained by bias illumination and
then the resultant rise in the voltage is measured. The light pulse is used separately
to measure the photocurrents transient under short-circuit conditions, which is used
to determine the injected charge induced by the light pulse. The ratio of injected
charge and voltage change is used to estimate the capacity. Integration of capacity
with respect to the range of open-circuit potentials gives the charge potential relation
[49].

6 Factors Influencing the Efficiency of DSSC

The low cost of the material and fabrication of DSSC is one of the crucial parame-
ters, but the most important is to improve the efficiency of DSSCs. The efficiency of
DSSC extremely depends on the internal conversion of the absorbed photon into the
number of electron flowing through the circuit and is termed as internal photoelectri-
cal conversion efficiency (IPCE) or monochromatic current yield. It is defined as the
total number of injected electrons passing through the external circuit generated after
absorption of light divided by the number of incident photons, which is plotted as a
function of excitation wavelength [1, 63, 108]. The typical anatase TiO2 nanoparticle-
based photoanode DSSC has shown remarkable power conversion efficiency (PCE)
owing to their large specific surface area for adsorption of the dye molecules. The
poor conversion process in TiO2 films is mainly due to the structural disorders such
as misaligned crystallites, unwanted impurities, and lattice mismatches at the grain
boundaries, which limits the electron transport mechanism and reduces the electron
lifetime [63]. In order to resolve such issues, many researchers are developing one-
dimensional (1D) nanostructures (nanorods (NRs), nanowires (NWs), or nanotubes
Basic Concepts, Engineering, and Advances … 199

(NTs)) and mesoporous structure as photoanode materials due to their excellent

electron transport and light-scattering ability [17, 109, 110]. DSSC based upon Ru
complex dyes is very efficient to convert light energy into the current. The IPCE of
90–100% can be achieved in the ITO/FTO (or other TCO substrates) as the losses due
to light reflection and absorption are considerably small [63]. IPCE at a wavelength
(λ) can be calculated by the following equations [1, 63, 108]:
 
1240(eV nm) × Jsc μA cm−2
IPCE(%) =   × 100 (8)
λ(nm) × ∅ μW cm−2

IPCE can be directly determined by the light-harvesting efficiency (LHE) of the

dye adsorbed on the photoanode material (or TiO2 film) [1, 8, 36, 63]:

IPCE or ηi (λ) = LHE (λ).∅in j ηe (9)

kin j
∅in j =  −1  (10)
τ + kin j

LHE(λ) = 1 − T = 1 − 10−A (11)

and

A = .σ (λ) = α.d(for film) (12)

where J SC is the short-circuit photocurrent density for monochromatic irradiation,

is the monochromatic light intensity, LHE (λ) is defined as the fraction of incident
light flux that is absorbed by the dye, ∅in j is the quantum yield of electron injection,
ηe is the electron collection efficiency of the injected electrons collected at the back
contact of photoanode, which is measured as the ratio of electric current to the
incident photon flux at a given wavelength, kin j is the rate constant for electron
injection, τ is the lifetime of excited state in the absence of electron injection. T
is the transmission, A is the light absorbance by the photoanode material,  is the
number of moles of dye molecules per square centimeter of working surface area on
the photoanode film, and σ (λ) is the absorption cross-sectional area per unit mole
(unit cm2 /mol) which can be obtained from the decadic extinction coefficient (unit
M−1 cm−1 ) by multiplication with 1000 cm3 /L, α is associated with the reciprocal
of the light absorption length (1/α), and d is the film thickness [1, 63, 108]. Finally,
the power conversion efficiency (ηglobal ) from solar energy to electric energy under a
source of white light illumination (e.g., AM1.5) can be determined by the following
equation:

Voc × Jsc × F F
ηglobal (%) = × 100, (13)
∅
200 M. C. Mathpal et al.

FF can be written as:

Vmax × Jmax
FF = , (14)
Voc × Jsc

where ∅ is the incident photon energy (ideally 100 mW cm−2 for AM1.5), Jsc is the
short-circuit current density and V oc is the open-circuit voltage, FF is the fill factor,
J max and V max are the current density and voltage obtained, respectively, at the point
of maximum power output in the current versus voltage (J–V) graph [45, 58, 63].
The V OC in DSSC can be written as a function of the injection current,
 
nkT Iin j
VOC = × ln +1 , (15)
q I0

where k (R/N A ) is the Boltzmann constant, n is the ideality factor whose value is
between 1 and 2 for the DSCC, q is the magnitude of the electron charge, T is the
absolute temperature, photocurrent density measured at short-circuit (I inj ) condition,
and I 0 is the dark current. I inj and I 0 are given by

Iin j = q.η.∅ (16)

 
I0 = q.η0 ket I−
3 (17)

where η is the quantum yield for photogenerated electrons, is the photon flux of
incident radiation, n0 is the density of electron in the CB of the semiconductor in the
dark condition, k et is the rate constant for recombination, and [I−3 ] is the concentration
of I−
3 oxidized redox mediator in the electrolyte solution. The open-circuit voltage in
DSSC can be increased if the rate constant for triiodide reduction (k et ) is decreased.
The electron transfer rate from the dye molecules to the CB of semiconductor (TiO2
or other materials) depends on how the sensitizing dye is adsorbed on the surface of
the semiconductor and the energy gap between the LUMO level of the sensitizing dye
and the CB of the semiconducting materials. The rate constant for electron transfer
to CB of semiconductor is given by the equation of Fermi’s golden rule:
 
4π 2
K in j = × |V |2 × ρ(E), (18)
h

where V is defined as electronic coupling which largely depends upon the gap
between the sensitizing dye molecules and the semiconducting material surface,
ρ(E) is the density of states of the CB of the semiconductor, and h is the Planck
constant [63]. The slow response of the photocurrent in DSSC is due to the very
small electronic conductivity of TiO2 . The electron conductivity and photocurrent
response can be improved if the diffusion coefficient of the electron is increased due
to the filling of the trap site and/or surface defects by injected electrons in the TiO2
film. The recombination rate due to the backward electron transfer can be calculated
Basic Concepts, Engineering, and Advances … 201

using the open-circuit photovoltage decay (OCVD) curves after switching off the
light irradiation for the DSSCs. The electron lifetime (τn ) can be determined from
the OCVD curve by using the following equation [107]:
 −1
−kT dVoc
τn = , (19)
q dt

where dV oc /dt is the first-order time derivative of V oc . To improve the conversion

efficiency of DSSC, it is essential to collect the maximum photogenerated charge
carriers. Most of the photogenerated charge carriers can be collected if the electron
diffusion length (L n ) is greater than the film thickness (d) [8]:

1 
L n > d, and d > , where L n = 2 De τn (20)
α
where De is the diffusion coefficient and τn is the electron lifetime. To obtain this,
the film thickness (d) should be significantly thicker than the light absorption path
(1/α).
As seen from the above equations (Eqs. 8–20), the efficiency of DSSC is directly
influenced by several factors such as IPCE, incident wavelength range, spectral sen-
sitivity, and dark current. These parameters depend on the choice of sensitizing dye,
preparation of photoanode materials, catalytic activity of photocathode, and redox
activity of electrolyte solution. To improve the performances of the DSSC, the absorp-
tion property of dye can be extended up to IR range (e.g., using black dye), modifying
anode materials by doping or preparing composite materials, taking the benefits of
light-scattering properties, integrating the plasmonic nanostructures, reducing dark
current by using appropriate absorbers, increasing electron injection, reducing the
recombination between the injected electrons and the redox species, and reducing the
charge recombination between the oxidized dye sensitizer and the injected electrons
in the CB of TiO2 semiconductor [54, 55, 61, 107].

7 Engineering and Advances in DSSC

Several researchers are currently involved in modifying the basic structure of the
DSSC and re-engineering the fabrication of its component separately. The recent pro-
gresses and advancement to beat the main challenges associated with the fabrication
of highly efficient DSSC and its counterparts are briefly addressed here.
202 M. C. Mathpal et al.

7.1 Role of Nanomaterial Properties in DSSC

In order to improve the light absorption, a large amount of dyes need to adsorb on the
anatase TiO2 nanoparticle (NP) surface. So far, anatase TiO2 NPs are considered bet-
ter than any other phase of TiO2 (such as rutile or brookite) for fast electron transport
and superior adsorption of dye molecules. One-dimensional (1D) nanostructures such
as nanowires (NWs), nanorods (NRs), or nanotubes (NTs) have drawn huge atten-
tion due to their excellent charge transport properties and light-scattering ability for
DSSC applications [17, 38, 111, 112]. Wu et al. [17] group have successfully synthe-
sized hierarchical anatase TiO2 nanowire arrays by the hydrothermal method of two
different morphologies on FTO substrates where one was grown with tiny branches
in nanowires while another with long trunks in nanowires to replace TiO2 NPs. A
significant improvement in photovoltaic performance was recorded for hierarchical
TiO2 nanowire arrays (7.34%) as compared to commercial P25 nanoparticle (6.35%)
[17]. The enhanced efficiency was attributed to the high specific surface area, supe-
rior light-scattering ability which increases light-harvesting efficiency, fast electron
transport and longer lifetime of the electron because of its 1D nanostructure with
less grain boundaries and defects, which reduces the charge recombination in the
DSSC. The high efficiency of DSSC was achieved with introducing a compact TiO2
blocking layer of 100 nm thickness (size ~5 nm NPs) between FTO glass substrate
and hierarchical anatase TiO2 arrays film by spin coating, which improves the power
conversion efficiency by 9% (from 6.74 to 7.34%). The engineering for hierarchical
TiO2 nanowires array-based DSSC device is shown in Figs. 6 and 7a, whereas their
photocurrent density–voltage (J–V) graph is depicted in Fig. 7b, where the inset in

Fig. 6 Schematic for the formation of hierarchically anatase TiO2 arrays on FTO glass as a function
of hydrothermal reaction time. The figure is adopted from Ref. [17]. Open access journal; reproduced
under Copyright 2013, nature scientific report
Basic Concepts, Engineering, and Advances … 203

Fig. 7 a Hierarchical anatase TiO2 nanoarray-based DSSC with a blocking layer and platinum
counter electrode, b J–V characteristics of DSSC shown in (a), and the IPCE spectrum is shown
in the inset image. The figure is adopted from Ref. [17]. Open access journal; reproduced under
Copyright 2013, nature scientific report

the graph is the IPCE spectrum for Fig. 7a. The main role of blocking layer was to
reduce charge recombination in FTO/electrolyte interface and enhance the adhesion
between hierarchical anatase TiO2 arrays and FTO glass surface due to its high den-
sity and large contact area of quantum size TiO2 nanoparticles [17]. In a similar work
performed by their group on the hierarchical anatase TiO2 nanowire arrays consisting
tiny branches grown on Ti metal foil has also shown remarkable enhancement in PCE
as compared to that of TiO2 nanowire without the branches [111]. In traditional TiO2
photoanode, the electrons generated from the dye molecules have to travel through
various grain boundaries in order to reach the FTO/ITO surface of the electrode, and
the migration of electrolytes solution is not efficient due to the irregular distribution
of the pores. To avoid traditional TiO2 photoanode, Kim et al. [113] have designed a
simple, cost-effective novel hierarchical pore structure with high surface area having
large number of tiny internal pores (~diameter 10.5 nm) on TiO2 sphere (~ diameter
250 nm) and large external pores (~diameter 150–300 nm) among the bridging spher-
ical TiO2 nanostructures to act as nanoporous TiO2 photoanode. DSSC formed by
using the 250-nm-sized TiO2 spherical structures had also shown a good scattering
effect with a high light conversion efficiency of 10.2% [113].
Law et al. [18] reported the use of crystalline ZnO nanowires as photoanode in
the replacement of traditional mesoporous TiO2 nanoparticles. Their results showed
a fast collection of charge carriers generated throughout the device, with a full power
conversion efficiency of 1.5% which is limited by the surface area of the nanowires.
In their engineering, first FTO substrates (TEC-7, 7 /square) were cleaned by ace-
tone/ethanol sonication and then ZnO QDs of 3–4 nm in diameter were deposited
by dip coating followed by an array of ZnO nanowires. The rapid electron injection
was attributed to the direct electrical pathways, higher crystallinity, and an internal
electric field which assists charge carrier collection by separating injected electrons
from its surrounding electrolyte [18]. Miao et al. [22] have developed multilayered
204 M. C. Mathpal et al.

photoanode material-based DSSCs with a high efficiency of 11.05% by a simple

film transfer technique. They used two different dyes for independent absorption in
visible and near-IR (NIR) region (two different spectral regions) of the spectrum for
broadening the absorption spectra. The multilayered photoanode design was stacked
as TiO2 /dye 1/transferred TiO2 /dye 2. Two model dyes N719 and BD were used to
improve the efficiency and confirm the cell structure [22]. The film transfer tech-
nique showed a new way to develop the DSSC where the V OC of visible and NIR
dye has mismatch problem. Interestingly, the V OC of multilayered DSSC was closer
to the higher V O when two dyes with different V OC were used, which resembles
with the different degree of back reactions at the TiO2 /dye/electrolyte interface [22].
Subramanian et al. [80] reported a DSSC based on mixed-phase (anatase 88% and
rutile 12%) TiO2 photoanode (NP-450) which has two morphologies of nanoparticle
(NP) and nanotube (NT) had good conversion efficiency of 5.1% as compared to pure
anatase NT photoanode (3.2% efficiency of NT-450 DSSC). It is believed that, in only
anatase NT photoanode-based DSSC, the high concentration of surface states and
oxygen vacancies triggers the recombination of back-electrons and reduce the resis-
tance between TiO2 photoanode and electrolyte interface, whereas the recombination
is weakened for 12% rutile content of NP-TiO2 photoanode-based DSSC to show
enhanced light harvesting [80]. Special attention was paid by Jiang et al. [114] on the
structural and optical properties of TiO2 blocking layer prepared by spray pyrolysis
method for the application in all solid-state DSSCs. They optimized and studied the
influence of deposition temperature and post-annealing temperature on the perfor-
mance of solid-state DSSCs. The best-achieved efficiency (4.6%) was recorded for a
blocking layer deposited at 300 °C with post-annealing at 550 °C, which is attributed
to the high purity, smooth surface, dense grain packing and increased crystallinity of
the post-annealed films [114].
In recent years, many other tactics have been used for engineering the photoanode
materials in highly efficient DSSCs. The few uncommon approaches to improve the
power conversion efficiencies are deposition of TiO2 NPs on the surface of titanium
oxide nanotube (NT’s) by surface anodizing for a DSSC of 7.4% PCE [115]; PCE
of 8.71% with nanoporous TiO2 -based photoanode [116]; PCE of 6.9% by growing
vertically aligned TiO2 nanotubes on FTO [19]; modifying the surface chemical
states of TiO2 [117]; cubic aggregates of Zinc Tin Oxide (Zn2 SnO4 or ZTO) NP-
based photoanode material (PCE of 4.9%) [118]; natural cellulose fiber-based bio-
derived photoanodes in combination with biopolymer electrolyte for paper-based
quasi-solid DSSCs with a PCE of 3.55% [48]; using titanium metal foil as substrates
for DSSC [77]; depositing TiO2 (anatase and rutile mixed phase) by spray coating
onto CdS nanorods for photoanode [119]; ZnO nanowire network within a TiO2
nanoparticle film [82]; PCE of 9.3% with single crystal-like anatase TiO2 nanowires
by exposing (101) plane [84]; solvothermal-modified TiO2 photoanode with a PCE
of 8.51% [120]; using high surface area thin anatase TiO2 nanoleaves with TiO2 NPs
with a PCE of 6.5% [121]; PCE of 7.32% by using tri layer TiO2 as photoanode in
quasi-solid electrolyte-based DSSC [122]; ZrO2 as a barrier layer on TiO2 nanofibers
(PCE 6.72%) [123]; N/TiO2 nanobelt-based photoanodes [124]; nanoscaled Ag/TiO2
photoanode [125]; multishelled ZnO hollow microspheres of large surface area and
Basic Concepts, Engineering, and Advances … 205

good scattering properties with a PCE of 5.6% [126]; using TiO2 nanoparticles (15–
30 nm) and TiO2 cubic particles (100–600 nm) as the scattering layer to achieve a
PCE of 8.21% from 7% for without cubic TiO2 [127]; and metal ion (Al + W)-doped
TiO2 photoanode [128].

7.2 Dyes and Electrolytes Compatibility in DSSC

The selection of dyes and electrolyte solution between the photoanode and the photo-
cathode inside the cell plays a crucial role for stable performance of a DSSC because
the electrolyte solution is responsible for continuous charge transport and oxida-
tion/reduction mechanism for regeneration of dye molecules. The solvent being used
for electrolytes should be of low viscosity for rapid and uniform diffusion of charge
carriers of the redox couple. The solution must be compatible with most of its compo-
nents such as dye to avoid desorption of the dye, electrode to prevent disintegration of
photoanode materials, and sealing materials of the DSSC. To avoid the degradation
and leakage in traditional DSSC due to liquid electrolyte solution, the development
of quasi-solid-state DSSC has also been explored. In these, DSSC liquid electrolyte
is replaced by a hole transport layer which can be made of grafted nanoparticle com-
posite electrolyte, polymer gels, and ionic liquids [43]. Chung et al. [88] showed a
low-cost solution processable p-type semiconductor material CsSnI3 having a direct
bandgap of 1.3 eV and can be used for hole transportation instead of a liquid elec-
trolyte solution. Their solid-state DSSC structure has shown a high PCE of up to
10.2%, which was consist of nanoporous TiO2 as photoanode, CsSnI2.95 F0.05 (doped
with SnF2 ) as hole transport layer and a compatible dye N719 [88]. The main problem
associated with solid-state DSSC is the higher recombination and low injection of
charge carriers to the CB of photoanode, whereas the rare metal Ru-based traditional
dye complexes are expansive. Han et al. [129] have designed simple donor–acceptor
type co-adsorbents (Y1) for black dye and used with I− /I− 3 redox mediator to obtain a
highly efficient DSSC with PCE of 11.4%. The main role of co-adsorbents is to reduce
the charge recombination, overcome the light absorption by I− /I− 3 , and avoid dye
aggregation in the DSSC [129]. Yella et al. [51, 130] have followed a new approach
to avoid an excessive loss of voltage during the dye regeneration reaction from I− /I− 3
redox couple and achieved a high PCE of 11.9%. They used Co(II/III) tris(bipyridyl)
redox electrolyte and developed new inexpensive sensitizers based on D-π-A zinc
(Zn) porphyrin dye, which is designated as YD2-o-C8 [51, 130]. Here an electron
donor (D) moiety is connected to an electron acceptor moiety (A) through a conju-
gated π bridge (π-bonded). The alkoxy chains were attached to the sides of these
molecules to effectively prevent the recombination between electrons in the TiO2
lattice and holes in the Co complexes. They found that the efficiency can be further
improved up to 13.1% by reducing the light irradiation intensity by 50% because it
is less important for the ions to diffuse to the electrode quickly with the lower carrier
density [51]. Yum et al. [4] achieved a high PCE of more than 10% with the use
of cobalt complex (tridentate ligands [Co(bpy-pz)2 ]3+ /2+ (PF6 )3/2 ) as redox mediator
206 M. C. Mathpal et al.

with a cyclopentadithiophene-bridged donor–acceptor dye (Y123) and PProDOT-

based counter electrode. Recently, Freitag et al. and Michael Grätzel group [13]
developed a DSSC of high PCE of 11.3% by combining two dye sensitizers named
as D35 (Dyenamo commercially available) and XY1 with the copper(II/I) complex-
based electrolyte solution. Their proper engineering and research on co-sensitizing
activity of two dyes paved the way to improve the efficiency of DSSC by mixing of
dyes of different spectral absorbance in visible region and replacing the commonly
used iodide/triiodide and cobalt trisbipyridine ([Co(bpy)3 ]2+/3+ ) electrolytes by using
a new copper(II/I) complex-based electrolyte solution [13, 131]. D35 absorbs mainly
blue and green light, whereas the XY1 was used to covers the yellow and red spec-
tral region of the solar light. It has shown that electrolyte proportion and type of
solvents strongly influence the performance of DSSC. Organic solvents are stable
and considered better in PCE performances than that of inorganic solvent owing to
its lower viscosity for preparing electrolyte solution of DSSC [132]. A comparison
of PCE of DSSC based on widely used different dyes such as Ru complexes, organic
dyes, and porphyrin dye is shown in Fig. 8 [38]. Kuo et al. [133] have developed a
technology for the fast fabrication of DSSC, which is equally efficient like traditional
methods and saves lot of time by rapid bombardment of dye solution droplets on the

Fig. 8 Comparison of PCE performances of different dyes for TiO2 -based DSSCs. Reproduced
with permission from journal Ref. [38], Copyright 2018, The Royal Society of Chemistry
Basic Concepts, Engineering, and Advances … 207

Fig. 9 Schematic for

electron dynamics and
lifetime in the
cis-Ru(dcbpy)2 (NCS)2 -
sensitized TiO2 with I− /I−
3
redox mediator in DSSCs.
Reproduced with permission
from journal Ref. [94],
Copyright 2009, American
Chemical Society

photoanode surface. Boschloo et al. [94] have studied the charge dynamics of the
cis-Ru(dcbpy)2 (NCS)2 -dye-sensitized TiO2 solar cell with I− /I− 3 redox mediator (see
Fig. 9). Figure 9 clearly shows the different transition, including from dye absorption,
electron injection, and dye regeneration, takes different timescale for the successful
operation of DSSC. Charge dynamics helps to improve the performances of DSSC
by understanding the migration of charge carriers and recombination losses inside
the cell. Antila et al. [134] used transient absorption (TA) spectroscopy to monitor the
charge transport with ruthenium bipyridyl dyes N3 and N719 dye separately inside
the solar cell. Injection dynamics in both the N3 and N719 dyes were found to be
similar in order of femto- to picosecond timescale, whereas in the presence of the
I− /I−
3 electrolyte solution, it was nanosecond time domain indicates the slower charge
injection process as compared to the presence of only dyes. Moreover, the excited
state lifetime of the dyes was increased in the presence of the electrolyte solution
implying that injection efficiency remains high despite the slower electron injection
process as compared to neat solvent. Beside this, it is important to note the first time
initial dye regeneration takes place in a few picoseconds after the electron injection
[134]. Hao et al. [135] have studied the effects of three electrolytes solvents (3-
methoxypropionitrile, N,N dimethylformamide, and g-butyrolactone) on the charge
transport and electron recombination at the semiconductor–dye–electrolyte inter-
face. Their observation showed that V oc of the DSSC varies linearly with the dipole
moment of the solvents, dipole moment of the solvents can modulate the CB edge of
TiO2 with respect to the redox potential of the electrolyte and charge collection effi-
ciency can be changed. Kakiage et al. [136] have achieved a highly efficient DSSC
with PCE of 14.3% by co-photosensitization of alkoxysilyl anchor dye ADEKA-1
and a carboxy-anchor organic dye LEG4 with an optimized cobalt(III/II) complex
redox couple-based electrolyte solution and a graphene nanoplatelets (GNP)-based
CE. The collaborative sensitization of carboxy-anchor organic dye LEG4 with the
silyl-anchor dye ADEKA-1 and the strong adsorption of ADEKA-1 to the TiO2
photoanode are mainly responsible for the large enhancement in the photovoltaic
performances of the DSSC. In collaborative sensitization, the efficiency of elec-
tron injection is increased because the LEG4 molecules exist near the ADEKA-1
208 M. C. Mathpal et al.

molecules on the TiO2 surface; therefore, the electron from the excited ADEKA-1
dye molecules also transferred to the co-adsorbent LEG4 dye, and then, an electron
is immediately injected from LEG4 to the CB of the TiO2 photoanode. The effi-
ciency for the occurrence of this phenomenon is much higher than the direct electron
injection to the CB of the TiO2 photoanode from the light-excited dye molecules of
ADEKA-1 [136]. Recently, Sahito et al. [137] have added LiCl in poly(vinylidene
fluoride) nanofiber as a separator between photoanode and the counter electrode to
improve the ionic conductivity and overall cell efficiency from 8.73 to 7.87%.

7.3 Catalytic Ability of Different Counter Electrodes

The counter electrode is an integral part of DSSCs which collects electrons from
the external circuit and works as a catalyst for the redox reduction in the electrolyte
solution. Many conducting polymers are easy to process, cheap, stable, flexible, and
transparent with tunable properties. Lee et al. [96] have reported a highly conductive
polymer based on PEDOT materials with high catalytic and charge transportability
as an alternate of Pt- and TCO-free counter electrodes. A simple in situ polymer-
ization method was used to prepare highly conductive PEDOT films, which resulted
into a power conversion efficiency of 5.08% as compared to Pt/FTO-based CE of
5.88% efficiency. The PCE is proportional to electric conductivity of the PEDOT film
which can be further increased by modifying the film preparation techniques [96]. The
low-cost PANI-based CE has also shown promising catalytic activity [35]. Mostly,
carbon-based CE is also cost-effective with good stability and good catalytic activity
as an alternate of Pt-free photocathode [35, 97, 136]. So far the highest PCE of 14.3%
was achieved by the use of FTO/Au/GNP (graphene nanoplatelets)-based DSSC [35,
136]. In recent years, many transition metal chalcogenide (TMC)-based CE for DSSC
is also investigated but some of these suffers with the poor conductivity, poor elec-
tron transport, and poor catalytic activity as compared to the Pt-based CE, which
have further scope to improve the use of TMC-based materials as counter electrodes
[16, 35, 138]. TMC based upon 1T metallic phase of molybdenum disulfide (MoS2 )
grown on a FTO glass by a simple temperature-controlled hydrothermal method has
shown excellent catalytic and charge transport properties as a CE for a DSSC of high
PCE of 7.08% [138]. Currently, various 2D materials, TMC-based composites CE,
and alloy-based CE have either comparable or a higher PCE values than that of stan-
dard Pt CE. These are MoS2 /carbon, MoS2 and MoSe2 /thin films deposited on Mo
foil, MoS2 /graphene, MoS2 /CNTs, MoSe2 /PEDOT:PSS, FeS2 , FeSe2 nanosheets,
Fe–Se nanoporous alloy, CoNi alloy, CoNi alloy incorporated porous N-doped car-
bon hybrid (CoNi–NC), TiS2 /graphene, graphene nanoplates, NbSe2 , ternary cobalt
diindium sulfide nanosheet (CoIn2 S4 ), oxygen, and sulfur doping in mesoporous
carbon pillars with a PCE of 10.2%, and NiS2 /graphene hybrid systems for the
fast reduction of triiodide (I− −
3 ) to iodide (I ) [12, 35, 139–142]. Wu et al. [143]
have shown that the platinum nanotubes prepared by simple polycarbonate tem-
plate method-based counter electrode are highly catalytic and much efficient than
Basic Concepts, Engineering, and Advances … 209

the traditional Pt coating on FTO. The PCE of 9.05% was achieved by introducing
MgO as block layer on TiO2 film with Pt NTs as a photocathode. Zhang et al. [144]
have demonstrated a single wire-based DSSC by wrapping a carbon nanotube (CNT)
film around Ti wire-supported TiO2 tube arrays a for transparent electrode having a
comparable PCE to commonly used twisted Pt wire. The PtNi1.07- based CE on ZnO
nanostructure templates prepared by hydrothermal method for DSSC have shown a
high power conversion efficiency (9.08%) with a 43% enhancement as compared to
only Pt-based CE in DSSC (6.35%) [145]. PtNi1.07- based CE is expected to reduce
the cost of DSSC as well as to enhance the catalytic activity and stability of the cell.
Recently, Cheng et al. [146] have designed a highly catalytic CE for I− −
3 /I redox
couple based on 2D MoS2 nanosheets (NS)-supported by Pt nanoparticles (Pt-NPs).
The Pt-NPs/MoS2 NS CE-based DSSCs showed a PCE of 7.52%, which was 8.7%
higher PCE than conventional thermally deposited platinum CE (PCE = 6.92%)
[146].

7.4 Role of Plasmonic Nanostructures in Improving

the Efficiency of DSSC

Noble metal-based plasmonic nanostructures are widely used in various semicon-

ducting oxide materials, and their device structure enables the routing and manipula-
tion of light at the nanoscale for many optical and electronic applications. Plasmons
are a type of wave that moves through the electrons at the surface of a metal when they
are excited by incident light. The study of plasmons wave at the metal–dielectric inter-
face gives an exciting new technology that has recently emerged called plasmonics.
It is based on the interaction process between electromagnetic radiations and con-
duction electrons at metallic interfaces or in small metallic nanostructures, leading to
an enhanced optical near-field of subwavelength dimension. In metal, nanoparticles
localized surface plasmons are collective oscillations of the conduction electrons.
Movement of the conduction electrons upon excitation with incident light leads to
a build-up of polarization charge on the particle surface. This acts as a restoring
force, allowing a resonance to occur at a particular frequency, which is known as the
dipole surface plasmon resonance frequency [147]. To fabricate many optical systems
at metal/dielectric interfaces, where electromagnetic modes called surface plasmon
polaritons (SPPs) offer unique opportunities to confine and control light at length
scales below 100 nm [148]. The surface plasmon–polariton waves, propagates along
with the interface in a plasma-like medium [149]. This includes plasmonic chips that
function as ultra-low-loss optical interconnects, plasmonic circuits, and components
that can guide light within ultra-compact optically functional devices, nanolithog-
raphy at deep subwavelength scale, superlenses that enable optical imaging with
unprecedented resolution, and new light sources with unprecedented performance
[150–153]. Scattering and absorption of electromagnetic waves depend on the size
of the particles. Metallic particles that are much smaller than the wavelength of
210 M. C. Mathpal et al.

light tend to absorb more, and hence, extinction is dominated by absorption in the
metal particles. Metal nanoparticles are strong scatterers of light at wavelengths near
the plasmon resonance, which is due to a collective oscillation of the conduction
electrons in the metal. For particles with diameters well below the wavelength of
light, a point dipole model describes the absorption and scattering of light well. The
scattering and absorption cross sections are given by [154]:
 4
1 2π 2π
Cscat = |α|2 , Cabs = Im|α| (21)
6π λ λ

ε /ε
where α = 3V εpp /εm+2 −1

m
α is the polarizability of the particle. Here V is the particle volume, εp is the
dielectric function of the particle, and εm is the dielectric function of the embed-
ding medium. We can see that when εp = − 2 εm, the particle polarizability will
become very large [154]. This is known as the surface plasmon resonance. At the
surface plasmon resonance, the scattering cross section can well exceed the geo-
metrical cross section of the particle. Nowadays, the main purpose is to exploit the
effect of surface plasmon resonance for increasing the efficiency of plasmonic thin
film-based solar cells, IR photodetectors, biochemical sensing, optical computing,
gas sensors, and even cancer treatments. The surface plasmons offer a promising
way to improve the efficiency of thin film solar cell structures, to avoid large recom-
bination. The photovoltaic loss due to the recombination of electron–hole carriers
mainly interrupts in photovoltaic conversion process of the solar cell, decreasing the
photoexcited photovoltaic current due to defects in the device material and structure.
The defects can result in the recombination of electron–hole carriers before conver-
sion into photovoltaic current, reducing the conversion efficiency [155]. By proper
engineering of these metalloid, dielectric structures such as composition, geometry,
and dimensions the light (or LSPR) can be concentrated, tuned, and “folded” into
a thin semiconductor layer to harvest specific wavelengths of solar light, thereby
increasing the absorption by light trapping in the photoanode materials. Both local-
ized surface plasmons excited in metal nanoparticles and surface plasmon polaritons
(SPPs) propagating at the metal/semiconductor interface are of great interest [156].
The resonant wavelength and SPR intensity depend not only on the nature of the
metal, but also on the size and shape of metallic nanostructures. By manipulating
the composition, shape, and size of plasmonic nanoparticles, it is possible to design
nanostructures that interact with the entire solar spectrum and beyond [150–154].
The effect of surface plasmons based on silver nanoparticles as a means of improv-
ing the efficiency of thin film and wafer-based solar cells has been well explained by
Pillai et al. [147]. Liu et al. [29] have shown the surface plasmon resonance (SPR)
effect enhances PCE (8.91%) by 20% with doped Au@ZnO plasmonic nanoparticles
within the photoanode layers as compared to bare DSSC (PCE 7.5%). In a similar
study, Dhonde et al. [157] showed that the Cu doping in TiO2 matrix induces the
localized SPR effect, which not only reduces the charge carrier recombination but
also enhances the absorption in the visible region and therefore leading to 26% of
Basic Concepts, Engineering, and Advances … 211

PCE (8.65 from 6.41%) enhancement in comparison with undoped TiO2 photoan-
ode. Metal@Oxide core–shell nanostructure of Ag@TiO2 -based photoanode has
shown a high efficiency of 9.0% as compared to bare TiO2 electrode (7.8% PCE)
[158]. The PCE is enhanced by localized electromagnetic field which increases
the optical absorption of dye molecules in solution and decreasing the thickness
of photoanode by 25% for improved electron collection [158]. Brown et al. [159]
have integrated core–shell of Au–SiO2- based plasmonic nanostructure, which exhibit
intense absorption due to surface plasmon resonance in the visible region of the spec-
trum, into dye-sensitized solar cells employing both the iodide/triiodide redox cou-
ple and a solid-state hole transporter spiro-OMeTAD (2,20,7,70 tetrakis-(N,N-di-p-
methoxyphenylamine)-9,90-spirobifluorene). The core–shell structure was designed
to electronically and chemically insulate the Au metal with SiO2 shell, preventing the
possibility of any corrosion at photoanode and allowing unattenuated propagation of
the optical field around the metal nanoparticles. In general, metal nanoparticles can
enhance the absorption in the DSSC by either scattering light which enables a longer
optical path length; or by near-field coupling between the SPP and the excited state of
dye molecules; and by dipole–dipole interaction and resonant energy transfer [159].
Plasmonic monolayer with only Ag, only Au, and both Ag–Au mixed nanopar-
ticles via P4VP on a photoactive mesoporous TiO2 layer has shown a very high
PCE of 9.33% (from 8.82%), 9.53% (from 8.82%), and 10.2%, respectively [160].
A detailed study on Au–ZnO nanocomposites for solar cell application deposited
onto the glass and tin-doped indium oxide (ITO)-coated glass substrates by a simple
and cost-effective spray pyrolysis technique (SPT) at 450 °C has been reported by
Tarwal et al. [161]. They observed the effect of Au concentration on the proper-
ties of ZnO thin films. A compact distribution of spherical grains/clusters of size
~60–80 nm had a clear indication of localized surface plasmon resonance (LSPR)
in optical studies. Moreover, the bandgap energy decreases with Au content in thin
film. A size-dependent study of Au nanoparticle on conversion efficiency was per-
formed by Deepa et al. [24] in DSSC to enhance the power conversion efficiency via
scattering from surface plasmon polaritons by varying the particle size from 20 to
94 nm. It was found that, the conversion efficiency is highly dependent on the size
of the Au nanoparticles [24]. For larger particles (>50 nm), the efficiency was found
to be increased due to constructive interference between transmitted and scattered
waves from the Au nanoparticle while for smaller particles, the efficiency decreases
due to destructive interference [24]. In a similar study, due to the localized surface
plasmon resonance the Au nanoparticles embedded in the nanoparticulate-TiO2 film
strongly absorb the light [162]. Gold nanoparticles of 100 nm in diameter were
incorporated into TiO2 nanoparticles for dye-sensitized solar cells (DSSCs). At the
optimum Au/TiO2 mass ratio of 0.05, the power conversion efficiency of the DSSC
improved to 3.3% from a value of 2.7% (without Au) [162]. A clear physical differ-
ence between the SPP resonances and the dominant metasurface collective resonance
has been studied by Li et al. [163] through the fabrication, characterization, numerical
simulations, and theoretical analysis of plasmonic metasurface with subwavelength
features of two-dimensional Au patch arrays on ITO-coated glass substrate. They
observed the difference between these two resonant phenomena is because of their
212 M. C. Mathpal et al.

sensitivity to the incident angle [163]. The collective metasurface resonance is based
on the plasmonic resonance of an individual metasurface element and only weakly
affected by the array coupling, whereas the SPP-coupled grating modes are lattice
effects that are very sensitive to the incidence angle. Thus, high tolerance of incident
angles and polarization in transmission and reflection of the metasurface resonance
is potentially suggested to be useful for plasmonic solar cell [163]. Chen et al. [164]
have tuned the SPR by varying Au NP’s size in Au-embedded TiO2 nanotubes array-
based photoanode material. The overall PCE of 4.63% was recorded for Au/TiO2
NT with 19.0% enhancement in comparison with the bare TiO2 NT-based DSSC.
The enhanced PCE was attributed to the coupling effect of SPR of small-sized parti-
cles (~10 nm) and scattering effect of large-sized particles (50–200 nm) [164]. Rho
et al. [112] reported an enhancement in PCE of DSSC made with TiO2 nanopar-
ticles (NPs)/nanotubes (NTs)–silver nanoparticle composites. PCE for only TiO2
NPs film is 8.04%; for TiO2 NPs/NTs is 8.78%; and for TiO2 NPs/NTs-Ag@TiO2
NP’s composites is 10.6%. The significant enhancements in PCE were recorded due
to the fast electron transport through nanotubes and plasmonic enhancement of Ag
NPs [112]. Many other common plasmonic structures that have been used so far
for enhancing the efficiency of DSSC are TiO2 –Au plasmonic nanocomposite (PCE
6%) [165]; Au–TiO2, and Ag–TiO2 plasmonic hybrid nanocomposites [166]; Ag
nanoparticle/Nb2 O5 composite as plasmonic surface passivation layer on SnO2 pho-
toanodes with an enhancement of 32% in PCE (total PCE 6.5%) [167]; designing
of Au plasmon-based SiO2 @Au@TiO2 microspheres embedded with Au nanopar-
ticles as photoanode (PCE 7.75%) [168]; post-annealing of Ag plasmonic compact
layer with anatase TiO2 (PCE 9.45%) [169]; TiO2 –Zn nanocomposite photoanode
materials (PCE 1.34% for Zn-doped TiO2 as compared to undoped TiO2 of 0.66%
PCE) [27]; and integration of 1D plasmonic Ag nanowires into the mesoporous
TiO2 photoanode with an enhanced PCE of 9.41% from 7.5% [25]. A schematic for
the incorporation of Ag nanowires-based plasmonic nanostructure in TiO2 layer is
shown in Fig. 10 [25]. A modified two-step injection method was used to synthesize
the Ag nanowires. These Ag nanowires of different concentrations were mixed in
mesoporous TiO2 paste, which was then coated by the doctor blade technique on the
top of a spin-coated TiO2 compact layer on FTO substrate. The J–V characteristics
and IPCE curves for different concentrations of Ag nanowires in mesoporous TiO2
photoanode are shown in Figs. 11 and 12.
Basic Concepts, Engineering, and Advances … 213

Fig. 10 Schematic design of DSSCs with Ag nanowires plasmonic nanostructure-based meso-

porous TiO2 photoanode. Reproduced with permission from journal Ref. [25], Copyright 2017,
Elsevier Ltd

Fig. 11 a J–V characteristic

curve of DSSC and b IPCE
curve for different
concentrations of Ag
nanowires in mesoporous
TiO2 photoanode.
Reproduced with permission
from journal Ref. [25],
Copyright 2017, Elsevier Ltd
214 M. C. Mathpal et al.

Fig. 12 a Short-circuit current density (J sc ) and power conversion efficiency (PCE) plotted as a
function of Ag nanowires concentration in mesoporous TiO2 photoanode, and b open-circuit voltage
(V oc ) and fill factor (FF) are plotted as a function of Ag nanowires concentration in mesoporous
TiO2 photoanode. Reproduced with permission from journal Ref. [25], Copyright 2017, Elsevier
Ltd

7.5 Tandem Dye-Sensitized Solar Cell

A new class of solar cell named as “Tandem solar cell” based on dye sensitization has
recently emerged and showed high light conversion efficiency as compared to simple
DSSC. Conventional DSSC operates on the concept of photocurrent flowing through
the circuit due to the electron injection in the conduction band of n-type photoanode
materials as a result of the dye sensitizations (usually named as n-DSC). A similar
concept is applicable for photocathode materials which operate in inverse mode to
n-DSC are named as p-DSC [170]. In p-DSC, the dye molecules are excited by rapid
electron transfer from a p-type semiconductor material to the dye molecules. If these
p-DSCs and n-DSCs structures are combined together to construct a solar cell, then
Basic Concepts, Engineering, and Advances … 215

it is called as tandem solar cells (T-DSSCs) [170]. In a simple tandem solar cell, an
electrolyte layer is sandwiched between one n-DSC and one p-DSC layer. Yanagida
et al. [171] and Arakawa et al. [172] reported tandem DSCs sensitized by using N719
and black dye (BD) and achieved high PCE of 10.6% and 10.4%, respectively. Chae
et al. [173] have reported a monolithic tandem solar cell of 6.1% PCE by combining
a TiO2 -based n-DSC and a p-DSC consist of solution-processed CuInx Ga1−x Sey S1−y
(CIGS) thin-film solar cell. A systematic design for DSSC/CIGS-based tandem solar
cell is shown in Fig. 13a [173]. The transmittance curve of Y123 dye and IPCE of
CIGS system is shown in Fig. 13b; photon flux of one sun irradiation and transmit-
ted from different components of tandem solar cell is shown in Fig. 13c; and I–V
curve of a single CIGS solar cell with and without a mask is depicted in Fig. 13d.
The [Co(bpy)3 ]2+ /[Co(bpy)3 ]3+ ) redox couple, Y123 organic dye as a sensitizer, and
well-matched counter electrode of PEDOT:PSS were used to achieve high durability
of more than 1000 h in tandem solar cell. The high stability in the tandem solar
cell was due to the less corrosion by the Co2+ /Co3+ electrolyte solution in compar-
ison with iodide (I− /I−3 ) redox couple. In a similar work by Moon et al. [174], a
solution-processed tandem solar which consists of monolithic DSSC/CIGS system
was fabricated with high PCE of 13.0%.

Fig. 13 a Design for a simple DSSC/CIGS tandem solar cell, b IPCE curve of CIGS single
junction solar cell and transmittance curve of Y123-sensitized, TiO2 /PEDOT:PSS-coated FTO
glass, c Photon flux of one sun irradiation (black line), transmitted photon flux from Y123-sensitized,
TiO2 /PEDOT:PSS-coated FTO glass (filled black line), and intergraded photocurrent (blue line),
and d current density (I–V) curve of a single CIGS solar cell with and without a mask. The figure is
adopted from Ref. [173]. Open access journal; reproduced under Copyright 2016, nature scientific
report
216 M. C. Mathpal et al.

Recently, Kwon et al. [175] have engineered a highly efficient two-terminal

DSSC/Si monolithic tandem solar cell with PCE of 17.2%, which is of maximum
efficiency reported among all DSSCs fabricated so far. The cell was fabricated by
controlling and optimizing the optical properties of a PEDOT interfacial catalytic
layer for CE and amount of dye adsorption on TiO2 NP’s surface. They individually
optimized the top DSSC cell and bottom Si cell in order to achieve the best tandem
solar cell. The top n-DSC was designed with coating of a mesoporous TiO2 layer
on a FTO substrate. Porphyrin dye (SGT-021) for sensitization and an intermediate
transparent PEDOT:FTS film as a catalytic layer for CE were used in top DSSC of
tandem solar cell. The absorption band edge for porphyrin dye (SGT-021) is ~800 nm,
whereas ~1200 nm for c-Si layers, both of which act as light absorption layers in
tandem solar cell. When a solar light is irradiated on this tandem solar cell, the top n-
DSC based on dye-coated TiO2 photoelectrode mainly absorbs the short wavelengths
light up to around 800 nm, whereas the low energy radiations up to 1200 nm wave-
lengths are absorbed by the bottom Si solar cell. The high efficiency of this tandem
solar cell was attributed to the elimination of one TCO glass that is used as CE in
conventional DSSC, low resistance, and high transparency of PEDOT interlayer and
excellent current matching between the top and the bottom solar cell. In the bottom
solar cell, a phosphorous spin-on-dopant (SOD) is spin coated on the front surface of
the Si wafer for an n-type emitter and the back surface is coated with 2-mm-thick Al
for a P+ back surface field (BSF) by e-beam evaporation, which is co-fired using rapid
thermal annealing at 950 °C for 1 min. Then the surface passivation of an emitter
surface was done by an 80-nm-thick SiNx thin film deposited by plasma-enhanced
chemical vapor deposition (PECVD). An ITO thin film as a recombination layer
was further deposited on the top of the SiNx passivation layer by using sputtering
method. This ITO layer is desired for the recombination of electrons generated from
the bottom Si cell and the holes coming from the top DSSC [175]. The design of
this tandem solar cell is depicted in Fig. 14. Figure 15a shows the schematic of the
bottom Si solar cell. Figure 15b shows the J–V characteristics of bottom Si solar

Fig. 14 Design of the

tandem solar cell reported by
Kwon et al. [175].
Reproduced with permission
from journal Ref. [175],
Copyright 2016, The Royal
Society of Chemistry
Basic Concepts, Engineering, and Advances … 217

Fig. 15 a Schematic design of the Si solar cells, b J–V curves for a single junction cell with
passivation, c, d energy band diagrams and J–V curves, respectively, for the top and the middle
silver grid of single junction solar cells

cell with emitter layer, SiNx passivation, and BSF layers, respectively. The current
density is drastically increased with the coating of passivation and BSF layers on Si
substrate. Figure 15c represents the energy band diagram for the top and the middle
silver grid of single-junction solar cells. Ag ohmic contact layer of 300 nm thickness
was introduced to reduce the energy barrier between the ITO and n-type Si interface
down to 0.15 from 0.65 eV. Figure 15d shows the J–V characteristics of the bottom
Si solar cell in two different configurations; one is with the Ag grid patterns formed
between the n-type Si and ITO (emitter/Ag/ITO) as shown in Fig. 15a while another
is the Ag grid patterns on top of the ITO layer (emitter/ITO). The high current density
was observed in the case of Ag grid patterns formed between the n-type Si and ITO
(emitter/Ag/ITO). Figure 16a–d shows the comparison of photovoltaic properties for
various kinds of tandem solar cells.
The few main contributions in the advancement of DSSCs have been summarized
in Table 1.
218 M. C. Mathpal et al.

Fig. 16 Comparison of various kinds of tandem solar cells: a 4-terminal (external) and 2-terminal
(internal) tandem solar cells, b IPCE curve of the masked Si solar cell and DSSC, c various tandem
solar cells which are based on TiO2 photoanode in DSSCs, and d other hybrid structure types
of tandem solar cells. Reproduced with permission from journal Ref. [175], Copyright 2016, The
Royal Society of Chemistry

8 Merits and Demerits of DSSCs

Most of the components in dye-sensitized solar cells do not have harmful materials.
The materials used to fabricate the DSSC are easy to use, separate, and get back for
recycling or even can be reused for DSSC panels. The electron injection and operation
principle of DSSC are different than traditional Si solar cell. The major advantage
over other commercially available silicon solar cells or thin-film solar cells, whose
PCE generally lies between 5 and 17%, is the comparatively low-cost fabrication and
to use like rooftop solar collectors owing to their lightweight and mechanical robust-
ness. The different charge dynamics of the photocathode and photoanode inside the
DSSCs allows it to work even in low intensity of light such as under cloudy skies and
non-direct sunlight, whereas in other traditional Si solar cell or thin-film-based solar
cells; usually, the PCE is reduced to a certain limit. The Si solar cells need to cover
in a glass box for the safety reasons which causes heating inside the cell and results
Table 1 Summary of important contributions of DSSC’s development (AM1.5–100 mW cm−2 )
Reference Substrate Photoanode Counter electrode (CE) Dye used Electrolytes used Efficiency
No. and and sheet (PCE—%)
year resistance
[142] FTO glass TiO2 -coated FTO Oxygen and sulfur dual-doped N719 (cisdiisothiocyanato- Iodide/triiodide (I− /I−
3 ) electrolyte 10.2
2019 electrode (total 20 mm (OS-doped) carbon bis(2,29-bipyridyl-4,
in thickness with 49-dicaboxylato)
16 mm absorber thick ruthenium(II)bis-
film and 4 mm for tetrabutylammonium))
TiO2 light-scattering
layer, respectively)
[107] FTO glass, TiO2 paste Pt/FTO Phenothiazine dyes 3-propyl-1-methyl-imidazolium 8.3
2018 TEC8, (PREDCN2) with iodide (PMII, 1M), lithium iodide
Pilkington, 3,4-ethylenedioxythiophene (LiI, 0.2 M), iodide (I2 , 0.05 M), and
8–10 /sq (EDOT) units tert-butylpyridine (TBP, 0.5M) in
acetonitrile/valeronitrile (85:15, v/v)
Basic Concepts, Engineering, and Advances …

[25] FTO glass, Plasmonic Ag Pt/FTO 0.3 mM N719 dye solution Iodide/triiodide (I− /I−
3 ) electrolyte 9.4
2017 10–15 /sq nanowire-based (1:1 vol. ratio of acetonitrile
mesoporous TiO2 and TBP)
photoanode (10 μm) +
TiO2 NPs 4 μm
scattering layer
[13] FTO glass 8 μm of TiO2 (4 μm Poly(3,4-ethylenedioxythiophene) combination of D35:XY1 Copper(II/I) complex-based 11.3
2017 30NRD + 4 μm (PEDOT)-covered FTO dyes (4:1) electrolyte
scattering layer) conducting glass Cu(II/I)(tmby)2 TFSI2/1 (tmby,
4,4 ,6,6 -tetramethyl-2,2 -bipyridine;
TFSI, bistrifluoromethane
sulfonimidate)
(continued)
219
Table 1 (continued)
220

Reference Substrate Photoanode Counter electrode (CE) Dye used Electrolytes used Efficiency
No. and and sheet (PCE—%)
year resistance
[176] FTO glass One transparent layer Pt/FTO Cosensitized (D35/Dyenamo TPAA/Co complex electrolye 10.5
2016 (4 μm) that was Blue) mixture of D35 and TPAA-tris(p-anisyl) amine
printed with colloidal Dyenamo Blue in the ratio of
TiO2 paste (Dyesol 4:3 (0.1 mM: 0.075 mM) in
DSL 30 NRD-T) and tert-butanol: ACN (1:1 (v/v))
one light-scattering
layer (4 μm) prepared
by another paste
(PST-400C, JGC
Catalysts and
Chemical Ltd.)
[175] FTO glass Mesoporous TiO2 PEDOT:FTS conductive polymer Porphyrin dye (SGT-021) Co(bpy)2+/3+
3 redox couple 17.2
2016 and Si (tandem solar cell) and ITO top layer on p-Si (electrolyte solution of 0.22 M
substrate substrate (tandem solar cell) Co(bpy)3 (BCN4 )2 , 0.05 M
Co(bpy)3 (BCN4 )3 , 0.1 M LiClO4 ,
and 0.8 M 4-tert-butylpyridine in
acetonitrile)
[173] FTO glass TiO2 paste PEDOT:PSS, and Al-doped zinc Y123 [Co(bpy)3 ]2+ /[Co(bpy)3 ]3+ 6.8
2016 oxide (AZO) window layer in
bottom CIGS cell
(continued)
M. C. Mathpal et al.
Table 1 (continued)
Reference Substrate Photoanode Counter electrode (CE) Dye used Electrolytes used Efficiency
No. and and sheet (PCE—%)
year resistance
[136] FTO glass, Nanocrystalline-TiO2 FTO/Au/GNP (GNP—graphene Collaborative sensitization of Cobalt(III/II) tris(1,10 14.3
2015 9-11 /sq.; thin layers (JGC nanoplatelets) carbazole/ phenanthroline) complex
Asahi glass Catalysts and hexyl-functionalized [Co(phen)3 ]3+/2+
Chemicals, oligothiophene/
PST-18NR9) trimethoxysilyl-anchor dye
(ADEKA-1) with
Dibiphenylmonophenylamine
(LEG4 dye)
[9] FTO glass, Mesoporous TiO2 Graphene nanoplatelets/FTO glass SM315 [Co(bpy)3]2+/3+ cobalt(II/III) redox 13
2014 10 /sq. films shuttle
[135] FTO glass, Mesoporous TiO2 Pt/FTO N719 dye, Solaronix, I− /I−
3 electrolyte solution 5.8
2013 15 /sq., layer TiO2 paste Switzerland
Basic Concepts, Engineering, and Advances …

nippon (commercial P25

sheet Glass nanoparticles (Degussa
Co. AG, Germany) and
ethyl cellulose in
terpineol solvent
[17] FTO glass Hierarchical TiO2 Pt/FTO N719 I− /I−
3 electrolyte solution 7.34
2013 nanowire
[88] FTO glass, Nanoporous TiO2 Pt/FTO N719 All solid-state, replacing liquid 10.2
2012 TEC8, films (all solid-state electrolyte by p-type direct bandgap
8 /sq. DSSC) semiconductor CsSnI3
[22] FTO glass, TiO2 multilayers Pt/FTO N719 I− /I−
3 electrolyte solution 11.05
2011 13 /sq.
(continued)
221
Table 1 (continued)
222

Reference Substrate Photoanode Counter electrode (CE) Dye used Electrolytes used Efficiency
No. and and sheet (PCE—%)
year resistance
[15] FTO glass, 5 μm mesoporous Pt/FTO YD2-o-C8 (zinc porphyrin Co(II/III)tris(bipyridyl) 12.3
2011 10 /sq. TiO2 layer dye) tetracyanoborate complexes redox
shuttle
[4] FTO, 4 mm 4.0 + 4.5 scattering Nanoporous Y123, (3-{6-{4-[bis(2,4- [Co(bpy-pz)2 ]3 +/2 + 10.3
2011 thickness, layer with PProDoT poly(3,4-propylenedioxythiophene dihexyloxybiphenyl-
10 /, (PProDOT-coated FTO) 4-yl)amino-]phenyl}-4,
nippon 4-dihexyl-
sheet glass) cyclopenta-[2,1-b:3,
4-b2]dithiphene-2-yl}-2-
cyanoacrylic acid)
[11] FTO glass, Nanocrystalline-TiO2 Pt/FTO 0.5 mM N-719 dye solution 0.6 M BMII, 0.03 M I2 , 0.10 M 10
2008 10 /sq. (20 nm, paste A) and in a mixture of acetonitrile guanidinium thiocyanate and 0.5 M
microcrystalline-TiO2 and tertbutyl alcohol (volume 4-tert-butylpyridine in a mixture of
(400 nm, paste B) ratio, 1:1) acetonitrile and valeronitrile
(volume ratio, 85:15)
[95] FTO glass TiO2 NPs and SnO2 Graphite/carbon Ruthenium complex I− /I3 − electrolyte solution 6.7
1997 TCO 2,2’-bipyridine-4,
4’-dicarboxylate ligands
[108] FTO glass, Colloidal TiO2 NPs Pt/FTO N3 dye I− /I−
3 electrolyte solution 10
1993 7-8 /sq.
[1] FTO glass, Anatase colloidal TiO2 Pt/FTO Trimeric ruthenium complex I− /I−
3 electrolyte solution 7.9
1991 80 /sq. NPs
M. C. Mathpal et al.
Basic Concepts, Engineering, and Advances … 223

into the loss of overall efficiency, whereas in DSSC a thin conducting plastics layer
on front side can solve the problem of heat dissipation to maintain the lower tem-
perature and overall efficiency of DSSCs. In the current scenario, the most efficient
DSSCs have a PCE of as high as 14.3% [136], or a DSSC based on tandem solar
cell with a PCE of 17.2% [175] under continuous illumination of 1 sunlight energy
(100 mW cm−2 ). The main challenges associated with the fabrication of highly effi-
cient commercial DSSC are the absorption in a wide range of the solar spectrum
(UV-visible to IR region); achieving high surface area; choosing suitable redox elec-
trolyte solution (or a hole transport layer in solid-state DSSC) to avoid degradation
of any component or electrolyte itself from other components; to reduce the recom-
bination losses and improve the charge dynamics; avoiding degradation from the
exposure of ultraviolet radiation; avoiding liquid electrolytes to prevent leakage and
electrode corrosion but at the same time keeping in mind that solid-state DSSCs have
low efficiency; enhancing the charge collection efficiency by improving the contacts
between electrodes; and low stability as compared to traditional Si solar cell [61, 93].
However, the careful designing of DSSC can have high durability and work as long
as 10–20 years. The iodine-based electrolyte solution for DSSC is corrosive enough
to rust the resistant metals such as aluminum and stainless steel [52, 88]. The major
disadvantage in DSSC is the use of liquid electrolyte, which can either easily freeze
during winter season or if somehow heated in summer up to 80 °C (on a rooftop,
for instance) then it can either stop functioning and damage or expand and rupture
the sealing of the solar cell [88]. However, the DSSCs of high efficiency are not yet
considered for large-scale production and field replacements, but an approach for
further enhancement in the PCE of all solid-state DSSC (without liquid electrolyte)
will make them attractive for commercialization. The high cost of Pt-based counter
electrodes and ruthenium-based dye complexes is an additional disadvantage: though
recently carbon, graphene layer, PEDOT:FTS, graphene nanoplatelet (GNP)-based
CE, whereas Co and Cu complex-based dyes are emerged as good alternates to fur-
ther reduce the cost of DSSC [9, 13, 57, 136, 175]. The DSSC-based tandem solar
cells have shown remarkable improvements in PCE to be considered for future solar
cell technologies [52, 175].

9 Summary and Future Directions

So far, various approaches, such as increasing the photoanode specific surface area
by using TiO2 NPs while increasing the red absorption through large particles by
light-scattering effect, modifying dyes properties, improving the transport and con-
duction mechanism of electrolyte solution, enhancing catalytic activity of the counter
electrodes, reducing molecular aggregation, using noble metal NPs for enhancing
the absorption of light and reducing leakage, have been adopted to improve the
efficiency of DSSCs. The characteristic of compact blocking layer to reduce the
recombination losses should be carefully investigated. In addition, several research
articles are dedicated in the direction to reduce the cost of DSSC by searching for an
224 M. C. Mathpal et al.

alternative of the traditional platinum counter electrode and ruthenium-based redox

complexes. Porphyrin dye has shown promising absorption properties as an alternate
of Ru complex-based expansive dyes. The absorption spectra of the dye sensitizer
can be broadened by attaching strong electron donor and acceptor groups to the dyes
through a π-bonded bridge. Iodine-based redox mediator is reported to be corrosive
and unstable. To the date, cobalt and copper-based redox couples are found to be a bet-
ter choice in the replacement of traditional iodine-based redox couple. Graphene film
has got huge attention as a good replacement for Pt/FTO-based counter electrodes as
it has several features including low-cost, high catalytic activity, low sheet resistance
and a transmittance over 90% after doping. Different NIR dyes can be prepared
and used in the combination of different semiconductors of different bandgaps to
construct a multilayered photoanode to absorb the light in the entire region of solar
spectrum. The active ongoing research to improve the efficiency of all solid-state
DSSC will be a major breakthrough to enhance the durability and overall perfor-
mance of the DSSCs by replacing wet-type DSSCs for outdoor applications. The
surface plasmon resonance (SPR) effect can be exploited to enhance the efficiency
of the solar cell by appropriate substitution of gold, silver, and copper nanoparticles
at the metal/dielectric interface in photoanode. The rigorous investigation on shape
and size effect of noble metal nanosize particles to enhance surface plasmon activity
and the maximum absorbance in DSSC will be further helpful. So far, tandem solar
cells have been very efficient so one can think to improve the efficiency by tuning
the n-DSC and p-DSC junction for absorbing UV-visible and NIR light so that the
net electron injection can be increased in DSSCs.

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Quantum Dot Solar Cells

Hafeez Anwar, Iram Arif, Uswa Javeed, Huma Mushtaq, Khuram Ali
and S. K. Sharma

Abstract Energy crisis has become one of the main hurdles in the path of develop-
ment and technology due to the rapid reduction of fossil. Renewable energy resources
have gained the great importance in last few decades. Solar technology is consid-
ered as a potential candidate for energy in future. Solar technology has evolved in
different generations from single crystal semiconductor wafer to quantum dot solar
cells. Quantum dots act as absorbing photovoltaic material instead of bulk materials
like silicon or copper indium gallium selenide in quantum dot solar cell (QDSC).
Quantum dots have tunable band gaps that depend on their size that makes them
a promising candidate for multi-junction solar cells. The photovoltaic conversion
efficiency of quantum dot solar cells is much higher as compared to traditional solar
cells. Various types of quantum dots like CdSe, CdS, PbS, GaAs, CdTe, ZnSe and
graphene are used in different designs of quantum dot solar cells. In this chapter, we
discussed the quantum dot solar cells (QDSCs), their design along with their various
architectures and materials selection approaches in detail.

Keywords Solar cell · Quantum dots · Photovoltaic conversion · Band gap ·

Efficiency · Bulk materials

1 Introduction

Climate change and depletion of traditional energy resources made man to search for
other energy sources. Various renewable resources like geothermal, hydrothermal,
nuclear, wind and biomass are introduced to replace the traditional one but to meet
the need of today’s energy demand above mentioned technologies have no scalable
capacity.

H. Anwar (B) · I. Arif · U. Javeed · H. Mushtaq · K. Ali

Department of Physics, University of Agriculture, Faisalabad 38040, Pakistan
e-mail: [email protected]
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago

© Springer Nature Switzerland AG 2020 235

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_9
236 H. Anwar et al.

Sun is the largest natural source of energy on earth. Energy provided by the sun in
one minute is sufficient for the world’s need in one year [5]. In fact, the solar energy
provided to earth in three days is as same as the amount of energy stored in all
fossils. From centuries, man tried to get maximum energy from sun. The discovery
of photoelectric effect in late nineteenth century laid the foundation of first solar
cell where it was observed that when sunlight falls on metal surface it generates
electric current [11]. It is predicted that after fifty years energy needs will be doubled
[21]. Solar cell technology shows the most promising candidate to meet the energy
demand of the world. A French physicist, A.E. Becquerel observed for the first-time
photovoltaic effect in 1839 [28]. In 1883, Charles Fritts build up the first solar cell,
a thin layer of gold has been coated on the selenium to produce solar cell [68]. In
1954, first silicon-based solar cell was developed by Daryl Chapin, Gerald Pearson
and Calvin at Bell Labs with 4% efficiency that was later increased up to 11% [20].
From then, it has become one of the major research fields, and various kinds of solar
cells are reported in past few decades. One of the major purposes is to develop such
technology that must be cost effective and eco-friendly. Recently, a solar cell with
record efficiency of 24.2% on a wafer measuring 244.62 cm2 is reported at very low
production cost. This achievement boosts the solar technology as next major energy
source of the world.
In recent years, quantum dot solar cells emerged as a promising candidate and
growing very fast. These solar cells can be fabricated with the help of cheap solution-
phase process. Furthermore, these can work in a wide range of lighting conditions.
For the next-generation solar cell applications, quantum dots are most favorable
materials. As these can have ability to overcome the Shockley-Queisser power con-
version efficiency limit of existing conventional single-junction solar cells. Also, due
to tweaking and shape changing properties of quantum dots make these preferable
than the conventional materials. In this chapter, we have discussed solar cell in gen-
eral, its different generations and especially quantum dot solar cells and their various
architectures in detail.

2 Solar Cell and Generations of Solar Cell

In photovoltaic effect, generation of electrons occurs when the sunlight falls on the
material; this causes the flow of electricity. Solar cell is a solid-state device in which
electrons moved from valance to conduction band that results building up the voltage
between electrodes. There are mainly three generations in which solar cells have been
classified. Research has been conducted in all three generations but commercially,
first-generation solar cells’ production is over 85% of all cells [23]. These generations
are discussed in the following section and Fig. 1 shows the schematic diagram of all
generations of solar cells.
Quantum Dot Solar Cells 237

Fig. 1 The schematic diagram of the generations of solar cells

2.1 First-Generation Solar Cell

Generally, these are silicon-based photovoltaic cells. The efficiency of these cells
is due to their pentavalent nature; till now, 33% theoretical limiting efficiency has
been achieved by single-junction silicon [2]. Sand is the main source of silicon but
extracting silicon before its growth of crystal makes it expensive. First-generation
solar cell usually based on silicon [6]. First-generation silicon-based solar cells fur-
ther classified into four categories for commercial applications i.e., monocrystalline
silicon cell, polycrystalline silicon cell, ribbon silicon solar cell [22], amorphous
silicon cell and hybrid silicon cell [30]. To fabricate a solar cell, silicon must be
purified [16]. Mostly casting method is used for the production of silicon [43]. This
process involves the following steps: molten silicon is poured to the mold and after
setting it, wafers are cut [57]. It is less expensive method to produce polycrystalline
as compared to the other methods such as photolithography and MCZ method. [7].
To produce solar cell, n-type or p-type silicon is obtained by doping which produces
p-n junction [39]. Temperature diffusion process is used for doping. In thin-film solar
cell, dopant impurity is added during deposition. When photon falls on it, electrons
are knocked out by these photons and energy is absorbed by silicon, and hole is gen-
erated. The movement of holes and electrons are toward respective electrode. In this
way, current is generated in solar cells. The schematic diagram of first-generation
solar cell is given below in Fig. 2.
238 H. Anwar et al.

Fig. 2 The schematic diagram of first-generation solar cell

2.2 Second-Generation Solar Cells

The second-generation solar cells are known as thin-film solar cells, these are cheaper
than the first-generation solar cell [6], production cost of CdTe thin-film solar cell is
less than 1$ per peak watt [54]. Thin-film solar cells are less efficient, but these have
been using commercially since 2008. Thin-film solar cell is required less amount
of material for deposition. Mostly used second-generation solar cells are based on
amorphous silicon, microcrystalline silicon and cadmium telluride.
Cadmium telluride thin-film solar cell is 30% less costly as compared to the
copper indium gallium selenide solar cell, but if the cadmium is released from the
cell, it will be toxic [65]. Amorphous silicon (a–Si) solar cells are non-toxic and have
greater ability to absorb light in visible region but due to disorder in structure, it is
bad conductor for charge carrier. a-Si has higher band gap of 1.6 eV as compared to
crystalline silicon (1.1 eV) [49].
Thin film of material is an effective way in reducing the size of the cell design.
Thin-film solar cells are less efficient than silicon (wafer-based), but thin-film solar
cells are cost effective. Most common second-generation solar cells are based on
cadmium telluride (CdTe), amorphous silicon (a–Si) and micromorphous silicon. In
CdTe solar cell, thin layer of CdTe (semiconductor layer) absorb and change sunlight
to electricity. The schematic diagram of second-generation solar cell is given in Fig. 3.
The disadvantage of CdTe solar cell is that if the cadmium present in it released
then the cell becomes toxic. But this is the low-cost solar cell i.e., its cost is 30%
less than the copper indium gallium selenide (CIGS) and 40% less than amorphous
silicon technology (a–Si).
Amorphous silicon (a–Si) solar cell is very promising as amorphous silicon present
in a huge amount, and unlike CdTe, it is non-toxic in nature. It is low cost, can be
flexible and also it needs low processing temperature. The structure of this cell is
consisted of amorphous or microcrystalline silicon and it formed a p-i-n architecture.
The thin layer of amorphous silicon is photo-electrically active and it absorbed
more light as compared to the crystalline cells. Because it is amorphous in nature,
Quantum Dot Solar Cells 239

Fig. 3 The schematic diagram of second-generation solar cell

so it is bad conductor of charge carriers due to the dangling bond and irregular
arrangement of atoms. It shows a wider band gap.

2.3 Third-Generation Solar Cells

In these days, focus of researches is shifted toward third-generation solar cells. Third-
generation solar cells are also known as organic solar cells. In these solar cells, p-n
junction is not formed as compared to other generations of solar cell. There are many
types of third-generation solar cells including, dye-sensitized solar cells, perovskite
solar cells and quantum dot solar cells etc. [73]. The working of all type of third-
generation solar cells is almost same [42]. Research on sensitizer-based solar cells
was started in 1970s. Dye-sensitized solar cell (DSSC) is based on a photo electro-
chemical system. It consists of a photo anode or working electrode, a cathode or
counter electrode and electrolyte along with organic dyes. The generation of elec-
trons occurs due to sunlight that hits dye layer; electrons are collected for powering a
load at cathode. These electrons are re-entered in the electrolyte while reducing triio-
dide to iodide after passing through the external circuit [26]. The schematic diagram
of third-generation solar cells is given in Fig. 4.
Later on, organic dyes are replaced by inorganic sensitizers i.e., quantum dots and
perovskite materials. Till now, 21% efficiency is achieved that is a great milestone.
In the next sections, we will discuss about the quantum dots, quantum dot solar cells
and its design. Also, we will discuss about material selection in quantum dot solar
cells.
240 H. Anwar et al.

Fig. 4 The schematic diagram of third-generation solar cell

3 Quantum Dots

Quantum dots are the semiconductor nanostructures mostly assembled from the
group II-VI or III–V of the periodic table [61]. Quantum confinement is most com-
mon term in nano world, this is important because of the change in structure of atom
due to influence of very small length scale on energy band structure. It further corre-
sponds to the quantum confinement regime i.e., 1–25 nm for semiconductors. Due to
geometrical constraints, electron adjusts its energy in response to change in particle
size. This is known as the quantum size effect. It becomes much important when
the properties of the materials are size dependent. Moreover, quantum confinement
changes the concept of continuous energy bands of bulk materials to discrete energy
levels.
Schematic diagram as shown in Fig. 5 represents that the semiconductor shows
the discrete energy spectrum which is the main difference to bulk semiconductor.
In quantum confined structure, motion of charge carriers are restricted by potential
barrier in one or more directions. There are three categories of quantum confined
structure on the basis of confinement direction, i.e., quantum well, quantum wire and
quantum dots. Quantum confined structure’s types are given below.

Structure Quantum confinement Number of free dimensions

Bulk 0 3
Quantum well 1 2
Quantum wire 2 1
Quantum dots 3 0
Quantum Dot Solar Cells 241

Those charge carriers who are remained confined to the three dimensions these
electrons show a discrete energy spectrum. When the two dimensions are confined
then quantum wires are formed. In quantum well, electrons are confined to move in a
plane. This shows that energy levels change from continuous to discrete. The density
of charge carriers is higher near conduction and valance bands.
These possess tunable optical properties as compared to others due to their three-
dimensional (3D) quantum confinement. This quantum confinement is due to the
artificial electrostatic potentials [55], presence of semiconductors surfaces and under-
surfaces among hybrid nanostructures [51] that binds the electrons when the size is
of few nanometers i.e., less than Bohr exciton radius [12]. In semiconductors, the
conduction and valance bands are separated by band gap. The motion of electron
hole present in these bands has been restricted due to quantum confinement. The
charge carrier confinement energy of quantum dots increases that is observed as blue
shift in their optical properties [14]. The energy spectrum of quantum dots is dis-
crete in nature and its corresponding wave function is spatially localized within the
quantum dot that may extend over few folds in crystal lattice [9]. A small number
of elementary particles i.e., electrons and holes in conduction and valance bands
ranging of the order 1–100 present in quantum dots that limits its size up to few
nanometers [44]. A quantum dot contains only 10–50 atoms in diameter that leads
only 100–100,000 atoms within its volume whereas self-assembled quantum dots
have range only between 10 and 50 nm [10].
The interface present in hybrid nanostructures like core-shell particles also give
rise to the quantum confinement that provides them extraordinary optical properties.
The band gap of the shell is larger than the core particles that helps to improve the
optical properties of core particle and separates it from surrounding medium [13]. A
schematic diagram of core-shell quantum dot is shown in Fig. 6.
For the construction of a realistic solar cell, core-shell quantum dots are most
important. The core-shell quantum shell contains materials which have high crystal
quality, well-controlled hetero interface and surface passivation. There are different
categories of core-shell quantum dots exist, depending on the energy gap between
valance band and conduction band in semiconductor. In type I, the core has a large
band gap than the shell and vice versa for inverse type I. In type II, the conduction
or valance band of core could be present within the band gap of the shell.
The physico-chemical and optical properties of quantum dots are different as
compared to its bulk form. They have tunable band gap ranging from ultraviolet to
the infrared that depends on its size [62]. As the size of quantum dots decreases,
its spectrum shifts toward the blue, i.e., higher energy [45, 58]. Generally, the syn-
thesis approaches for the quantum dots are divided into two categories i.e., ex situ
preparation of Quantum dots and in situ preparation of Quantum dots.
242 H. Anwar et al.

Fig. 5 Discrete energy level of semiconductor

Fig. 6 A schematic diagram of core-shell quantum dot

4 Quantum Dot Solar Cells

Quantum dot solar cells (QDCs) belong to the third-generation solar cells. The quan-
tum dot solar cells show low resistance as compared to conventional solar cell. As in
conventional solar cells when semiconductors are absorbed light, this shows much
higher resistance as compared to the metals. Silicon, cadmium telluride and copper
indium gallium selenide are absorbed photons, and electrons jumps from valance to
conduction band, but those electrons which move higher than the conduction band,
relax and give off phonon and heat up the solar cell without providing energy. This
damages the cell and decreases the cell performance. The quantum dots solar cells
generate more electrons as compared to the conventional solar cell for absorption
of each photon. The changing in size and shape of the quantum dots, it can change
Quantum Dot Solar Cells 243

the wavelength of the absorbed light. In quantum dot solar cell (QDSC), quantum
dots are used as photovoltaic material instead of cadmium telluride, copper indium
gallium selenide or silicon wafer. Till now, 16.6% efficiency is achieved for quantum
dot solar cells. There are various types of quantum dot solar cell (QDSC) depend-
ing upon the captivating photovoltaic material. These are discussed in the following
section.

4.1 Metal-Semiconductor Junction Solar Cell (Schottky Cell)

Metal-semiconductor junction solar cells are also known as Schottky junction quan-
tum dots solar cells. These are the first kind of quantum dot solar cells (QDSCs)
that achieved the efficiency up to 1% [38]. Quantum dots in the form of thin film
are sandwiched between the indium-doped tin oxide (ITO) counter electrode and
metallic electrode. The ITO-based counter electrode acts as a photo electrode. A
schematic diagram of metal-semiconductor junction solar cell is shown in Fig. 7.
The design of cell based on the transparent conducting oxide (TCO) having large
work function such as indium-doped tin oxide with the p-type quantum dot film to
create an ohmic contact [24]. Then, a suitable band-bending to extract electrons is
created by evaporating a metal having low work function such as magnesium and
aluminum [63].
This kind of solar cells have few limitations such as short diffusion length and
immobilization of the Fermi level due to defect states that affect the open-circuit
voltage [66]. These issues can be resolved by post treatments, optimization of material
synthesis and hole selective contacts. Till now, 5.2% efficiency is achieved [40].

Fig. 7 A schematic diagram of metal-semiconductor junction solar cell

244 H. Anwar et al.

4.2 Quantum Dot-Sensitized Solar Cells

The working principle of quantum dot-sensitized solar cells (QDSCs) is almost same
as dye-sensitized cells (DSCs) with a slight exception that is quantum dots are used
in quantum dot-sensitized solar cells (QDSCs) instead of dye as a current injector
[27].
The structure of the three important parts of the quantum dot-sensitized solar cell
includes counter electrode, photoanode having layer of nanostructured TiO2 with
quantum dots layer on it and electrolyte.
Photoanode consists of films of semiconductor which increase the power conver-
sion efficiency. There are two main features of photoanode: (i) It provides smooth
path for the transfer of the photoexcited electrons, which move toward conducting
substrate and then to external circuit. (ii) It offers enough surface area to load enough
quantum dots for light absorption. In short, a good photoanode must have fast elec-
tron transport rate for high electron collection efficiency and a large surface area for
quantum dots for light absorption. 7.55% power conversion efficiency is obtained by
controlling photoanode.
To transfer charge between counter electrode and photoanode, redox electrolyte
plays role of medium. It helps both in stability and efficiency of the quantum dot
solar cell. I− /I3− (iodide/triiodide) are not stable in chalcogenide quantum dot-based
quantum dot solar cell. Therefore, aqueous solution of polysulfide (S2− /Sn2− ) redox
couple is used in quantum dot solar cells as it provides stability to QDSCs. Counter
electrode in quantum dot solar cells transfer electrons from external circuit and
catalyzing the reduction reaction of oxidized electrolytes at electrolyte/CE interface.
The quantum dot-sensitized solar cell is shown schematically in Fig. 8.

Fig. 8 The structure of the quantum dot-sensitized solar cell

Quantum Dot Solar Cells 245

In dye-sensitized solar cell (DSC), dyes do not directly play any role in recombi-
nation process. The electrons firstly, injected into nanostructured TiO2 and holes are
regenerated within a time scale of life of nanostructured TiO2 , whereas in the quan-
tum dot-sensitized solar cell, quantum dots directly participated in the recombination
process [25].

4.3 p-I-n Quantum Dot Solar Cell

This architecture of solar cell is also known as multi quantum well solar cell. The
three-dimensional (3D) array of quantum dots in core region of p+ –I–n+ structure is
used in this configuration. The interspacing of the quantum dots is small to achieve
the strongest electronic coupling that allows the long-range electron transportation
and this three-dimensional (3D) array of the quantum dots acts as photo electrode
[48]. The schematic diagram of multi quantum well solar cell is shown in Fig. 9.
The miniband states present in quantum dots solar cells are delocalized and quan-
tized and slow down the cooling that allows the transportation and collection of
charge carriers at their respective contacts (p or n). It permits to enhance the photo
potential in solar cell.
The delocalized quantized 3-D miniband states slow down the cooling of charge
carriers, allows the transport of charge carriers and their collection at the respective
p and n contacts to produce. The limitations of this kind of solar cells are the nature
of electronic states as a function of inter dot spaces, transportation properties, shape,
order and disorder of arrays and orientation of quantum dots [47].

Fig. 9 Schematic diagram of p-I-n quantum dot solar cell (adapted from [27]
246 H. Anwar et al.

4.4 Polymer-Semiconductor Structure Configuration

The hybrid polymer-semiconductor quantum dot solar cells were firstly introduced
by Huynh in 2002 with the efficiency of 1.7% [27]. A junction is created between
organic polymer and semiconductor quantum dots. The efficiencies of these solar
cells are not much higher but they are cost effective and stable as compared to other
configurations.
Polymers are attached to the electrode, when light falls on it holes are generated.
The polymer present in the solar cell is not completely responsible for the recombi-
nation process due to the presence of quantum dots that have much higher absorption
[50]. The donor present in solar cell have much higher lowest unoccupied molecular
orbitals as compared to acceptor and the Fermi level of cathode is slightly lower than
the conduction band of acceptor (quantum dots) that allows the electrons to flow
from polymer to cathode. A schematic diagram of hybrid polymer-semiconductor
quantum dot solar cell is shown in Fig. 10.
The role of polymers in recombination process is still not completely clear, there
is a general rule followed in this regard, i.e., the II–VI and IV–VI quantum dots are
capped by small chain quantum dots (Quantum dots) to enhance the photovoltaic
performance of the cell. The limitations of these solar cells are unbalanced charge
mobilities [31].

Fig. 10 A schematic diagram of hybrid polymer-semiconductor quantum dot solar cell

Quantum Dot Solar Cells 247

Fig. 11 A schematic and energy diagram of heterojunction quantum dot solar cell

4.5 Depleted Heterojunction Quantum Dots Solar Cells

The heterojunction quantum dot solar cells are mostly based on lead chalcogenide
quantum dots. The highest efficiency achieved by these solar cells is 12.35% [17].
These solar cells overcome the limitation of Schottky quantum dot solar cell, i.e., low
built-in voltages. The structure of these solar cell consists of a quantum dot layer that
is sandwiched between metal electrode and electron transporting layer usually TiO2
is used for this purpose. The electrons mostly transport toward TiO2 layer instead
of evaporated metal contact that creates an inverse polarity [15] and holes transfer
from TiO2 layer to quantum dots is restricted that allows better charge separation. A
schematic and energy of heterojunction quantum dot solar cell is shown in Fig. 11.

5 Material Selection in Quantum Dot Solar Cells

5.1 CdSe-Based Quantum Dot Solar Cell

CdSe quantum dots are coupled with comparatively stable and large band gap metal
oxide, i.e., TiO2 to produce quantum dot solar cells. CdSe Quantum dots are synthe-
sized by using pyrolysis of organometallic reagents by injection into a hot coordinat-
ing solvent; it provides controlled growth of CdSe quantum dots. 0.08% efficiency
of the solar cell is obtained under 100 mW/cm2 under solar illumination [29].
Different-sized CdSe quantum dots have been assembled on TiO2 nanoparticles
and nanotubes by using a bifunctional linker molecule. CdSe Quantum dots inject
electrons in TiO2 (as shown in Fig. 12) and produce photocurrent in photo electro-
chemical solar cell. It is interesting to note that by controlling the size of the CdSe
Quantum dots photo electrochemical response can be tuned and by facilitating trans-
portation of charge through TiO2 nanotube architecture, photo conversion efficiency
can be improved [8].
248 H. Anwar et al.

Fig. 12 To Harvest Light TiO2 film Functionalized with CdSe quantum dots

Sensitized-type solar cell which was based on TiO2 inverse opal and CdSe quan-
tum dots are used as the sensitizer. By using chemical bath deposition method,
CdSe quantum dots were grown at appropriate place on TiO2 inverse opal electrode.
Improvement in the photovoltaic performance can be observed by modifying sur-
face with zinc sulfide and fluoride ions [18]. With the increase in the adsorption
time, the size of the CdSe increases. To obtain the best photovoltaic conversion effi-
ciency, there is a specific adsorption time for CdSe. Under a solar illumination of 100
mW/cm2 for CdSe quantum dot solar cell, 2.02% efficiency is observed [59]. Light
harvesting ability can be enhanced by stacking quantum dots of PbS, CdS and CdSe
on mesoporous layer of TiO2 in different combination. Solar efficiency of 6.2% has
been achieved by three layers of PbS/CdS/CdSe quantum dot solar cell while solar
cell efficiency of two layers of quantum dots solar cells consisted of PbS/CdS and
CdS/CdSe was obtained 5.8 and 4.2% respectively [41]. Two steps ion exchange
process utilized to obtain CdSe/ZnO at lower temperature. Analyses showed that
greater size of ZnO quantum dots is obtained which enhances the light harvesting.
Quantum dots solar cell which consisted of CdSe/ZnO showed 5.08% efficiency
[52]. The performance of the quantum dot-sensitized solar cell (QDSC) might be
increased with the presence of both CdS and CdSe quantum dots. Fill factor of CdS
is greater than the CdSe-DSSC as for electron injection it provides greater driving
force [34].

5.2 CdS-Based Quantum Dot Solar Cell

CdS-based quantum dot solar cells absorb light in the visible region [71]. Quantum
dot solar cell as compared to other conventional solar cell decreases the dark cur-
rent and enhances the efficiency of the solar cell [60]. Anodic oxidation in a NH4 F
Quantum Dot Solar Cells 249

organic electrolyte is used to synthesis highly ordered TiO2 nanotube films. Sequen-
tial chemical bath method is used to deposit CdS Quantum dots onto TiO2 nanotubes.
Fill factor of 0.578 and 4.15% cell efficiency are achieved by this system. The high
efficiency is due to geometry of the film which permits the faster transfer of photo
generated electrons from CdS quantum dots to TiO2 substrate [64].
CdS quantum dot-sensitized solar cell based on modified polysulfide electrolyte
shows 3.2% energy conversion efficiency with high photo voltage of V oc = 1.2 V
under air mass 1.5 G illumination and fill factor is 0.89 (shown in Fig. 13). CdS
quantum dots are attached to nanoporous TiO2 by using thioglycolic acid (TGA)
[35].
Mercaptosuccinic acid (MSA) modified the surface of CdS Quantum dots and
it behaves as N3 dye in terms of adsorption legend which attaches onto the bare
TiO2 substrate. Modification on the TiO2 surface can also be made by using linker
molecules to render a surface with amine or thiol group. It is observed that the power
conversion efficiency of CdS sensitized TiO2 electrode is 20%, 13% TiO2 film which
is modified by 3-mercaptopropyl trimethoxysilane and 6% for TiO2 film modified
by 3-aminopropyl-methyl diethoxysilane. Moderate absorption rate of MSA-CdS
Quantum dots using carboxylic acid/TiO2 provide the efficient assembly of quantum
dots on to TiO2 film [60].
Successive ionic layer adsorption and reaction (SILAR) method is used to deposit
undoped and Pb-doped CdS Quantum dots on TiO2. In the visible region, 2% Pb-
doped CdS Quantum dots show highest absorption rate and show 1.19% power
conversion efficiency [70]. Quantum dot solar cell is competitive only when it shows
the higher power conversion efficiency, the quantum dot solar cell based on Mn-
doped- CdS/CdSe quantum dot on TiO2 substrate shows improved efficiency of
5.4% [56].

Fig. 13 Schematic diagram of the CdS quantum dot solar cell

250 H. Anwar et al.

5.3 PbS-Based Quantum Dot Solar Cell

It is a low-cost new-generation solar cell. It is interesting to note that the power

conversion efficiency of the PbS-based quantum dot solar cell increases to 8.45% by
introducing of the conjugated polymer as anode buffer layer. The open-circuit voltage
also increases dramatically due to modification of anode [37]. In fabrication of PbS
colloidal quantum dot-based solar cell, fullerene derivative is used as the electron
transporting layer. Structure of quantum dot films is modified by thiol treatment and
oxidation process and quantum dot solar cell shows fill factor of 62%. Under one
sun AM 1.5 illumination, the power conversion efficiency is 1.3% [79].
By using lead sulfide quantum dots, a large area which is present in between
TiO2 and organic charge transport material is sensitized to visible light. The inci-
dent photon-to-electron efficiency is up to 45% and under simulated sunlight of
10 mW/cm2 , 0.49% energy conversion efficiency is observed [53]. The colloidal QD
solar cell which is prepared by using solution processing method with ZnO/PbS-
EDT/carbon shows remarkable photovoltaic response. It shows greater power con-
version efficiencies (5.9%), fill factor (51.8%) as compared to Au-coated colloidal
quantum dot solar cell [3].
PbS quantum dots developed by non-hot injection synthetic route simplifies the
fabrication of Pb-chalcogenide QD solar cell. PbS QD of size 2.2 nm is produced
having band gap 1.7 eV. Photoluminescence quantum yield of chloride-terminated
Quantum dots is higher as compared to the other conventional synthesis techniques
and these showed improved air stability but the solar cell performance of chloride-
passivated PbS Quantum dots is much better than traditional synthesis [77], Fig. 14.
As on large scale, it is not economic to deposit many layers of film in solar cell.
A simple and efficient way of deposition is to replace the methanol with acetonitrile
(ACN). During the solid-state ligand-exchange process, the film cracks generated
from the volume loss, this problem can effectively be cured by using ACN which
enable thick and dense deposition of film with less deposition steps. CPVT-certified

Fig. 14 Preparation of PbS quantum dots and the photovoltaic performance of PbS quantum dot
solar cell (Reproduced with the permission of [77]
Quantum Dot Solar Cells 251

IPCE of 11.21% is achieved which is highest efficiency reported for PbS Quantum
dots solar cells [36].

5.4 InP-Based Quantum Dots Solar Cells

As InP has ideal band gap (1.35 eV) and it is also environment friendly. It harvests
more light than other materials used in photovoltaic cells. By using one pot nucleation
doping method, Sn-doped InP quantum dots are synthesized. Sn-doped InP quantum
dots are used as sensitizer in quantum dot solar cell. Capping ligand induced self-
assembly is used to load quantum dots on mesoporous TiO2 film. Sn-doped InP
quantum dot solar cell shows power conversion efficiency of 3.54% under AM 1.5
G. With the increase in size of the Sn:InP Quantum dots, the absorption peak is
gradually red-shifted and also broadened. Sn:InP quantum dots have nearly spherical
shape and lattice spacing is equal to those of InP Quantum dots as shown in Fig. 15
[74].
By using an intermediate band within the band gap, efficiency beyond the
Shockley-Queisser limit can be attained. InP quantum dot is in In0.49 Ga0.51 P host
is most promising for intermediate band solar cell. Metal organic chemical vapor
deposition (MOCVD) is used for the growth of InP quantum dots. With both 3 and 5
layers of InP Quantum dots in the i-region, several n-i-p In0.49 Ga0.51 P solar cells are
grown. Enhancement of 0.11 mA/cm2 , in sub-band gap is observed due to absorption
and collection from InP Quantum dots [32], Fig. 16.
InGaP-based InP quantum dot solar cells are also intermediate band solar cells.
To fabricate this system, solid-source molecular beam epitaxy is used and optical
absorption of InP is observed as ~850 nm which is greater than optical absorption
range of the host InGaP solar cell. Thermal carrier escape still occurred despite the
deep confinement of electrons in InGaP-based InP QD solar cells. This solar cell
shows efficiency 0.38% [1].

5.5 Graphene Quantum Dot-Based Solar Cell

Graphene quantum dots show promising properties in quantum confinement and edge
effect. Due to its unique optoelectronic properties, it is used in photovoltaic devices.
Graphene quantum dots are used as sensitizer in dye-sensitized solar cell [78]. Hybrid
zinc oxide/graphene electrodes in quantum dot solar cells are more efficient than
TiO2 /ZnO films. From Fig. 17, it is observed that for both materials, absorption
peaks lie in the ultraviolet region and hybrid dots are red-shifted. A luminescence
quenching effect of graphene shell is about 72% observed by photoluminescence
measurement. System consisting of these hybrid electrodes shows power conversion
efficiency of 35% which is quite higher than that is obtained by ZnO electrode as
shown in Fig. 16 [67].
252 H. Anwar et al.

Fig. 15 a UV-vis spectra of Sn: InP Quantum dots (Sn/In ¼/0.1) with various absorption wave-
lengths, b XRD patterns of InP and Sn: InP Quantum dots. c HR-TEM images of Sn:InP Quantum
dots and d InP Quantum dots. Insets are HR-TEM images and column charts of the size distribution
(Reproduced with the permission from [74]

Fig. 16 Schematic
illustration of the structure of
InGaP-based InP quantum
dot solar cell
Quantum Dot Solar Cells 253

Fig. 17 Optical properties of hybrid ZnO/G Quantum dots as compared to pristine ZnO nanopar-
ticles. a UV-Vis spectrum of the colloidal solutions in DMF (24 mg/ml). b PL spectrum of CQD
films (300 nm) prepared by spin coating (Reproduced with the permission from [67]

Zinc oxide nanowires are coupled with the graphene quantum dots (which synthe-
sized by direct chemical method) prove their potential as light harvesting material in
photovoltaic cells and show 0.8 V open-circuit voltage [19]. The efficiency of n-type
Si heterojunction solar cells is enhanced about 16.5% due to the presence of graphene
quantum dots. In depletion region, more electrons are absorbed for effective carrier
separation, due to photon down conversion phenomenon of the graphene quantum
dots. Fill factor increases from 70.29 to 72.51% [69].

5.6 Other Quantum Dot Solar Cell

PbSe quantum dots show enhancement in the photocurrent due to multiple exci-
ton generation (MEG). PbSe quantum dots that are synthesized by a direct cation
exchange show air stability and sustain their photoluminescence quantum yield under
ambient condition for more than thirty days [76]. Improvement in the efficiency of
InAs/GaAs quantum dot solar cell (from 11.3 to 17.0%) is observed by direct silicon
doping in InAs Quantum dots. Molecular beam epitaxy is used to grow five stacked
quantum dots in i-region of the devices. Open-circuit voltage also increases to 0.84 V
due to the Si-doping [75]. Five layers of InAs/GaAs Quantum dots with different
levels of Si-doping are placed in the middle of the i-region are shown in Fig. 18.
To increase photocurrent in the solar cell, quantum dots are embedded into the
intrinsic layer of p-i-n solar cell. It is observed that the presence of defects increases
carrier extraction from InAs [72]. Another approach of quantum dot solar cell is
growth of In(Ga)As/GaAs quantum dot on the silicon substrate by using molecular
beam epitaxy. By inserting forty layers of In(Ga)As/GaAs quantum dots in hetero-
junction pin GaAs/n+ -Si spectral response increases up to 1200 nm [4]. GaSb/GaAs
254 H. Anwar et al.

Fig. 18 Structure of the QD

solar cells. Five layers of
InAs/GaAs Quantum dots
with different levels of
Si-doping are placed in the
middle of the i-region

quantum dot solar cell showed enhanced infrared spectral response as from 0.9 to
1.36 µm as compared to GaAs cell which is considered to be reference [33].
For broad absorption and efficient carrier extraction type II, ZnSe/CdS quantum
dot solar cell are fabricated. In type II, ZnSe/CdS system minimal conduction band
edge in CdS shell and maximal valence band in ZnSe core i.e., these conduction and
valence band lie in the different semiconductor, which provide a smaller band gap
for a broad absorption spectrum [46].

6 Conclusion

Renewable energy resources especially photovoltaic have become the promising

solution for the energy crisis. Many countries are adding solar technology in main
grid system. Third-generation solar cells like DSSC, perovskite solar cells, organic
solar cells and quantum dot solar cells have dominated the research from past few
decades. Quantum dots solar cells overcome the limitations of dye-sensitized solar
cells and also cost effective. Various types of quantum dots are used to enhance the
efficiency of solar technology. To overcome the world energy crisis, it is necessary
to implement the transformative technology.
Quantum Dot Solar Cells 255

Acknowledgements H. Anwar is grateful to Pakistan Science Foundation for funding under the
project PSF-NSF/Eng/P-UAF (05).

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Organometal Halide Perovskite-Based
Materials and Their Applications
in Solar Cell Devices

Amna Bashir and Muhammad Sultan

Abstract Perovskite Solar Cells (PSCs) based on organometal trihalide materials

have gained enormous attention for photovoltaic applications due to its outstanding
optical and electronic properties such as high absorption coefficient long carrier diffu-
sion lengths, long carrier mobility and unique defect physics. As a result, the power
conversion efficiency (PCE) of PSCs rapidly enhanced from 3.8 to 24% through
the advancement made in processing methods, compositional tuning, and interface
engineering. The dominant PSCs architecture has been evolved; n–i–p and p–i–n
with mesoporous and planar heterojunction. In both configurations, i.e. planar or
mesoporous, the perovskite material is sandwiched between electron and hole trans-
porting layers and top electrode. The basic function of charge transporting layers is
to improve charge collection efficiency and reduce charge recombination at inter-
faces. In the following chapter, we present the critical survey of the recent progress
in perovskite absorber and charge transporting materials for the exceptionally higher
PCE of perovskite devices. Furthermore, numerous fabrication techniques and device
architectures are summarized.

Keywords Photovoltaics · Third-generation solar cells · Perovskite materials ·

Perovskite solar cells · Heterojunction

1 Introduction

The perovskite solar cells are evolved from dye-sensitized solar cells (DSSC). The
mesoscopic DSSC was first reported by Micheal Gratzel and O’ Ragan in 1991
[1]. A power conversion efficiency (PCE) of 7% was reported using Ruthenium dye
absorbed on mesoscopic film of nanocrystalline TiO2 [1]. This discovery opened
a new frontier in the race of developing the solar energy harvesting technologies.
A characteristic liquid DSSC consists of a photoanode, which is usually a glass

A. Bashir
Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan
A. Bashir · M. Sultan (B)
Nanoscience & Technology Department, National Centre for Physics, Islamabad 44000, Pakistan
e-mail: [email protected]
© Springer Nature Switzerland AG 2020 259
S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_10
260 A. Bashir and M. Sultan

coated with the transparent conducting oxide (TCO), a mesoporous TiO2 with the
sensitized dye absorbed onto it, and electrolyte (typically an iodine/iodide redox
couple), and a platinized counter electrode. The schematics representation and the
working principle of DSSC and device architecture are shown in Fig. 1 [1]. After
the absorption of photons, the electrons are excited from Highest Occupied Molec-
ular Orbital (HOMO) to Lowest Unoccupied Molecular Orbital (LUMO) of dye.
Meanwhile, the electrons are injected from LUMO into the conduction band of the
TiO2 , which is acting as electron transporting layer. The electrons are collected at
corresponding electrode via diffusion process through mesoporous TiO2 layer. At
counter electrode, the electrolyte is reduced by the electrons approaching through
the external circuit [2, 3]. Until now, an impressive efficiency up to 13% has been
achieved for the devices made in the laboratory and 10% for the prototype modules
[4, 5]. However, electrolyte leakage, instability and its corrosive nature are the main
difficulties towards the commercialization of liquid DSSC [6]. Subsequently, Batch
et al. in [7] first reported solid-state dye-sensitized solar cells (ss-DSSC) with PCE
of 0.74% [7]. In 2011, a record PCE of 7.4% has been achieved by optimizing the
various components of ss-DSSC [8]. In 2012, thin-film photovoltaics technologies
have been revolutionized with the substation of dye with the organic-inorganic hybrid
perovskite (PS) absorber [9, 10].
Perovskite solar cells (PSCs) based on organometal trihalide material (MAPbI3 )
have engrossed enormous research interest for solar cell applications [10–12], due
to their outstanding optical and electronic properties such as high absorption coeffi-
cient [13], long carrier diffusion lengths [14, 15], long carrier mobility and unique
defect physics. [16] As the result, the power conversion efficiency (PCE) of PSCs
rapidly enhanced from 3.8% to 22.1% [17] through the advancement made in pro-
cessing methods via compositional engineering [18], interface engineering [19, 20].
The advantage of PSCs over conventional silicon solar cells is their low cost and
simple manufacturing process. However, for the conventional silicon solar cells, the

Fig. 1 Schematic representation of, a components of solid-state dye-sensitized solar cell (ss-
DSSC), b working principle of ss-DSSC, reproduced with permission from royal society of
chemistry, Ref. [92]
Organometal Halide Perovskite-Based Materials … 261

manufacturing process is multistep, and each step being operated at high temperature
(>1000 °C) in highly evacuated chamber. However, synthesis of perovskite material
is simple by wet chemical method in non-evacuated ambient conditions.

2 Perovskite Material for Solar Cell Applications

The PSCs based on the light harvester and charge carrier conductor that is actually
an organic-inorganic lead or tin halide compound also called perovskite compound.
The perovskite refers to the class of material that has the general formula of ABX3 ,
where A and B are the cations having different atomic radii, and X is an anion bond
to both. The crystal structure of methylammonium lead halide perovskite is shown
in Fig. 2. In methylammonium lead halide (CH3 NH3 PbX3 ), the CH3 NH3 + cation
ion is surrounded by the octahedra of PbX6 . The X ions are highly mobile and can
be localized through the whole crystal structure. The activation energy of X ions is
0.6 eV, which is dependent on the axial to axial, equatorial to axial or equatorial to
equatorial bond position of halide anions. With the CH3 NH3 PbI3, the record PCE od
>20% has been achieved successfully after an extensive research [11]. This PCE is
higher than the traditional DSSC and organic solar cells [17, 19].
The perovskite material CH3 NH3 PbI3 and CH3 NH3 PbBr3 firstly reported as
light harvesting material for solar cells by Kojima et al. [17] with the record effi-
ciency of 3.81%. Later, this PCE had been further improved to 6.54% by intro-
ducing the CH3 NH3 PbI3 quantum dots (QDs) spin-coated TiO2 surface using per-
ovskite precursor solution [21]. The PCE of PSCs had been improved further up
to 9.7% by the development of mesoscopic heterojunction solar cells with the use

Fig. 2 Typical crystal

structure of perovskite
materials, based on the data
of Ref. [93]
262 A. Bashir and M. Sultan

of CH3 NH3 PbI3 as light harvester [21]. These perovskite materials were produced
by reaction between methylammonium iodide and lead iodide, and then deposited
on the TiO2 surface having the thickness of micrometre. The 2,2 ,7,7 -tetrakis (N,N-
di-p-methoxyphenyl-amine)-9,9 -spirobifluorene (spiro-OMeTAD)was used as hole
transporting layer (HTL). Later, Lee et al. [17] have reported comparatively low
cost, solution-processable PSCs with the improved PCE up to 10.9%. This type of
solar cells employed mesoporous alumina (Al2 O3 ) as a chemically inactive layer
which acts as scaffold for perovskite material and also forces the electron to move
within the perovskite film [17]. Liu et al. [22] have proved that the nanostructure is
not an essential requirement to obtain higher performance with perovskite material.
They fabricated the planar heterojunction (PHJ) solar cells with vapour deposited
perovskite film and achieve PCE of 15% under one sun illumination conditions
[22]. This achievement has demonstrated that the PSCs with simple structure can
attain higher power conversion efficiencies, therefore avoiding pointless complica-
tions related with the use of nanostructures. The efficiencies of PSCs have been further
improved by the Zhou et al. [19] group. They use yttrium (Y) doped TiO2 as electron
transport layer (ETL) to boost up the carrier concentration and modified indium tin
oxide (ITO), yielding an PCE of 19.3% [19]. Jeng et al. [23] developed a new method
to construct inverted planar heterojunction (PHJ) PSCs. The device architecture for
PHJ solar cells can be of two types depending on the p–i–n heterojunction scheme
employed: (a) normal devices having poly(3,4-ethylenedioxythiophene) polystyrene
sulphonate (PEDOT:PSS) acting as a hole transporting layer, perovskite as intrinsic
layer, and PCBM or fullerene derived [6, 6]-phenyl-C61 -butyric acid methyl ester as
an electron transporting layer [23], (b) an inverted structure with compact TiO2 as
n-doped, perovskite as undoped or intrinsic and organic semiconductor as p-doped
region [24]. Nie et al. [25] have employed solution-based hot casting technique to fab-
ricate highly uniform pinhole free film of perovskite material having millimetre-sized
crystalline grain, approaching PCE of 18% [25]. The power conversion efficiency
has been increased further to 18.3% by growing perovskite film with large grain size
on several HTLs, and decreasing recombination of carrier at grain boundaries [26].
The advantages of exploiting conventional and inverted PHJ structure are that the
mesoscopic metal oxide layer can be dispensed, that leads to the fabrication pro-
cess more facile [27]. Figure 1 depicted the device architecture of conventional and
inverted PHJ perovskite solar cells. The electron and hole transporting layers act as
an interfacial modifier, while metallic layer and TCO layer function as conducting
electrode. The perovskite layer acts as light harvester and transports the charges till
their arrival to the corresponding electrodes. Thus, research has been focussed on the
development of techniques to prevent the recombination of charges, including inter-
facial engineering which is the main technique to suppress the charge recombination
at electrodes and perovskite interface [28, 29].
Organometal Halide Perovskite-Based Materials … 263

3 Compositional Aspect of Perovskite Material

The most frequently considered perovskite materials for photovoltaics (PV) applica-
tions are CH3 NH3 PbI3 , CH3 NH3 PbI3−x Clx , CH3 NH3 PbBr3, CH3 NH3 Pb(I1−x Brx )3,
HC(NH2 )2 PbI3, CH(NH2)2 Pb(I1−x Brx )3, CH3 NH3 SnI3. The properties of perovskite
material can be tuned further by substituting various cations and anions at the AMX3
sites of the perovskite.

3.1 ‘A’ Site

The electronic properties of perovskite material are not directly affected by the A
cation. However, it has been demonstrated via simulation that the crystal structure
of perovskite material is affected by the size of A cation, which ultimately chang-
ing the electronic properties of the perovskite material [30]. A three-dimensional
symmetrical crystal structure can be achieved by substituting a ‘A’ site vacancy
with a small cation like caesium (Cs), rubidium (Rb), methylammonium (MA) and
formamidinium (FA) [31].
Methylammonium (MA): The most frequently used cation in organic-inorganic
hybrid perovskite material is the methylammonium (MA). The PSCs employing
MA cation in hybrid perovskite material has attained the efficiencies of more than
15%. The MA cation is most commonly used in methylammonium lead triiodide
(CH3 NH3 PbI3 or MAPbI3 ) perovskite material. The MAPbI3 develops the tetrago-
nal crystal structure rather than the cubic structure, which might be due to the very
small size of MA+ cation. The resulting band gap of 1.51–1.55 eV is obtained which
is greater than the optimized Shockley–Queisser limit for mono-junction device [32,
33]. The band gap was further tuned by replacing the MA+ cation with the bigger
cation, which improves the light absorption throughout the spectrum. The replace-
ment of smaller cation with the bigger one imparted the better crystal symmetry
which results in smaller band gap and improved light absorption. The other cations
that have been explored are ethylammonium (EA), formamidinium (FA) and caesium
(Cs).
The replacing MA+ cation with bigger cation “of having larger ionic radii” such as
EA results in distortion of three-dimensional crystal structure. The ethyl ammonium
lead triiodide (CH3 CH2 NH3 PbI3 ) develops a two-dimensional orthorhombic crystal
structure having band gap of 2.2 eV. A relatively lower PCE of 2.2% was recorded
for PSCs employing CH3 CH2 NH3 PbI3 as light harvester under standard illumination
conditions [31].
Formamidinium (FA): FA cation has been estimated to result in a better symmetry
than that of MA and therefore has been broadly investigated. The FA crystal possesses
advantageous bad-gap of 1.43–1.48 eV. However, Formamidinium lead triiodide
(FAPbI3 ) develops a yellow colour hexagonal one-dimensional non-perovskite poly-
morph at room temperature showing serious band coordination with TiO2 [31]. This
264 A. Bashir and M. Sultan

results in lower photovoltaic performance of PSCs using FAPbI3 as light harvester

[31]. It has been anticipated further that the complete removal of this non-perovskite
polymorph state of FAPbI3 would increase the PCE of FA-based devices even more
than that of MA-based PSCs.
Caesium (Cs): The Cs-based perovskite was first explored by the Scaife et al.
[32]. It was investigated that the caesium tin triiodide (CsSnI3 )-based perovskite
showed highly intense photoluminescence (PL) peak for near infrared region of the
solar spectrum [34]. The four different crystal structure of CsSnI3 that was present
independently at room temperature was investigated by Chung et al. [35]. The small
size of Cs as compared to MA results in a higher band gap of 1.73 eV for CsPbI3
over MA PbI3 (1.57 eV), more than the appropriate bang-gap of 1.4 eV [33] suitable
for PV applications.
Mixed A cations perovskites: Mixed A cations perovskites combine the strong
characteristics of individual components. It was first reported by the Pellet et al. [29].
They modify the band gap of mixed A cation perovskite material by changing its
composition. They reported the mixed A cations perovskite, i.e. methylammonium
formamidinium lead triiodide (MAx FA1−x PbI3 ) with the different compositional ratio
of MA to FA and ultimately achieving the PCE of 14.9% [29]. The improved PCE of
these devices compared with MA-based PSCs is due to the higher light absorption
by perovskite layer in red region of solar spectrum. Mei et al. realize perovskite
solar cells built on 5-aminovaleric acid (5-AVAI)x MA1−x PbI3 perovskite material
with reduced defects [36]. This results in improved carrier lifetime and reduced
recombination as compared to the unchanged MAPbI3 . A PCE of 12.8% was reported
with enhanced stability under light and ambient conditions.

3.2 ‘M’ Site

The M site of organic-inorganic hybrid perovskite material is usually occupied by

the metal cations of group IV A. The most commonly used ions of group IV A in +2
oxidation state are Lead (Pb), Tin (Sn) and Germanium (Ge). The most extensively
used metal of group IVA is the lead metal, as it showed much better performance and
stability as compared to the tin metal (Sn) [37, 38]. However, Ge has not often been
explored in +2 oxidation state due to its mercurial characters in this state [39]. Due to
the inert electron pair effects, the +2-oxidation state becomes less stable as we move
down the group IV A, i.e. from Pb to Ge. However, reduction in band gap is observed
due to increase in ionic characters moving down the group. Hypothetically, MASnX3
shows band-gap value of 1.2–1.4 eV as compared to MAPbX3 that has the band-gap
value of 1.6–1.8 eV. However, the drawback of MASnX3 is the instability of Sn in
+2 oxidation state. It is readily oxidized in air producing volatile SnI4 compound.
MASnX3 -based PSCs showed better current density (Jsc ) than the solar devices based
on MAPbX3 , yet its unstable nature has hindered its further development [38].
Mixed M cations: The band gap has been changed effectively by changing the
ratio of Pb to Sn in CH3 NH3 Sn1−x Pbx I3 perovskite-based devices [31, 40]. It has been
Organometal Halide Perovskite-Based Materials … 265

observed that by increasing the Sn contents up to x = 0.5, a quasi cubic tetragonal

structure is formed similar to the pure MASnI3 [31]. By increasing the Sn con-
tents further, a tetragonal structure has been observed. A tetragonal structure with
increased absorptivity and decreased band gap was observed by further increasing
the Sn contents [31]. A lot of development has been accomplished in dual metal
hybrid perovskite devices as elaborated elsewhere [41].

3.3 ‘X’ Site

Changing the halide ion is the best method to probe the performance characteristics
of hybrid perovskite photovoltaics. In moving down the group VIIA, atomic size
increases, absorption spectra shifted towards longer wavelength, and a decrease in
energy is observed [40].
Iodide (I): The PSCs based on iodide ions are the most important one reaching
PCE over 20% [23, 42]. The electronegativity value of iodine (2.66) is closer to that
of lead (2.33) thus leading to the most stable perovskite structure. The bond between
iodine and lead is neither covalent nor ionic rather mixed characters. Although
iodide forms the most basic components of hybrid halide perovskite, its instabil-
ity towards humidity is a problem. Therefore, more study is encouraged to realize
iodide substitute and mixed halide perovskite.
Chloride (Cl): The PSCs containing Cl-based perovskite material showed better
efficiencies as incorporation of Cl in perovskite material results in longer carrier dif-
fusion lengths and better charge carrier lifetimes [43]. MAPbCl3 exhibits the cubic
structure at ambient temperature; nevertheless, blended CH3 NH3 PbI3−x Clx produced
remarkably aligned crystalline arrangement [44]. Furthermore, X-ray diffraction
(XRD) studies have confirmed the arrangement of CH3 NH3 PbI3−x Clx similar to
MAPbI3 , having maximum 3–4% Cl to I ratio [45]. Dar et al. [46], however, showed
that Cl remains unconverted into CH3 NH3 PbI3−x Clx as PbCl2 that works as nucle-
ation vacancies leading to improved surface masking of perovskite layer [46]. It
is proposed that crystallization starts with the formation of complex ion agglom-
erates due to the limited solubility of the precursor containing chlorine. Chlorine
allows freezing of redundant organic components by restructuring of components
ions amid crystal growth, that in-turn ascertain the crystal and grain structure of per-
ovskite material. Thus, chlorine incorporation controls the morphological evolution
of the film and hence plays a role in tuning material characteristics and solar cell
efficiency.
Bromide (Br): Bromine is effectively used to tune the band gap of the perovskite
material [33]. It has been proposed by the Moscon et al. [43] that the introduction of Br
ions in iodide-based perovskite materials results in increased in band gap of material
as the result of crystal distortion [43]. Pure MAPbBr3 showed cubic crystal structure
at room temperature [44]. The PSCs based on CH3 NH3 PbI3−x Brx showed superior
efficiency and stability by changing the band gap through chemical combination
[47]. Moreover, Eperon et al. established the result of changing the I:Br ratios on
266 A. Bashir and M. Sultan

mixed halide FAPbI3−x Brx perovskite, representing an variable band gap from 1.48
to 2.23 eV with a range of film colour [33]. The highest PCE achieved was 14.2%
with higher Jsc of 23 mA/cm2 .
Complex ions: Lately, mixed perovskite MAPbI3−x (BF4 )x was synthesized by
the Nagane et al. [48]. They replaced the X ion with the BF4 − molecular ion [48]. The
MAPbI3−x (BF4 )x perovskite showed better electrical conductivities and improved
response to photons under one sun illumination conditions in contrast to MAPbI3 .
Because of strong hydrogen bond between halide BF4 − ion and MA ion, a lower
degree of vitalization of MA ion is expected [30].

4 Structure, Phase Transformation and Electronic

Characteristics of Perovskite Materials

Perovskites refer to a class of materials that have the general formula of ABX3 ,
where A and B are the two cations with very different atomic radii and X an anion.
The A cation is always occupied the cubooctahedral site of perovskite material,
while B cation is always present in an octahedral site. The oxidation states of A
and B cations depend mainly on the nature of X anion. If X = Oxygen, then A
and B sites are commonly filled by the divalent and tetravalent cations. However,
when X = halogen, then A and B sites are occupied by the monovalent and divalent
cations [49]. Perovskite material is broadly studied as light harvesting material for
PV devices because one can substitute a variety of elements having varied oxidation
states at A and B sites of this material. The most meritorious CH3 NH3 PbI3 has
CH3 NH3 + occupying A site, while Pb+2 present at B site as demonstrated in Fig. 2.
The optical, electronic and structural properties of perovskite material are directly
influenced by the ion arrangement and crystal constituents.
The formability and stability of perovskites are determined by a dimensionless
factor called Goldschmidt tolerance factor (t) given below,

0.707(rA + rX )
t=
rB + rX

where r A is the radius of cation A, r B is the radius of cation B, and r X is the radius
of X anion. A cubic structure is predicted for the perovskite material containing
transition metal cation and oxide anion with t = 1, whereas octahedral distortion is
observed when t < 1 [50]. When t < 1, the loss in symmetry is observed which in
turn effects the electronic properties of perovskite material [50]. For the perovskite
material, the stable crystal structure is formed when tolerance factor is 0.813 < t <
1.107 [51]. It is reported in literature that cation with ionic radii of 1.66 and 2.50 Å is
suitable for the formation of stable APbX3 (X = Cl, Br, I) type perovskite material.
The crystal structure of perovskite material has been confirmed by the XRD stud-
ies. The reported crystal structures for perovskite material through XRD studies are
cubic (Pm3 m), tetragonal (14/mcm) and orthorhombic (Pnma) [52]. At ambient
Organometal Halide Perovskite-Based Materials … 267

temperature, perovskite material possesses cubic crystal structure, which undergoes

series of phase transformation with decreasing temperature [53]. Perovskite crystal
structure becomes more symmetric as temperature increases: at room temperature,
MAPbI3 attains tetragonal structure, whereas MAPbBr3 and MAPbCI3 acquire cubic
structures [54]. Phase transition in methylammonium (MA), formamidinium (FA),
lead (Pb), Tin (Sn) and perovskite has been studied by Kanatzidis et al. [31]. They
pointed out the three different transition states: at high temperature α state exists,
while at intermediate temperature β state and at low-temperature gamma (γ ) state
exist as depicted in Table 1 [31]. It is clear from Table 1 that the FA-based perovskite
materials do not undergo phase transformation even at high temperatures; this prop-
erty is highly substantial to fabricate solar cells for field operation. Thus, phase
transformations that occur due temperature and pressure variation are the significant
factor to be considered for practical application of PSCs.
In Table 2, the selective physical, electronics and spectroscopic properties of per-
ovskite material used in PSCs are summarized. All perovskite materials have long
carrier diffusion length with the almost equal exciton binding energy and thermal
energy [55]. Furthermore, owing to very small exciton binding energy, both free
electrical charges and infirm bound exciton coexists [56]. All perovskite materi-
als possess direct band-gap and high absorption coefficient, i.e. 1.5 × 104 cm−1 at
550 nm [56]. The average diffusion length (LD) for MAPbCI3−X Clx has been calcu-
lated using relation LD = (Dτe )1/2 where D and τe are the coefficient of diffusion and
recombination lifetime in the inexistence of a quenching components, respectively
[56]. The values of D and τe were determined by the Stranks et al. by using photo-
luminescence quenching measurements. There reported values for MAPbCI3−X Clx
are more than 1 μm (Table 2).

5 Band-gap Tuning of Perovskite Materials

Hybrid perovskite materials exhibit larger absorption coefficient allowing the usage
of very thin films for light absorption [57]. Perovskite material with the thickness of
500 nm absorbed the solar radiation that is equivalent to the absorption by 2 μm thick-
ness of required by the typical silicon solar cells [30]. The perovskite material like
MAPbI3 and MASnI3 has direct band gap that ranges from 1.50 to 1.55 eV as deter-
mined from the ultraviolet photoelectron and ultraviolet-visible spectrophotometer
[17, 22, 28]. Nevertheless, the band gap of 1.55 eV is not enough for panchromatic
absorption due to the relatively shorter absorption wavelength limited to 800 nm [28].
To increase the absorption of energy towards higher wavelength without cooperating
for absorption coefficient, we can change the band gap of perovskite material. There
are two possible ways to attain this: (a) replacing the MA cation with other organic
cations, since replacement of MA with another cation alter the bond length and bond
angle in M–X–M of ABX3 without changing the valence band maximum [58]. For
example, the decreased in band gap of about 0.07 eV has been detected by replacing
the MA cation with FA cation. The absorption wavelength is also increased by 40 nm
 268

Table 1 Phase transformation of some common hybrid perovskite materials [30, 31, 99]
Perovskite State Temperature (K) Crystal structure Space group Lattice Parameters (Å) Volume (Å)
MAPbI3 α 400 Tetragonal P4 mm a = 6.3115 b = 6.3115 c = 6.3161 a = 8.849 b = 8.849 c = 251.6
β 293 Tetragonal I4 cm 12.642 a = 5.637 b = 5.682 c = 11.182 990
γ 162–172 Orthorhombic Pna21 959.6
MAPbCl3 α 178.8 Cubic Pm3 m a = 5.675 182.2
β 172.9–178.9 Tetragonal P4/mmm a = 5.655 c = 5.630 180.1
γ <172.9 Orthorhombic P2221 a = 5.673 b = 5.628 c = 11.182 375
MAPbBr3 α >236.9 cubic Pm3 m a = 5.901 206.3
β 155.1–236.9 Tetragonal 14/mcm a = 8.322 c = 11.833 819.4
γ 149.5–155.1 Tetragonal P4/mmm a = 5.8942 c = 5.8612 –
δ <144.5 Orthorhombic Pna21 a = 7.979 b = 8.580 c = 11.849 811.1
MASnI3 α 293 Tetragonal P4 mm a = 6.2302 b = 6.2302 c = 6.2316 241.88
β 200 Tetragonal I4 cm a = 8.7577 b = 8.7577 c = 12.429 953.2
FAPbI3 α 293 Trigonal P3m1 a = 8.9817 b = 8.9817 c = 11.006 768.9
β 150 Trigonal P3 a = 17.791 b = 17.791 c = 10.91 2988.4
FASnI3 α 340 Orthorhombic Amm2 a = 6.3286 b = 8.9554 c = 8.9463 507.03
β 180 Orthorhombic Imm2 a = 12.512 b = 12.512 c = 12.509 1959.2
A. Bashir and M. Sultan
Organometal Halide Perovskite-Based Materials … 269

Table 2 Physical, spectroscopic and electronic properties of some important perovskites

Properties MAPbI3 Ref MAPbCI3−X Clx Ref MAPbBr3 Ref
wt% Pb 33.4 – 39.2 – 43.3 –
Density (g/mol) 4.1 [31] – – – –
Mobility 66 [31] – – – –
(cm2 /V/s)
Dielectric 6.5 [100] – – 4.8 [101]
constant
Electron LaD 129 ± 11 [56] 1069 ± 204 [56] – –
(nm)
Hole LbD (nm) 105 ± 32 [56] 1213 ± 243 [56] – –
Exciton binding 37(1.5)–50 (2.0) [100] – – 2.9 [101]
energy (meVKT)
Absorption 100 [56] 100–200 [56] – –
length (1/α) (nm)
ELUMO (eV) −3.9 [23] −3.75 [102] −3.36 [27]
EHOMO (eV)c −5.4 [23] −5.3 [102] −5.38 [27]
Band-gap energy 1.5 – 1.55 – 2.02 –
(eV)
a is the diffusion length, b is the LUMO energy level and c is the HOMO energy level

approximately [31]. (b) directly altering the M–X bond [28]. For instance, when lead
ion (Pb2+ ) in MAPbI3 is partially replaced by the tin ion (Sn2+ ) ion, the band gap
reduces from 1.55 to 1.17 eV [59]. Therefore, one can change the band gap by chang-
ing the compositional ratio of Pb2+ to Sn2+ . Moreover, direct modification of M–X
bond in the perovskite material will consequently affect the valence band maximum
(VBM) and conduction band minimum (CBM), as band edges are adjudged by the
orbitals of B-position metals as established by fundamental computational studies
[60]. Furthermore, band gap is also varied by changing the halide ions of M–X bond.
A current study based on density functional theory (DFT) computations has
discovered that electronic structures of CH3 NH3 PbI3 (X = Cl, Br and I) and
CH3 NH3 PbI2 X [43, 60], where the calculated band gap were in rough conformity
with the experimental band-gap values for CH3 NH3 PbI3 with tetragonal (1.66 (1.55),
1.83 (1.78) and 1.64 (1.55))eV for X = I, Br and Cl, correspondingly. The band-gap
values for CH3 NH3 PbI3 with cubic structure are ((1.57 (1.55), 1.80 (2.00) and 2.34
(3.11)) eV for X = I, Br, and Cl, respectively, (the brackets values are experimental
values). Figure 3a, b shows the band-gap value diagram for ABX3 (A = MA and
FA, B = Pb, Sn, and X = Cl, Br or mixed Cl and Br) [60].
The perovskite materials containing both Pb and Sn ions are divine con-
tenders for very efficient PSCs, due to their appropriate optical band-gap and
absorption characteristics. Pb-based perovskite materials like CH3 NH3 PbI3 and
HC(NH2 )2 PbI3 have greater absorption coefficient as compared to the Sn-based
perovskite materials [31].
270 A. Bashir and M. Sultan

Fig. 3 a Electronic absorption spectra of MAPb1−x SnxI3 [59], b graphical sketch of energy
level for MAPbBr3 , MAPbI3 , FAPbI3 , MAPb1−xSnxI3 , MASnI3 and TiO2 [94], reproduced with
permission from WILEY-VCH Verlag GmbH and American chemical society

6 Construction of Perovskite Solar Cells

To attain the superior performance of PSCs it is very important to produce the high-
quality perovskite film during the solar cell fabricating process. Therefore, research
has been focussed to fabricate the high-quality perovskite film in term of crystallinity,
morphology and better optoelectronic characters. The optoelectronic properties of
perovskite film profoundly depend on the crystallinity which sequentially controls
the morphology. Furthermore, the morphology of the perovskite film influences the
efficiencies of charge separation, carrier diffusion lengths and charge recombina-
tion process in resultant perovskite film [30]. The morphology of perovskite film
is controlled by several factors, such as method of deposition, heating temperature,
annealing time, precursor materials ratio, and solvent and additives used [19, 61]. It
has been revealed that with the application of renewed and improved architecture in
PSCs the PCE has been enhanced from 6% through 12.3% to 15.4%. Still, even higher
efficiencies have been reported with the other superior design of PSCs [19]. Each
device type is manufactured on the standard architecture containing TiO2 acting as
electron transporting layer (ETL). The electron transporting layer can be produced
by several methods such as spray pyrolysis [42] or spin-coating [21] techniques.
Commonly, the thickness of ETL used is almost 100–500 nm [62].

6.1 Preparation Methods for Perovskite Films

The methods used for the fabrication of perovskite film have been broadly classified
into three types: (i) solution process technique, (ii) vapour deposition and (iii) vapour
assisted solution processing [22].
Organometal Halide Perovskite-Based Materials … 271

6.1.1 Solution Processing Techniques

Solution processing technique for perovskite deposition is the utmost protruding

technique as it is simplistic and low cost. The perovskite like CH3 NH3 PbI3 can be
deposited on the substrate via two routes: (i) spin-coating an already mixed solution
of CH3 NH3 I and PbI2 , also called one-step spin-coating technique, (ii) spin-coating
PbI2 with the subsequent deposition of CH3 NH3 I, also called two-step coating or
sequential deposition method. One-step spin-coating is the utmost desirable method
for manufacturing PSCs due to the compositional engineering of perovskite com-
ponents. The precursor solution is prepared by mixing CH3 NH3 X (X = Cl, Br, I)
powder and PbX2 (X = Cl. Br, I) in 1:1 stoichiometry, or in 3:1 in polar solvent
(like N, N-dimethylformamide DMF, gummabutyrolactone GBL or dimethyl sul-
foxide (DMSO) [60]. Followed by spin-coating process the perovskite film is dried
and annealed at different temperature depending upon the solvent used. In two-
step fabrication process, the PbI2 layer is first deposited on the substrate followed
by the spin-coating of CH3 NH3 I layer dissolved initially in 2-propanol (IPA). The
steps involved in both one-step and two-step spin-coating is demonstrated in Fig. 4a
Several factors affect the film quality through these methods such as spin-coating
speed and time, surrounding temperature, viscosity of solution and wettability. The

Fig. 4 Typical methods of perovskite layer formation: a one-step and two-step methods [95], b Co-
evaporation employing PbCl2 and MAI double sources [96], and d vapour assisted solution process
employing organic vapours of MAI, that react with already accumulated PbI2 films [63]. Reproduced
with permission from AIP [95], WILEY-VCH Verlag GmbH [96] and ACS [63] publications,
respectively
272 A. Bashir and M. Sultan

perovskite film deposited by two-step spin-coating method shows cubic structure,

whereas the film attained from one-step technique using dimethylacetamide (DMA)
shows amorphous morphology [63, 64]. A extra advance solution-based deposition
process is the two-step sequential deposition technique to develop more uniform
perovskite film as first introduced by the Liang et al. [57]. In this method, PbI2 film
is first spin coated over mesoporous TiO2 layer, using specific spin-coating speed
and time. The substrate is then soaked in the IPA solution containing appropriate
concentration of CH3 NH3 I [63]. The PSCs showed PCE of greater than 15%, when
perovskite film is deposited by the two-step sequential deposition process [42].

6.1.2 Vapour Deposition Technique

Vapour deposition technique was first developed by Snaith et al. [22] first used the
vapour deposition technique to produce the perovskite film. They fabricated the
CH3 NH3 PbI3−x Clx - based PSCs by co-evaporation of CH3 NH3 I and PbCl2 (Fig. 4b)
[22]. The whole process was carried out under nitrogen-filled glove box under vac-
uum. The CH3 NH3 Iand PbCl2 was co-evaporated on fluorine doped tin oxide (FTO)
substrate from the respective pots at 120 and 350 °C. The crystalline morphology
was obtained after annealing as-deposited perovskite film [22]. A highly uniform,
dense, pinhole free-perovskite film is obtained using this method. However, there is
a limitation associated with this technique; thermal evaporation required the evacu-
ation of chamber at higher vacuum level which involves the high cost and thus mass
production is not feasible [65]. This issue was overcome by the Yang et al. [66]. They
established a low-temperature deposition technique called vapour assisted solution
process (VASP) as shown in Fig. 4c. The perovskite films formed by this method
showed full surface coverage, high crystallinity and micrometre sized crystal grains.
Recently, VASP method had been used to fabricate the CH3 NH3 PbI3 film having
different thicknesses in planar device devices to get higher efficiency [66].

6.2 Device Architecture and Working Principle

The device structure and working principle of PSCs are analogous to that of ss-
DSSC as depicted in Fig. 5. Mainly two kinds of device architecture are reported in
PSCs (normal structure and inverted structure), as shown in Fig. 5. Both structures
mainly consist of transparent conductive oxide (TCO, like FTO or indium doped tin
oxide(ITO)), electron transporting layer (ETL) layer, perovskite layer, hole transport-
ing layer (HTL) and back contact (like Ag and Au). The energy level and working
principle of PSCs are shown in Fig. 2. When sunlight illuminates the perovskite
active layer, excitons are generated and then separated into free carriers. Afterwards,
generated electrons and holes can be transported to each interface and then injected
of ETL and HTL, respectively. Finally, the electrons and holes in ETL and HTL are
collected by working and counter electrodes, respectively, transported to external
Organometal Halide Perovskite-Based Materials … 273

Fig. 5 Schematics of architectures of perovskite SC in n–i–p and p–i–n configurations: a micro-

scopic n–i–p, b planar n–i–p, c planar p–i–n and d mesoscopic p–i–n [80]. Reproduced with
permission from Ref. [95]

circuit and produce current [42, 67]. According to the transient absorption spectro-
scopic studies, charge separation between perovskite and HTL was clearly detected,
while electron injection at open-circuit condition was not clearly detected [68]. This
indicates that HTL plays a critical role in carrier separation and transport in PSCs.
The various device architectures have been discussed in the following section.

6.2.1 The Mesoporous Scaffold Architecture

The most dominating architecture in PSCs is with the mesoporous structure. It usually
based on the solid-state DSSC architecture as shown in Fig. 5a. In this architecture,
the perovskite layer is fabricated within the interstice of mesoporous TiO2 layer [64].
This mesoporous TiO2 layer is essential to support the electron transport through the
perovskite layer and FTO electrode [64]. The mesoporous TiO2 NP layer is produced
by spin-coating a commercial TiO2 paste [42], followed by sintering at 500 °C
to afford improved connection among the TiO2 nanoparticles. Recently, TiO2 NP
composite with graphene oxide has been employed as highly efficient ETL scaffold
that improved the PCE up-to 15.6% [69]. The graphene nanoflakes impart excellent
charge collection dynamics within the nanocomposites that allow the fabrication of
entire device architecture at 150 °C [69]. In addition, nanocrystalline TiO2 blended
with the different metals have been reported [70]. More recently a researcher group
has created CH3 NH3 PbI3−x Clx PSCs built on the plastic film using amorphous SnO2
and mesoporous TiO2 layers as electrons collectors [71]. Later, same group fabricate
the brookite-based PSCs using CH3 NH3 PbI3−x Clx as a photoactive layer achieving
the PCE of 13.8% [72].
274 A. Bashir and M. Sultan

6.2.2 The Meso-Superstructure Architecture

The more development in the structure of PSCs has been attained by Lee et al. [17].
They substituted the mesoporous TiO2 scaffold with the inert mesoporous Al2 O3 net-
work. This structure was named as ‘meso-superstructured’ thin-film PSCs [73]. The
replacement of TiO2 scaffold with the inert mesoporous Al2 O3 network gave superior
optoelectronic characters to the perovskite film, which inspired researchers to further
developed the planar architecture PSCs [30]. Another advantage of replacement of
TiO2 scaffold with the inert mesoporous Al2 O3 is that one can overcome the chemical
instability issue of TiO2 under ultraviolet light (UV) [74]. The meso-superstructure
PSCs were further established by the Ball et al. [73]. They used mixed halide per-
ovskite material as light harvester and reported PCE of 12.3% [73]. The meso-
porous Al2 O3 reduces the crystallite size of perovskite down to 100 nm as revealed
by XRD and also acting as a shielding layer thwarting the current seepage at the
electrode [73].

6.2.3 The Planar Architecture

The planar heterojunction architecture was first established by the Liu et al. [22]. The
planar structure contains perovskite layer that was vapour deposited and reported
PCE was >15%. This type of architecture categorizes further into two types; one is
the normal with the normal configuration (n–i–p) and other with the inverted config-
uration (p–i–n) as depicted in (Fig. 5). The normal planar heterojunction consists
of glass/TCO/ETL/perovskite/HTL/metal, while inverted heterojunction contains
glass/TCO/HTL/perovskite/ETL/metal [30]. Generally, HTL/ETL acts as selective
charge extraction layers [30]. The silver (Ag) and Gold (Au) are the normally acting
as top electrode which collects the holes, though Ag is less commonly used as top
electrode owing to its chemical sensitivity towards perovskite material. Recently,
Nickel (Ni) and carbon have also been used as hole collector due to their improved
stability as compared to the Ag and Au [36].
The most important architecture in PSCs is the mesoscopic structure with n–i–p
configurations. Many high-efficiency solar cells implement this device configura-
tion. The normal mesoscopic n–i–p architecture is shown in Fig. 5a. This archi-
tecture consists of FTO acting as cathode, a thin compact layer of TiO2 (thickness
is about 50–70 nm) acting as ETL, a mesoporous layer of metallic oxide (normally
TiO2 or Al2 O3 , 150–300 nm thickness) acting as scaffold for perovskite material, a
perovskite absorber layer having thickness of about 300 nm, an HTL layer with thick-
ness of 150–200 nm, and top electrode with the thickness of 50–100 nm (normally
Au or Ag).
Previously, the perovskite film used as light harvester in PSCs has the thickness
of more than 500 nm. But, since the grain expansion of perovskite restricted in
the structure pores, a considerable measure of the substance exists in amorphous
phase [75], resultant comparatively lower open-circuit voltage (Voc ) and short-circuit
current density (Jsc ) [74]. However, by decreasing the thickness of mesoporous film
Organometal Halide Perovskite-Based Materials … 275

to 150–200 nm remarkably enhanced the device efficiency because of improved

crystallinity of perovskite film [24]. Further reducing the thickness below 150 nm
results in poor Jsc and device performance, Yang et al. reported the PCE of 20.2%
with the mesoscopic structure consisting of perovskite nanocrystals in-built in the
preceding ETM layer with the top uniform and compact perovskite layer [76].
The planar n–i–p architecture is demonstrated in Fig. 5b. Now highly efficient
PSCs can be fabricated without a mesoporous layer by careful supervision of growth
of perovskite film, the perovskite interface, carrier transport films and electrodes
[19]. Zhou et al. [19] fabricated the highly efficient planar n–i–p PSCs and reported
the PCE of 19.3% [19].
In the inverted architecture (p–i–n) the order in which the films are deposited is
inversed in contrast to n–i–p architecture as shown in Fig. 5c. In these types of PSCs,
a 50–80 nm thick HTL is deposited first on the top of TCO, later on the intrinsic
perovskite layer of 300 nm thickness is deposited on the top of HTL, followed by
the deposition of ETL of about 10–60 nm thickness. Finally, the whole device stack
is completed by the deposition of back contact of metal (Au/Ag/Al). Dong et al.
first fabricated the planar p–i–n PSCs and attained PCE of 18.9% [77]. With further
progress in the p–i–n solar cells architecture, the specific contact substitutes have
been extended from organic to inorganic matter [78, 79].

7 Challenges Related with the PSCs and Their Potential

Solutions

There are certain challenges that are related to the PSCs. The challenges related to
the PSCs and their possible solutions are discussed below.

7.1 J-V Hysteresis

The abnormal current-voltage hysteresis has been observed on PSCs. In J-V hystere-
sis, the efficiency of solar cells is anomalously dependent on the voltage scan rate
and scan speed (Fig. 6a). The three possible reasons for J-V hysteresis have been sug-
gested by the researchers [80], namely ferroelectricity (Fig. 6b) [81], ion migration
(Fig. 6c) [68], [82], and unbalance charge collection rates [83] (Fig. 6b). Recently, a
more consideration has been paid to the ferroelectric polarization of perovskite mate-
rial as their ferroelectric properties may be critical in enhancing the power conversion
efficiencies and stability [65]. Ferroelectricity influences the separation of photoex-
cited electrons and holes as well as recombination rate (Fig. 6b) [84]. Simulations
implied that the internal electric field pertaining to microscopic polarized regions
produce hysteresis in the current-voltage features of perovskite devices because of
alteration in the electron-hole reunion in the material volume [85]. According to Xia.
276 A. Bashir and M. Sultan

Fig. 6 a J−V hysteresis shown for various scan rates and scan directions [82]. b Ferroelectric
behaviour of CH3 NH3 PbI3 perovskite [97]. c Schematic that depicts the effect of ion drifting in
perovskite SCs [68]. d A considerable J − V hysteresis has been observed when the perovskite solar
cell is cooled down to 175 K [98]. Figures are reproduced with permission from royal chemical
society, ACS publications and nature publications under creative commons licence

et al. [86], perovskite material shows strong ionic characters, and in the presence of
electric field it gets polarized. Furthermore, a study based on impedance revealed that
higher value of dielectric constant at lower frequencies is the cause of J-V hysteresis
and this mainly arises due to the dipolar, ionic and electronic contributions [87].
Snaith et al. proposed that the abnormal hysteresis may be due to the ferroelectric
behaviour of the perovskite material owing to which material gets weakly polarized,
capacitive effects, defects that are present on the surface of absorber [88]. Further-
more, in case of mesoporous architecture PSCs, the hysteresis strongly dependent on
the crystal growth within mesoporous structure as well as thickness of mesoporous
layer [88]. The J-V hysteresis is also dependent on the charge transport rate at per-
ovskite/ETL and perovskite/HTL interface. The inverted p–i–n PSCs showed signif-
icant smaller hysteresis, likely because of uniform charge transport and passivation
of perovskite/HTL or perovskite/ETL interface [81, 89] (Fig. 6d).
The ferroelectric response of CH3 NH3 PbI3 has been probed by analysing the
polarization electric field, though it was strongly affected by leakage current and
hence cannot be treated as an incontestable evidence to the electric response [81].
Kutes et al. for the first time demonstrated the existence of ferroelectric domain in
high-quality CH3 NH3 PbI3 thin films fabricated by a solution processing method.
Organometal Halide Perovskite-Based Materials … 277

They reported the size of the ferroelectric domains to be approximately to the size
of the grains (approximately 100 nm).

7.2 Long-Term Stability

Another issue that is related to the PSCs is the long-term stability of these devices.
A further progressive consideration is needed to understand the degradation mecha-
nism, which is eventually necessary for the outdoor applications of PSCs. The reac-
tivity of perovskite films towards water has been confirmed by the standard negative
Gibbs Free energy for CH3 NH3 PbI3 degradation with humidity [90]. CH3 NH3 PbI3
perovskite undergoes hydrolysis in the presence of moisture due to its hygroscopic
nature. The decomposition takes place through the following paths as given below;

CH3 NH3 PbI2(s) → CH3 NH3 I(aq) + PbI2(s) (1)

CH3 NH3 I(aq) → CH3 NH2(aq) + HI(aq) (2)

4HI(aq) + O2(g) → 2I2(s) + 2H2 O(I) (3)

2HI(s) → I2(s) + H2(g) (4)

The reaction (Eq. 1) shows that CH3 NH3 + is separated from the structure of
perovskite and compound with the iodine to form aqueous CH3 NH3 Iand solid PbI2
salt. The CH3 NH3 I further decompose into aqueous methylamine and hydroiodic
acid (Eq. 2). Furthermore, hydrogen iodide (HI) can undergo further decomposition
to give water and I2 through a redox reaction due to the presence of oxygen (Eq. 3).
The HI also undergoes photochemical reaction in the presence of UV light to form
I2 and H2 gas. The perovskite degradation takes place even at lowest humidity level
of 55%, and film colour change from dark black to yellow is an indicator of this
phenomenon [47].
Snaith et al. [91] fabricated the PSCs with enhanced thermal and moisture stability
by replacing the organic HTL with single-walled carbon nanotubes (SWCNTs). The
SWCNTs was modified with the insulating polymeric matrix [91]. The PSCs using
this HTL showed improved thermal stability and performance as compared to the
PSCs based on organic HTL. Mei et al. [60] reported the PSCs without using HTL
and contain double film of mesoporous TiO2 /ZrO2 scaffold. The contact layer of 10-
micron thickness was a critical player in improving the resistance to water and the
cell registered a certified PCE with stability over 1000 h in full sunlight and ambient
air conditions.
278 A. Bashir and M. Sultan

8 Conclusions

This chapter has demonstrated the complete summary of gradual progress and limits
in the field of PSCs. This chapter also summarized the basics of perovskite materials
with a focus to explain their widespread applications in photovoltaics solar devices.
We have also discussed the recent progress on the compositional engineering and
interface features of perovskite layer and electric contacts, as these properties are crit-
ical to improve the power conversion efficiencies of PSCs. Such progressive bulk and
interface engineered architecture will be favourable for increasing perovskite grain
size and crystallinity, removing surface and bulk defects, refining film morphol-
ogy and enhancing film uniformity. Interface engineering improved charge carrier
dynamics across solar cell junction, charge extraction and transportation, and thus
helps to enhance the device performance. Furthermore, the perovskite film deposi-
tion techniques such as solution processing, vapour deposition and vapour assisted
solution processing have been discussed in detail. The perovskite film quality, crys-
tallinity and uniformity are strongly dependent on the deposition method employed.
The perovskite film morphology has been controlled by solvent engineering, hence
been an important player in improving the PCE of PSCs. Moreover, the band-gap
tuning of perovskite material has been discussed in detail. Finally, the problems
that are associated with the perovskite solar cells such as J-V hysteresis have been
demonstrated. These are the main factors that are preventing the further advancement
of PSCs. The next major issue which has been identified is the long-term thermal
and chemical stability of perovskite SCs, which requires to be focussed urgently to
launch them in the market for outdoor photovoltaic applications.

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Effect of Oxygen Vacancies in Electron
Transport Layer for Perovskite Solar
Cells
Mohamad Firdaus Mohamad Noh, Nurul Affiqah Arzaee
and Mohd Asri Mat Teridi

Abstract Metal oxide-based electron transport layer (ETL) is one of the vital com-
ponents in conventional n-i-p type perovskite solar cells (PSC) that enables efficient
electron extraction and transport within the device. Nonetheless, native point defect
associated with oxygen vacancies that naturally exist in the ETL materials such as
TiO2 , SnO2 and Nb2 O5 could deteriorate the overall performance of the PSC. In
this chapter, the intentional and unintentional formation of oxygen vacancies during
the fabrication process of the ETL will be firstly clarified. The properties of oxygen
vacancies in the viewpoint of structural, optical and electrical as well as surface wet-
tability will also be profoundly elaborated to provide valuable insight on the impact
of oxygen vacancies in the ETL towards efficiency, hysteresis and stability of PSC
devices.

Keywords Perovskite solar cells · Electron transport layer · Metal oxide · Point
defects · Oxygen vacancy

1 Introduction

Perovskite solar cells (PSC) have appeared as a shining star among the third genera-
tion solar cells owing to their excellent solar-to-power conversion efficiency (PCE)
of beyond 20% [1–3]. Now, the development of PSC has entered a new phase which
is aiming for vast fabrication for future commercialization but there are still sev-
eral issues related to long-term stability and hysteresis behaviour of the device that
require some degree of attention [4]. Many factors have been acknowledged as the
major causes for the instability of PSC and among those, existence of humidity in
ambient environment is the most crucial one [5, 6].
It is known that PSC is made up of several layers with electron transport layer
(ETL) being one of the most essential components for boosting the overall perfor-
mance of the device [7]. The ETL is necessary for enabling efficient transfer of the

M. F. M. Noh · N. A. Arzaee · M. A. M. Teridi (B)

Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 Bangi,
Selangor, Malaysia
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 283

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_11
284 M. F. M. Noh et al.

photoexcited electrons from the perovskite layer and to block the transition of holes
from the perovskite to the FTO substrate. This will prevent charge recombination
in the device that could deteriorate the short-circuit current density (JSC ) as well as
open-circuit voltage (VOC ). The ETL could also accelerate the transport of extracted
charges to external circuit via FTO. To date, the ETL is built based on inorganic or
organic material where the former is usually implemented in conventional structured
devices, while the latter is widely used in inverted structured devices. For devices
having conventional architecture, the ETL used is typically made up of wide band gap
metal oxide such as TiO2 [8], SnO2 [9], and ZnO [10]. All of these metal oxides are
chosen as ETL for PSC not only due to their electrical properties including excellent
charge transfer and transport ability, but also attributed to the compatible conduction
band and valence band with respect to perovskite as well as outstanding thermal,
chemical and photochemical stability.
Perfectly bonded atoms in metal oxides (i.e. metal oxides without defects) render
the material incapable to conduct electrical charges [11]. Hence, nonstoichiometric
defects related to oxygen vacancies are important characteristics for metal oxides that
govern a range of their properties including electrical conductivity, diffusion kinetics
and electronic structure [12, 13]. Together with other point defects such as cation
interstitial, cation vacancies and oxygen vacancies are the most common defects
that occurs in the lattice of nonstoichiometric undoped metal oxides. In relative to
other defect species, oxygen vacancies are well-known as the predominant one that
play pivotal role in determining the properties of metal oxides [14]. Figure 1a and b
schematically illustrate the formation of oxygen defects on the surface of TiO2 during

Fig. 1 Schematic diagram of oxygen vacancies. a Formation of doubly ionized oxygen vacancy
on the surface. Reproduced with permission from [15]. Copyright 2011, with permission from
American Chemical Society. b Oxygen vacancies in the crystal lattice of TiO2
Effect of Oxygen Vacancies in Electron Transport … 285

the interaction with oxygen as well as the oxygen defects in the lattice. The removal
of an oxygen ion from the surface creates oxygen vacancy which is fully ionized
at high temperatures. Meanwhile, the removal of one neutral oxygen atom from the
crystal lattice leads to the formation of one point defect and two under-coordinated
Ti3+ [15, 16].
Nevertheless, extremely high concentration of oxygen vacancies in the ETL of
PSC could result in poor device efficiency. To make things worse, oxygen vacancies
have been found as another factor that may accelerate the degradation process of
perovskite layer and adversely affect the hysteresis behaviour of the PSC [17]. Even
though investigation on this topic is not substantial up to now, the issue should not
be overlooked as it is still seen as one of the vital aspect that requires urgent attention
to allow mass production of highly efficient, stable and hysteresis-free PSC device
in near future. Therefore, in this chapter, the formation and properties of oxygen
vacancies in metal oxide-based ETL as well as their impact towards the performance
of PSC are clarified.

2 Formation of Oxygen Vacancies During Fabrication

During the fabrication process of metal oxide-based ETL, oxygen vacancies may
be formed either intentionally or unintentionally. Parameters that may lead to the
formation or elimination of oxygen vacancies in pristine metal oxides include the
quantity of oxygen that is available during the fabrication, precursor annealing, fab-
rication method adopted and introduction of dopant. Meticulous control on these
fabrication parameters could modify the concentration of oxygen defect generated.
Other strategies in manipulating the defect density have also been reported for other
solar energy-based technologies such as photocatalysts [18, 19] and dye-sensitized
solar cells [20, 21] but this chapter only focuses on the development that has been
conducted for PSC devices.

2.1 Oxygen Quantity

The presence or more specifically quantity of oxygen is the most critical aspect in
determining the amount of oxygen vacancies in the fabricated metal oxide thin films.
Intentionally tuning the quantity of oxygen present in environment during fabrication
is the easiest approach to regulate the density of oxygen deficiency in the film. This
includes annealing the metal precursor at different environmental condition or in con-
trasting oxygen pressure, applying plasma treatment and adjusting the oxygen flux
during direct current magnetron sputtering (DCMS) or radio frequency magnetron
sputtering (RFMS) process. Influence of annealing will be elaborated further in next
section. From the viewpoint of plasma treatment, Zhang et al. [22] demonstrated
that applying O2 plasma treatment towards pre-annealed compact TiO2 layer would
286 M. F. M. Noh et al.

decrease the intrinsic point defects, i.e. oxygen vacancies particularly at the surface of
TiO2 . On the other hand, inverse phenomenon was observed upon treating the sample
by Ar plasma where oxygen vacancies in TiO2 were remarkably amplified. Mean-
while, increasing the value of oxygen flux in DCMS or RFMS process would also
reduce the oxygen deficiency in compact metal oxide thin film providing that other
deposition parameters, such as sputtering time, total pressure, etc., are kept constant
[23, 24]. Here, it must be noted that oxygen flux even in small amount is required
during the sputtering process if pure metal is used as target. However, pure Ar
environment may be applied only if the target is already in the form of oxide metal.

2.2 Annealing

Indeed, formation of metal oxide is thermodynamically favourable since the enthalpy

of formation of most metal oxides is typically lower in comparison to the metal-
based precursor like metal chloride, metal nitride, etc. Yet, annealing process is a
crucial step in the fabrication of both compact and mesoporous metal oxide layers as
energy is required for activating the breaking and formation of the bonds during the
synthesis process. In addition, most metal oxides require high temperature thermal
treatment in order to function well as ETL. For instance, TiO2 must be annealed
at temperature range of 450–500 °C to allow nanocrystallite formation [25]. The
reason lies in the fact that TiO2 shows excellent electrical conductivity only after
it has turned into nanocrystallites [7]. Some metal oxides, such as SnO2 and ZnO
indicate higher performance after annealing at temperature of less than 200 °C as a
result of their distinguished electron recombination resistance [26, 27]. Therefore,
it can be generalized that annealing process is a vital procedure for enhancing the
electrical properties of the ETL which eventually affects the overall performance of
PSC device. It is worth mentioning that the thermal treatment may also influence the
crystallinity, morphology, electrical and optical properties of the metal oxide layer
which should be taken into consideration during the fabrication of highly efficient
device [7, 28].
Very low or very high temperature applied during processing of metal oxide may
induce the generation of oxygen vacancy defects in the crystal lattice or on the sur-
face of the film [17, 29, 30]. Under low-temperature operation, the energy supplied
is usually insufficient to fully convert the metal-based precursor to metal oxide espe-
cially when precursor based on metal with lower oxidation state is employed for
the synthesis. The low-temperature treatment subsequently slows down the rate of
oxygen vacancies annihilation. For instance, the use of SnCl2 instead of SnCl4 as
precursor easily creates non-oxidized Sn2+ in the low-temperature-synthesized SnO2
[29]. This is due to the fact that Sn and Cl atoms in SnCl2 are held together by ionic
bonds and hence, it is hypothesized that the forces that held the atoms together are
relatively strong [31]. Therefore, low-temperature processing would limit the heat
energy needed to break the ionic bonds and impede successful reaction between Sn
and O atoms. This concept is also applicable for other metal oxides. On the other
Effect of Oxygen Vacancies in Electron Transport … 287

hand, exposing the metal oxide to elevated temperatures intensifies the vacancy con-
centration almost linearly. As reported by Wendt et al. [32], oxygen vacancies in
TiO2 increase upon annealing the material up to approximately 676 °C. This could
be attributed to slight decomposition of metal oxide during thermal treatment which
leads to oxygen vacancies formation. Palumbo et al. [33] demonstrated that annealing
of TiO2 at temperature up to 500 °C generates oxygen vacancies which are reducible
through decreasing the processing temperature to 400 °C. Applying lower tempera-
ture treatment, however, has adverse effect in terms of organic residue on the surface
and crystallinity of TiO2 film.
The condition applied during annealing of metal oxide could also alter the den-
sity of oxygen vacancy sites in the film. For example, it was shown that annealing of
TiO2 in ambient air has greater potential to promote oxygen vacancies formation [34].
This could be attributed to the relatively low percentage of oxygen in environment
which reduces the probability of successful collision and reaction between oxygen
molecules and metal precursors. Although the oxidation of TiO2 begins from the
surface and gradually penetrates into the bulk of the film, the deficiency of oxygen
still appears throughout the film (i.e. both at the surface and in the bulk). This defect,
however, could be alleviated by either introducing oxygen environment annealing or
prolonging the annealing duration [32, 34]. As depicted by XPS spectra in Fig. 2,
shoulder peak centred at 457.3 eV which corresponds to Ti4+ bound to an oxygen
vacancy (Ti4+ –VO ) declines as annealing of TiO2 film was carried out in oxygen envi-
ronment instead of ambient air. Further reduction was detected upon extending the
duration of annealing process which verifies the impact of environmental condition
towards the generation of oxygen vacancies.

Fig. 2 X-ray photoelectron spectroscopy (XPS) analysis of Ti 2p3/2 peak in TiO2 film annealed in
air and O2 environment for 0.5 and 2 h. Main peak centred at 458.8 eV (light blue) and shoulder peak
centred at 457.3 eV (red) correspond to Ti4+ 4+
(2p/3) state and Ti bound to an oxygen vacancy, respec-
tively. Reproduced with permission from [34]. Copyright 2017, with permission from American
Chemical Society
288 M. F. M. Noh et al.

2.3 Fabrication Method

The choice of fabrication technique may also unintentionally manipulate the type
and amount of defect states such as oxygen vacancies and perhaps low-oxidation
state metal ions in the as-prepared metal oxide-based ETL. For instance, Noh et al.
[17] discovered that aerosol-assisted chemical vapour deposition (AACVD) which
represents vapour-based deposition method could eliminate the oxygen vacancies
in SnO2 thin film. On the contrary, high amount of oxygen vacancies appears upon
employing solution-based deposition method which is represented by spin coating
technique in the same study. Such phenomenon could be related to the film formation
mechanism induced by the fabrication environments. In the study conducted by
Noh et al. [17], SnO2 thin film was fabricated at low temperature rather than high
temperature as most PSC devices have been verified to perform efficiently using
low-temperature-treated SnO2 as ETL [35]. As described in the previous section,
low-temperature processing could induce oxygen vacancies generation due to the
inadequate energy supply for complete metal oxidation. Nonetheless, for deposition
using AACVD technique, the reaction between Sn-based precursor and oxygen (O2 )
occurred readily on the surface of the substrate. Since O2 gas is supplied excessively
during the deposition process, complete reaction between Sn-based precursor and
O2 is able to take place resulting in the formation of SnO2 . It should be emphasized
that O2 molecules react right after the chemisorption of Sn-based precursor which
lead to the growth of SnO2 layer and inhibit the formation of oxygen vacancies in
the film.
Conversely, oxygen vacancies may be created upon utilizing spin coating tech-
nique especially during annealing of the spin-coated precursor solution. The mecha-
nism for oxygen vacancies generation can be described as follows. During annealing
step, solvent and by-products start to evaporate and leave Sn-based intermediates
on the surface of the substrate. As the sample is continuously heated, the Sn-based
intermediates are converted to SnO and then, the SnO particles are oxidized by O2
molecules in environment which eventually produces SnO2 film. Since O2 molecules
are able to infiltrate only from the surface of the layer which is directly exposed to air,
this may cause incomplete oxidation of SnO to SnO2 particularly at the region near
to FTO. Consequently, high amount of oxygen vacancies is produced. The schematic
diagram in Fig. 3 depicts the effect of fabrication methods towards oxygen defects
formation in SnO2 films. Therefore, it could be generalized that solution-based depo-
sition techniques that comprise of annealing step similar or almost similar to spin
coating method such as dip coating, spray pyrolysis, etc., may lead to the formation
of oxygen vacancies in the oxide-based thin film.
Effect of Oxygen Vacancies in Electron Transport … 289

Fig. 3 Schematic diagram of a fabrication procedure and b film formation in spin-coated-SnO2

thin film which generates oxygen vacancies. c Fabrication procedure and d film formation in
AACVD-SnO2 thin film which annihilate oxygen vacancies. Reproduced with permission from
[17]. Copyright 2018, with permission from Elsevier

2.4 Doping

Doping is an effective approach in tuning the concentration of oxygen vacancies.

For the development of PSC device, a series of materials ranging from metal cations
(from monovalent to pentavalent) to non-metal anions such as Li+ , Co2+ , Fe3+ , Nb5+ ,
Ta5+ and F− , to name but a few, have been successfully adopted as dopant in the
host metal oxide-based ETL [36–42]. Successful doping could only take place if
the dopant is capable to diffuse as interstitial ion through the crystal lattice of host
material during the fabrication process [16]. In principle, the density of oxygen
defects typically shows decreasing trend initially up to a certain degree and followed
by an increment as the doping concentration increases. Here, it is worth mentioning
that extremely high amount of doping concentration would lead to formation of metal
oxides nanocomposite.
Appropriate quantity of dopant could reduce the oxygen deficiencies to a desired
amount which would be beneficial for the application in PSC. However, the opti-
mal percentage of dopant introduced depends on the oxidation state of the dopant
and density of defect in the ETL. For instance, Giordano et al. [36] and Liu et al.
[43] introduced Li+ ions into TiO2 crystal lattice by thermal diffusion and noticed
remarkable depletion of oxygen vacancies which they attributed this outcome to the
partial reduction of Ti4+ to Ti3+ induced by Li+ . In other words, the presence of Li+
290 M. F. M. Noh et al.

Fig. 4 Elimination of oxygen vacancies in TiO2 crystal lattice by introduction of Fe3+ dopant.
Reproduced with permission from [38]. Copyright 2017, with permission from Royal Society of
Chemistry

stabilized the Ti4+ bound to oxygen vacancy (Ti4+ –VO ) to Ti3+ through the removal
of the dangling bonds. Gu et al. [38] incorporated 1 mol% of Fe3+ as dopant into
TiO2 and found that two Fe3+ ions can replace two adjacent Ti4+ –VO as displayed in
Fig. 4. Comparable result was also observed by Pathak et al. [16] in which case they
developed Al3+ -doped TiO2 using 0.3 mol% of Al3+ as ETL. Substitution of one Ti4+
by Al3+ is in fact energetically unfavourable but it is believed that Al3+ tend to replace
two Ti4+ accompanied by a release of the bridging oxygen. Therefore, in TiO2 crystal
containing defect sites, substitution of Al3+ cations with Ti3+ and oxygen vacancies
is claimed to be thermodynamically and electronically favourable [44]. Since both
Fe3+ and Al3+ dopants are trivalent cations, the substitution of Ti4+ –VO causes the
dopant to form bond with only three adjacent oxygen atoms and therefore removes
the oxygen defect sites from the crystal lattice.
Most researches described here employed very low amount of dopant (less than or
equal to 1%) in the host metal oxides because such quantity could assist in reducing
the oxygen deficiencies which is highly advantageous for the performance of PSC
device. The use of high percentage of dopant, however, would foster the generation
of free charge carriers owing to the formation of new oxygen vacancy sites. This
argument has been proven by Wu et al. [45] where they demonstrated that inclusion
of 10% Fe as dopant in anatase TiO2 nanoparticles lead to substitution of Fe3+ for Ti4+
which deliberately creates oxygen vacancies. Such defect is favourable for boosting
the photocatalytic activity of TiO2 but is actually detrimental towards PSC perfor-
mance. This topic will be further clarified in the subsequent section of this chapter. It
should also be noted that reduction of oxygen vacancies is not the only critical factor
that determines the optimal performance of the ETL, but also morphology, electrical
properties and electronic structure which could also be affected by doping must be
taken into account [46–48]. Therefore, the quantity of dopant should be optimized by
considering every single aspect to balance the entire properties of the ETL to realize
Effect of Oxygen Vacancies in Electron Transport … 291

maximum cell performance. The impact of doping towards the overall properties of
metal oxides, however, would not be elaborated further in this chapter.

3 Properties of Metal Oxide with Oxygen Vacancies

Loss of oxygen in the metal oxide crystal may have decent effect on the structural
properties and surface wettability of the film. However, tuning the properties of ETL
is of great importance in order to achieve highly efficient and stable PSCs because
the existence or specifically concentration of oxygen vacancies in the metal oxides is
majorly responsible for determining the optical and electrical properties of the ETL.

3.1 Structural Properties

Oxygen defect usually has a negligible influence towards the crystal phase of a partic-
ular metal oxide. However, metal oxide film that consists of greater concentration of
oxygen vacancy sites would typically have larger lattice constant and vice versa. As
stated by Du et al. [23], the lattice constant of anatase TiO2 film increases as higher
amount of oxygen vacancies exist in the film. This characteristic manifested itself
in the shifting of X-ray diffraction (XRD) peak towards a lower diffraction angle
particularly at Bragg angle of 25.37° which is assigned to the (101) plane (Fig. 5).

Fig. 5 a Wide and b high-resolution XRD spectra of TiO2 film prepared via sputtering technique
with different oxygen flux. Lower oxygen flux represents higher density of oxygen vacancies.
Reproduced with permission from [23]. Copyright 2017, with permission from Royal Society of
Chemistry
292 M. F. M. Noh et al.

It is widely recognized that oxygen binds the cations in TiO2 film and hence, the
cation–cation overlap reduced as a consequence of underdeveloped oxygen content
which subsequently results in lattice constant enlargement. The occurrence of lat-
tice distortion in metal oxide could also be ascribed to the difference in ionic radius
between two states of metal cation. For instance, the ionic radius of Ti4+ is 0.61 Å
which is slightly lower than that ionic radius of Ti3+ which has a value of 0.64 Å [16].
Another example is Sn4+ and Sn2+ which have ionic radius of 0.69 Å and 0.62 Å,
respectively [29, 49]. Oxygen vacancy defects also have slight impact towards the
morphological properties of the film, such as surface roughness and layer thickness.
For example, the thickness and roughness of TiO2 thin film fabricated using DCMS
technique exhibited increasing trend up to a certain maximum value and then decreas-
ing again with increasing density of oxygen defect. The cause of such phenomenon
is still vague, but it is postulated that greater oxygen vacancies accelerate the growth
rate of TiO2 layer [23].

3.2 Wettability

In the fabrication of PSCs, wettability is actually an important characteristic for

the ETL as it can influence the resistance of the sample towards humidity-induced
degradation. In other words, wettability of metal oxide-based ETL could affect the
long-term stability of the device especially during exposure to ambient air. However,
most researches nowadays usually do not consider wettability as a critical issue since
the fabrication process is mostly conducted in glove box with ultra-low humidity
level and the completed devices are properly encapsulated [50–54]. Yet, for realising
commercializable perovskite devices with high stability which can be fabricated in
high-humidity condition, wettability of ETL must be taken into consideration.
Less wettable (i.e. less hydrophilic or more hydrophobic) ETL is highly desirable
for PSC devices as it would improve the resistance of the sample towards humidity
and ultimately enhance the long-term stability of PSC. Wettability of a surface could
be influenced by the surface roughness, crsytallinity and presence of oxygen vacan-
cies [55–61]. It has been reported that greater amount of oxygen vacancies would
increase the hygroscopic nature of particular metal oxide layer which in turn reduces
the value of water contact angle. As unveiled in Fig. 6, SnO2 film with low- and high-
defect sites have water contact angle of 93.9° and 63.3°, respectively. The presence
of oxygen vacancy encourages dissociative adsorption of water at the vacancy sites.
This is due to the fact that the single oxygen atom of water heals the vacancy, while
the other two hydrogen atoms bind to the oxygen atoms on the surface of metal oxide
to form hydroxyl groups [55, 56]. Since the hydroxyl groups that were created on
the film surface are polar molecules, they are able to form oxygen bonds with the
subsequent water molecules which consequently promotes the surface hydrophilicity
of metal oxide [17].
Effect of Oxygen Vacancies in Electron Transport … 293

Fig. 6 Water contact angle measurement of SnO2 surface with a low amount and b high amount of
oxygen vacancies. Reproduced with permission from [17]. Copyright 2018, with permission from
Elsevier

3.3 Optical Properties

Optical properties are another pivotal feature for metal oxide ETL as it affects the
absorption ability of the subsequent perovskite layer which in turn determine the pho-
togeneration rate of charge carriers. To achieve maximum device efficiency, metal
oxide ETL must possess high light transmittance (i.e. wide band gap) and compatible
electronic configuration (i.e. lower conduction band minimum (CBM) and valence
band maximum (VBM) with respect to perovskite light harvester) [7, 62–64]. These
properties are in part determined by the defect sites in the film and thus, meticulous
control on the capacity of oxygen vacancies in metal oxide is necessary to acquire
the desirable optical properties [65]. As displayed in Fig. 7, the colour of metal
oxides such as TiO2 and SnO2 becomes darker as the amount of oxygen vacancies
increases implying that the optical properties including light absorption, transmit-
tance and reflectance are affected by the defects. In another report by Guo et al. [66],
they detected that sputter-deposited Nb2 O5 layer possessing high oxygen vacancies

Fig. 7 a TiO2 thin films with different density of oxygen vacancies (from left to right: low to
high oxygen vacancies). Reproduced with permission from [22]. Copyright 2016, with permission
from American Chemical Society b SnO2 powders with different density of oxygen vacancies (left:
commercial SnO2 with low oxygen vacancies; right: SnO2 with high oxygen vacancies or Sn3 O4 ).
Reproduced with permission from [29]. Copyright 2017, with permission from Elsevier
294 M. F. M. Noh et al.

exhibits a relatively low light transmittance of less than 70% in comparison to sample
with low oxygen defect which achieved greater transparency of above 80%.
High percentage of defect sites (i.e. oxygen vacancies) on the surface and in crystal
lattice of metal oxide results in band gap narrowing [67, 68]. This causes greater light
absorption by the metal oxide which is observable from the red-shift in absorbance
spectra and reduction in light transmittance ability of the thin film (Fig. 8a) [17,
34]. Moreover, metal oxide with high oxygen defects apparently implies extended
absorption tail into visible light region which is basically originated from the electron
transitions associated with surface oxygen vacancies-induced electronic states near
the band edge (Fig. 8b). In other words, oxygen vacancies introduced new energy
level in the band gap near the band edge of metal oxide which enable photons with
lower energy to excite electrons trapped in localized states within the band gap
[69]. The amount of low energy photon that can be absorbed increases with the
increasing concentration of oxygen vacancies [17]. Strong absorption in the visible
region renders the metal oxides darker in colour. Low oxygen vacancies in metal
oxide layer are, therefore, required to widen the optical band gap in order to allow
more solar light passing through the ETL and being absorbed by the perovskite layer
to generate larger photocurrent [34].

Fig. 8 a Light transmittance spectra (inset is Tauc Plot for band gap determination) of TiO2 film
annealed in air and O2 environment for different duration to regulate the concentration of oxygen
vacancies. Amount of oxygen vacancies follows the ascending order: O2 2 h < O2 0.5 h < Air
0.5 h. Reproduced with permission from [34]. Copyright 2017, with permission from American
Chemical Society b Absorbance spectra (inset is Tauc Plot for band gap determination) of SnO2 film
fabricated using AACVD and spin coating. AACVD and spin coating represent low and high oxygen
vacancies, respectively. Reproduced with permission from [17]. Copyright 2018, with permission
from Elsevier
Effect of Oxygen Vacancies in Electron Transport … 295

3.4 Electrical Properties

Oxygen vacancies are advantageous towards the electrical conductivity of metal

oxide because the defect band assists in improving the conductivity by declining the
material band gap [70, 71]. This means that the resistivity of metal oxide declines
with increasing number of oxygen vacancies and hence, the electron mobility in
the bulk of ETL also improves [22, 72]. Despite the ETL having superior electron
transport ability, the presence of oxygen defect sites at the interface between metal
oxide-based ETL and perovskite light active layer severely deteriorates the charge
extraction process. Consequently, the electrons accumulated near the interface at per-
ovskite side and recombination of electron–hole pairs surges, plummeting the device
performance. The argument is supported by electrochemical impedance spectroscopy
(EIS) analysed by Du et al. as unveiled in Nyquist plot of Fig. 9a [23]. In this analysis,
the size of semicircle at high-frequency region and another incomplete semicircle at
low-frequency section corresponds to the electron transfer resistance and the charge
recombination at the ETL/perovskite interface, respectively [73, 74]. Apparently,
samples with lower concentration of oxygen vacancies indicate smaller electron
transfer resistance and enhanced recombination resistance, giving rise to charge car-
rier extraction and transport. Performance enhancement also manifested itself in
significant improvement of electron lifetime upon lowering the oxygen deficiencies
in the ETL as displayed in time-resolve photoluminescence spectra (Fig. 9b) [75].

Fig. 9 a Nyquist plot of EIS spectra for PSC based on sputtered compact TiO2 ETL using different
oxygen flux (higher oxygen flux represents lower oxygen vacancies). Reproduced with permission
from [23]. Copyright 2017, with permission from Royal Society of Chemistry. b Time-resolve pho-
toluminescence spectra of perovskite/ETL fabricated at different oxygen pressure (higher oxygen
pressure represents lower oxygen vacancies). Reproduced with permission from [22]. Copyright
2016, with permission from American Chemical Society
296 M. F. M. Noh et al.

4 Effect of Oxygen Vacancies Towards Device Performance

The ongoing struggle in the development of PSC has one main target, i.e. attaining
highly efficient and stable devices at low fabrication cost for rapid commercializa-
tion. Voluminous brilliant approaches have been proposed to reach that goal and
controlling oxygen vacancies would become another critical topic that can serve the
purpose. Since oxygen vacancies show significant impact on the properties of the
metal oxide, its presence in the ETL indisputably influences the overall efficiency,
hysteresis behaviour and long-term stability of the developed device which will be
elucidated profoundly in the following section.

4.1 Efficiency

Considerable strategies that are focusing on enhancing the efficiency of PSC have
been put in place including properly regulating the magnitude of oxygen vacancies in
metal oxide-based ETL [76–79]. Many studies have provided concrete evidences that
high oxygen deficiencies in ETL are detrimental towards the overall performance of
PSC. Eliminating or markedly minimizing the oxygen vacancies could improve the
short-circuit current density (JSC ), open-circuit voltage (VOC ) and fill factor (FF) of
the devices, ultimately ameliorating the solar-to-power conversion efficiency (PCE).
Depending on the fabrication procedures adopted and type of PSC device developed,
the relative enhancement of device performance could range from 0% to 15, 22, 24
and 40% for JSC , VOC , FF and PCE, respectively [34, 40, 72]. All of these increments
are undoubtedly attributed to the properties of ETL which change with the intensity
of oxygen vacancies. An example of device performance with respect to amount
of oxygen vacancies in TiO2 ETL is observable in Fig. 10a where in this case, the
efficiency of PSC measured through reverse scan mode improved from 12.51 to
15.40% upon reducing the capacity of oxygen vacancies in the sputter-fabricated
compact TiO2 ETL [23].
As described previously, electrical properties of ETL are one of the paramount
aspects that allow the enhancement of PSC performance. In principle, ETL facilitates
the collection of generated electrons from perovskite layer by allowing the injection
of electrons to its conduction band and independently transferred them to the FTO.
However, since the oxygen vacancies that are located close to the ETL/perovskite
interface inhibit efficient injection of electrons, it encourages the charge recombina-
tion particularly non-radiative recombination at the interface which diminishes the
VOC value. Sluggish electron transfer and high charge recombination processes at
the interface also lead to an obvious reduction of the amount of extracted charges
to the external circuit, leading to a lower JSC [22]. In addition, ETL containing high
oxygen deficiencies also possesses higher free electron concentration which could
easily recombine with holes in perovskite layer.
Effect of Oxygen Vacancies in Electron Transport … 297

Fig. 10 a J–V diagram and b IPCE spectra of planar perovskite solar cells based on sputtered
TiO2 compact layer as the function of oxygen flux. High oxygen flux corresponds to low oxygen
vacancies. Reproduced with permission from [23]. Copyright 2017, with permission from Royal
Society of Chemistry

Oxygen vacancies also narrow the optical band gap of the ETL, resulting in
greater generation of electrons in the ETL upon light absorption. Similarly, these
free electrons are unwanted as they would further magnify the charge recombination
rate. Besides, smaller band gap tends to increase the opacity of ETL, obstructing the
light to reach perovskite layer and in the end, reduces the photocurrent generation
owing to less photoexcitation of electron–hole pairs [26, 80]. As exhibited in Fig. 10b,
incident photon-to-current efficiency (IPCE) spectra of PSC consisting high vacancy
sites declines in comparison to that device with low oxygen defects. On top of that,
the contrasting wettability of ETL induced by oxygen defects could also influence
the growth of perovskite grains. Less wettable ETL (more hydrophobic layer due to
less oxygen vacancies) is preferable as it has lower surface tension dragging force
which increases grain boundary mobility and fosters the formation of larger and
well-defined perovskite grains [81]. The improved morphology of perovskite hinders
charge recombination at grain boundaries and gives a boost to the PCE of solar cell.
Therefore, diminishing oxygen vacancies is certainly beneficial for improving the
efficiency of PSC device.

4.2 Hysteresis

Hysteresis effect in power generation that accompanies the J–V measurement of

PSC device is one of the serious issues that needs further scrutiny, since the reported
device efficiency along with current hysteresis may cast doubts on the reliability of
this technology as the measured values may probably not represent the exact device
performance [54]. In contrast to inverted structured (p-i-n) PSCs, the conventional
type (n-i-p) PSCs usually suffers from stronger hysteresis behaviour due to the scan
speed and scan direction (forward bias or reverse bias). In most cases, conventional
298 M. F. M. Noh et al.

Fig. 11 a Reduction of device hysteresis upon eliminating oxygen vacancies in TiO2 through
Li doping (black = undoped-TiO2 , red = Li doped-TiO2 ) Reproduced with permission from [36].
Copyright 2016, with permission from Springer Nature b Schematic illustration of oxygen vacancies
migration in the ETL during J–V measurement. Reproduced with permission from [22]. Copyright
2016, with permission from American Chemical Society

PSCs would exhibit better device performance upon applying reverse scanning mode
(i.e. from VOC to JSC ) in relative to forward-scanning mode (i.e. from JSC to VOC ).
This hysteresis effect stemmed from several factors where the presence of oxygen
vacancies in ETL belongs to that group. In general, PSCs with high density of oxygen
vacancies exhibit greater hysteresis effect as shown in Fig. 11a.
The impact of interfacial oxygen vacancies towards device hysteresis has been
thoroughly investigated by Zhang et al. through experiments and simulations [22].
From transient absorption measurement and first-principles calculations, it was
revealed that oxygen vacancies could migrate within the oxide-based electrode under
electrical field during the voltage scans which lead to different photovoltaic perfor-
mance as the voltage is swept in different directions (Fig. 11b). The direction of
migration of oxygen vacancies, either away from or towards the interface of ETL,
is predictable with the aids of external electric field. Under reverse scan, an external
electric field pointing from perovskite light absorber to oxide-based ETL is exerted
on the PSC which consequently causes the oxygen vacancies to diffuse from the
perovskite/ETL interface to the bulk of the ETL [82]. This in turn slows down the
recombination dynamics and subsequently escalating the power output. On the other
hand, the oxygen vacancies would migrate to the perovskite/ETL interface upon
employing forward-scanning mode due to the inverse electric field. The accumula-
tion of oxygen vacancies at the interface minimize the electron collection efficiency
and substantially accelerate the charge recombination rate at the interface. As a result,
the same measured PSC device indicates poorer power output under forward scan.
It is also important to note that the electron–hole recombination rates at the per-
ovskite/ETL interface depend strongly on the positions of oxygen vacancies where
the difference in recombination rates could reach up to one order of magnitude.
Effect of Oxygen Vacancies in Electron Transport … 299

4.3 Stability

Another major concern in the field of PSC is to fabricate a highly stable device since
organic compound in the perovskite light absorber degrades at an alarming rate upon
exposure to moisture [54, 83]. To make things worse, some other external and internal
factors such as UV light, oxygen, high temperature and trapped charges could also
accelerate the degradation process of perovskite layer [84–88]. Oxygen vacancies
in the ETL made of metal oxide are also another reason for the poor stability of the
device that was often overlooked nowadays. Several research groups have discovered
that PSC employing ETL with high oxygen vacancies degrade much faster than that
PSC with low oxygen defects ETL. As described earlier in this chapter, one of the
reasons is that oxygen vacancies intensify the hydrophilic nature of the metal oxide
film. Consequently, this layer is prone to absorb more moisture from environment
particularly when the device is prepared in ambient air or encapsulation step is
neglected which expedite the degradation process of perovskite [17]. Furthermore,
Ahn et al. [87] claimed that the trapped charges at perovskite/ETL interface could
accelerate the degradation of perovskite in the presence of moisture. Therefore, it is
natural to deduce that oxygen vacancy defects in metal oxide-based ETL is one of
the major causes for degradation of PSC, since the defects impede efficient charge
transfer and induce charge accumulation in the perovskite layer.
From the above discussion, it seems like the most convenient way to mitigate
this problem is by applying encapsulation on the device to prevent the perovskite
layer from exposure towards humid air. Nonetheless, Leijtens and his team [88]
revealed that encapsulated PSC degraded much faster than non-encapsulated device
counterparts which they attributed this effect to the UV-radiation from sunlight and
oxygen vacancies defect (or Ti3+ surface states) in mesoporous TiO2 layer. This is
because oxygen molecules from environment are needed for healing or passivating
the Ti3+ surface states on TiO2 , as illustrated in Fig. 12. The oxygen vacancies which
are deep electron-donating sites interact with oxygen that adsorbs to the vacancy
sites forming O2 − -Ti4+ charge transfer complex. Absorption of UV light by TiO2
creates electron–hole pair and the hole in the valence band of TiO2 could recombine
with the electron at the oxygen adsorption site which simultaneously setting free
the neutral oxygen molecule. This unoccupied oxygen vacancy sites serve as trap
states [89]. Upon photoexcitation of perovskite layer, the electrons from perovskite
are injected either directly into the deep trap states or initially into the conduction
band and finally become deeply trapped. Since the trapped electrons are immobile,
they would recombine with holes in the hole-transport layer [90]. In oxygen-free
encapsulated device, the O2 − –Ti4+ complexes are depleted and the density of deep
electronic traps rises, amplifying the recombination process until a level where the
cell turns malfunctioning after several hours.
As mentioned before, omitting encapsulation step assists in TiO2 passivation due
to exposure to oxygen but at the same time, moisture in environment would react
irreversibly with perovskite causing rapid degradation of the layer. Other preventive
measures have also been suggested to address UV light-induced degradation issue
300 M. F. M. Noh et al.

Fig. 12 Schematic diagram illustrating the mechanism for degradation of perovskite due to UV
light. Reproduced with permission from [88]. Copyright 2013, with permission from Springer
Nature

such as blocking UV light illumination from reaching the device and replacing the
TiO2 with other metal oxide as ETL. However, the former could reduce the total
light absorption capability of the device which decreases the JSC , whereas the latter
requires much deeper studies to success which may delay the commercialization of
PSC. Hence, eliminating oxygen vacancies in metal oxide-based ETL while preserv-
ing the device from exposure to humidity is considered to be the most convenient
solution to alleviate the issues and ensure good stability of PSC [23].

5 Conclusion

Perovskite solar cells have experienced unprecedented advancements in terms of effi-

ciency, approaching and overtaking those of early generation solar cells technology.
One of the major contributors towards such achievement is the rapid progress in the
development of electron transport layer. As research on enhancing the capability of
ETL continues, point defects associated with oxygen vacancies in metal oxide-based
ETL which could act as traps for photoexcited electrons have been recognized as one
of the crucial parameters that governs the performance of a PSC. Even though the
Effect of Oxygen Vacancies in Electron Transport … 301

metal oxide shows superior electrical properties especially the electrical conductiv-
ity in the presence of high oxygen vacancies, the defect is found to be detrimental
towards the generated efficiency, hysteresis behaviour and long-term stability of PSC
devices. Low transparency, high hydrophobicity, enhanced recombination rate and
diffusion of the defect sites are the key characteristics of oxygen vacancies that neg-
atively affect the device performance. Thus, carefully tuning the density of defect in
ETL either through modification of fabrication protocols or introduction of dopant is
of great importance to ameliorate device stability while preserving excellent charge
transfer and transport by the ETL. Profound investigation regarding this topic is
urgently needed in the future to realize large-scale production of highly efficient and
stable PSC device for commercialization.

Acknowledgements The authors would like to thank Universiti Kebangsaan Malaysia (UKM) for
the financial support through the internal grant DIP-2016-003.

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Solar Cells and Optoelectronic Devices
in Space

Khuram Ali, Syedda Shaher Bano, Hasan M. Khan and S. K. Sharma

Abstract Optoelectronic devices including solar cells have been widely used in
space and are extremely sensitive to substantially shorter wavelength electromag-
netic radiations, e.g., gamma ray. Electrons and secondary photons are produced
when gamma rays pass through the matter and this phenomenon can be described as
Compton effect. When a photon interacts with a device, it removes the primary elec-
tron from an atom. That primary electron in each ionizing collision produces swift
secondary electron which may have nearly as much kinetic energy as the primary
photon. This secondary electron dissipates its energy as kinetic energy which results
in the ionization and excitation of the atoms in the absorber. This kinetic energy
eventually is dissipated in the medium as heat and imparted to the atom in order to
displace it from its normal site producing vacancy-interstitial pair. Ultimately, lattice
periodicity changes and give rise to additional energy levels and alter the electrical
properties of optoelectronic devices.

Keywords Defects · Radiation damage · Gamma irradiation · Solar cells · LEDs ·

Photodiodes

1 Introduction

Space cells have significant importance in atmospheric applications, extensively

important in communications, transmissions, investigation of resources, space
improvement applications and technical research. The use of space solar cells in
satellites is important as power sources [1]. The fundamental purposes to use and

K. Ali (B) · S. S. Bano

Nano-Optoelectronics Research Laboratory, Department of Physics, University of Agriculture
Faisalabad, Faisalabad 38040, Pakistan
e-mail: [email protected]
H. M. Khan
Department of Physics, The Islamia University of Bahawalpur, Bahawalpur, Pakistan
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago
© Springer Nature Switzerland AG 2020 307
S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_12
308 K. Ali et al.

develop space photovoltaic cells are to increase radiation resistance (life), reduce
cost and mass of arrays and photovoltaic cells and also enhance the conversion effi-
ciency. Both single junction and multi-junction solar cells are important in space
applications. However, multiple solar cells such as gallium arsenide/indium gallium
phosphide are important in space applications due to greater radiation resistance and
high conversion efficiency as compared to silicon solar cell [2]. Since, in the early
1990s the power requirements in satellites have increased significantly. Furthermore,
for the enhancement of space applications, the improvements in radiation resistance
and conversion efficiency of solar cells are required [3]. The large amount of solar
energy almost 50–60% is vanished on its way through the atmosphere of earth by the
special effects of absorption and reflection. However, the space-based photovoltaic
system helps to avoid these losses by converting the sunlight to microwaves outside
the atmosphere. The space photovoltaic system is important due to the production of
large amount of energy in the entire earth with very less ecological effect. Such as
the output of the sun is very large that is 2.3 billion but the earth receives only one
part from the sun. The largest available source of potential energy on earth is space
solar power [4]. Space solar energy system is important because it does not release
greenhouse gases while ethanol, coal, gas and oil plants do. Also, space cells do not
produce dangerous waste like nuclear power plants [5].

1.1 Radiations in Space

Gamma radiations are electromagnetic radiations consisting of high-energy photons

with high frequency and shorter wavelengths. Gamma radiations are present around
us which are the natural phenomena since the earth has come into existence [6].
Hundreds of years ago scientists have succeeded in investigating the main source of
emission of gamma radiations from unstable nuclei. This process is also known as
gamma decay and produced due to the transition of unstable nuclei from its high-
energy level to low-energy level [7, 8]. Another major source for the emission of
gamma radiations is the galactic center [9]. Galactic center consists of the complex
region containing massive X-rays, binding systems, star clusters, black holes and
massive stars. The presence of such dark matter inside the galactic center leads to
the excessive rate of matter annihilation which results in the emission of gamma
radiations [10, 11]. A detailed study of gamma radiations is observed from the galac-
tic central region. Gamma radiations-based maps indicate the existence of gamma
radiations at galactic center. Owing to the high penetrating power of the exposure
of these radiations on different devices of electronics has been a major course of
study for many scientists [12]. Gamma radiations even have high penetrating power
to such an extent that it can easily penetrate in the human body [13, 14]. In order
to prevent the penetration of gamma radiations, it must be covered by highly dense
materials such as uranium or lead [15]. Figure 1 shows the penetrating power of
gamma radiations in different objects [16]. It is clear that alpha particles have the
least penetrating power as compared to other radiations. These radiations are even
Solar Cells and Optoelectronic Devices in Space 309

Fig. 1 Penetrating power of radiations in paper, aluminum sheet and lead

blocked by few inches of papers. Irradiation of the alpha particles can produce many
harmful effects. On the other hand, beta radiations are more like electrons and have
slightly greater penetrating power as compared to alpha particles. Beta radiations
can pass through the sheet of 3 mm thick aluminum [17, 18]. Figure 1 demonstrates
the penetrating power of gamma radiations through lead. The penetrating power of
gamma radiations is more when lead is thinner in diameter. With the increase in
thickness, the transmission of gamma radiations starts to decrease.
Gamma radiations are the most powerful electromagnetic ionizing radiations.
These radiations are emitted from the radioactive materials. These ionizing radiations
have very high penetrating power. They may even penetrate into a thickness of several
centimeters distance. High ionizing gamma radiations can pass through the lead and
can be easily detected from other side as shown in Fig. 1. During gamma rays
interaction with matter, atomic electrons are knocked out in a way that it donates all
of its energy and terminates its existence [19, 20]. Some of the energy is being used
in overcoming the binding energy of the electron and remaining is transferred to the
free electron in the form of kinetic energy [21]. In order to conserve the momentum,
the minute amount of energy remains with the atom. This phenomenon is termed as
photoelectric absorption. Photons having visible light ejects electron from the metal
surface. Photoelectric effect is important because it can detect the gamma radiations
interaction with the atoms using full peak values [22].

2 Radiation Environment and Devices in Space

Optoelectronic devices are strongly affected by extreme radiation environment. These

radiations may produce ionization and displacement damage affects [23]. These
types of radiations are widely distributed in space and cannot be neglected [24, 25].
In order to avoid ionization and displacement damage affects, these particles need
to understand and evaluate using standard practical approach. Exposure of these
310 K. Ali et al.

radiations produces defects in optoelectronic devices [3, 26]. These defects create
additional energy levels in the band gap that alters the structure of semiconductor
devices. These energy levels affect the electrical properties of different optoelectronic
devices. Electron-hole pairs are generated near the energy band gap and produce
leakage current. [27, 28]. There are many factors that contribute toward the re-
coupling of electron-hole pairs with the radiation-induced centers and tunneling
of charge carriers. Different types of radiation-induced defects that may occur in
semiconductor-based devices are shown in Fig. 2 [29].
When crystal lattice is irradiated by gamma radiations then lattice defects are pro-
duced in the crystal’s geometry [30]. When the incident particles pass through the
solid, elastic and inelastic collisions are produced within the atoms of the semicon-
ductors. The formation and elimination of electron-hole pairs in the semiconductor
devices produce no net effect [31]. This process is termed as generation and recom-
bination, respectively. Electron-holes pairs are formed by generation are removed by
recombination [32]. Such mechanisms are basically restoring phenomena of nature.
The excess and deficit charge carriers are stabilized within the semiconductor. Radia-
tion environment produces damage defects in the semiconductor devices [33]. Gen-
eration and re-combinations can affect device efficiency. Extreme environmental
conditions may cause other draw-backs, i.e., tunneling, traps and compensation.
Carrier lifetime of semiconductors is decreased by electrons held in energy gaps.
Most of the electrons pass through the energy gaps by compensation that eventually
reduces the semiconductors stability [31, 34]. To reduce the impact of this defect,
compensation-capacitors are installed into system format. Tunneling is the most crit-
ical defect among all the defects that have been discussed so far. Without changing
the energy level tunneling causes the jumping of electrons across these energy levels.
This defect can cause the device instability and significantly affects the working of
optoelectronic devices [35].

Fig. 2 Different effects due to defect centers in the silicon band gap. Figure reprinted/adapted with
permission from Ref. [29]
Solar Cells and Optoelectronic Devices in Space 311

2.1 Displacement Damage Mechanisms

When gamma radiation interacts with atoms of different elements they knock out
electrons. This displacement causes many defects in the standard working phenom-
ena of devices. The topic under discussion helps in understanding the displacement
damage effects in electronic devices [24, 36]. When gamma radiations are incident
on silicon, there is probability of increased carrier recombination due to radiation-
induced levels in the silicon band gaps. In case of silicon new analysis and simula-
tions are being used in order to observe the cluster defects [37]. NIEL describes the
non-ionizing energy loss per unit distance being traveled by incident particles in the
silicone device.
Normally carriers are generated at radiation-induced centers and after that recom-
bination of these charge carriers carried out. This work largely emphasizes on the
experimental situations in which NIEL is kept constant with the penetration depth. It
is optimized in such a way that the range of high-energy particles is greater than the
thickness of devices [38]. Cluster and subclusters both terms are used for small defect
regions [39]. Clusters in irradiated silicon have been investigated by many scientists
with experimental findings [40]. It is observed that radiation-induced degradation
increases with the thermal generation rate. In case of the irradiated silicon, all the
silicon devices are independent of NIEL [41]. Radiation-induced displacement dam-
age defects depend upon the time (after irradiations) and bombardment conditions.
Many factors such as irradiations temperature, measurement temperature and par-
ticle types are also responsible for the device degradation [42]. Radiation defects
have great influence on the optical and electrical behavior of many semiconductor
devices [43, 44]. Displacement damage can also affect the efficiency of solar cells
[45]. Number of simulation models is being used for the evaluation of the irradiated
solar cells. There is a chance of catastrophic failure due to high fluence rates due to
carriers’ removal effects. These effects have been observed by many scientists and
developed a model, which totally agrees with the experimental results [46]. Figure 3
shows the high-frequency voltage and capacitance measurements of irradiated and
non-irradiated silicon. It is observed that after irradiation there is a gradual decrease
in the value of capacitance.

2.2 Ionization Damage Mechanisms

Gamma rays photons deposit energy in many devices by the process of ionization.
The energy that is used for the purpose of ionization is termed as “ionization dose.”
However, during whole exposure the energy observed is known as total ionizing
dose [48]. The ionizing effects are produced by different kinds of ionizing radiations
such as ultraviolet radiations, X-rays, gamma rays and by secondary recoil particles
[49]. Ionizing effects are produced in the bulk materials. These can be stated as
enhancement of conductivity by the production of excess amount of charge carriers
312 K. Ali et al.

Fig. 3 C–V characteristics at a frequency of 10 kHz on a p-type MOS capacitor and proton irra-
diation fluences of 1 × 1013 and 1 × 1014 protons/cm2 . Figure reprinted/adapted with permission
from Ref. [47]

and trapped charge carriers [50]. Compton and pair production take place under
high-energy photons like gamma rays. Many free electrons are produced which have
sufficient energy to move toward forbidden energy gaps and create electron-hole
pairs [51]. So the conductivity of bulk materials enhanced.
The pairs generated in semi-conductive material may diffuse or recombine accord-
ing to the electric field present between them [52]. Because of the trapping of the
charge in the silicon dioxide, the damage is caused at the edges (interfaces) of silicon
and silicon dioxide. When the gamma radiations are incident on the silicon structure
electron-hole pairs are generated. Some of the generated pairs combine with other
charge carriers while only few electrons leave the silica [53]. The mobility of elec-
trons is greater than the holes; therefore, there is very little chance of movement of
holes toward silicon through the interfaces. On the other hand, holes are responsible
for charge built up in silicon dioxide. During gamma irradiation of silicon dioxide,
the amount of charge generated in the silica depends upon the electric field across
the oxides [25]. Figure 4 demonstrates the curve between time and partial pressure
of oxygen. It is shown that linear values are obtained with constant oxidation rate.
Owing to the tunneling affect some of the traps can recombine and accelerates
under the induced electric field. Due to rearrangements of the bonds at the edges
of silicon and oxides, new interface states are produced. Due to radiation exposure
of electronic components, charges are trapped within these states and irregularities
are produced. These unwanted irregularities, greatly influence the electric properties
of electronic devices [54]. With the decrease in the thickness of silicon dioxide
Solar Cells and Optoelectronic Devices in Space 313

Fig. 4 Radiation aging during the predicted oxygen partial pressure. Figure reprinted/adapted with
permission from Ref. [58]

effect of these traps becomes more dominant specifically in submicron technologies.

When energetic particles are allowed to incident on the optoelectronic device, it
loses its energy in the form of ionizing and non-ionizing radiations as they travel
inside the materials [55]. As a consequence of this energy loss, electron-hole pairs
are generated and atoms start to displace. The defects which are produced as a
result of these incident radiations named as vacancies and interstitials [56]. Vacancy
is actually defined as the void space generated in the absence of an atom from its
normal lattice position. If the movement of that atom occurs into non-lattice positions
then the defect which is produced is called interstitial defect. The combination of the
interstitial and the adjacent vacancy is termed as Frenkel pair. In irradiated silicone
devices, the large amount of vacancies may occur and different types of defects can
be produced [57].

3 Interaction with Matter

Since the last few decades interaction of gamma rays with matter is of major impor-
tance for researchers. Gamma radiations are considered as the ionizing radiations,
scattered by the nuclei and electrons [55]. As a result, radiation fields with positive
ions and negatively charged electrons are generated [59]. The interaction of gamma
radiations with the matter may occur in the form of photonuclear, photoelectric, pair
314 K. Ali et al.

production and Compton effects. In addition many affects such as Rayleigh scat-
tering, Thomson scattering and photofission may also occur as a result of photonic
interaction of gamma radiations with matter [60, 61]. The existence of these affects
may occur in different forms and needs to be discussed in detail. Depending upon the
quantum mechanical properties of gamma ray photons, different types of scattering
may occur. In the vicinity of the nucleus electron and positron pairs can also be gen-
erated. Photoelectric effect helps in knocking out the electrons, whereas knocking
of the elementary particles from the nucleus deals with the photonuclear effect [62].
Gamma radiations are produced during the process of decay of many radioactive
isotopes. Gamma ray bursts are the main source of generation of gamma radiation
fields and mostly present in space at cosmic scale. In addition, terrestrial gamma rays
are present in the atmosphere and are different from the gamma rays that are present
on the surface of earth [63]. The kinetic energy of the gamma photon having zero
rest mass can be calculated with the help of the formula given below:

E = h f = hc λ (1)

In this equation, h represents the Planck’s constant, c is speed of light, and

wavelength of electromagnetic radiations is λ and f is the frequency of gamma
radiations.

3.1 Photoelectric Effect

In these phenomena, gamma photon interacts with the electron (orbiting in the outer
shell of an atom). During interaction, gamma radiation transfers its energy to the
outermost electron and as a result of this energy; the electron is knocked out from
the orbit of atom [64]. After the emission of electron a void space or a vacancy is
generated and then filled by the outermost electron. During the transition process of
electron, the energy is radiated in the form of soft electromagnetic (EM) radiations
which falls in the ultraviolet, X-rays and visible regions of the EM spectrum [65].
Photoelectric interaction has indirect relationship with the gamma photon energy
and has a direct relation with the number of electrons present in the elements. It
is observed that the photoelectric effect is larger for elements having high atomic
numbers and decreases with the rise of energy [66]. Photoelectric effect always takes
place by the secondary emission as atoms cannot exist in the form of excited state.
In most cases, atom emits X-rays and returns to the ground state. The emission of
Auger electrons is carried out from the outer most electronic shells and results in
the emission of the secondary radiations which are used in the detection of gamma
radiations [67].
Photons energy in mega electron volts (MeV) and percentage of total interactions
is shown in Fig. 5. The graph shows that at lower photon energies photoelectric effect
is dominant, whereas Compton effect becomes more dominant as the photon energy
values increase from 0.1 to 0.15 MeV.
Solar Cells and Optoelectronic Devices in Space 315

Fig. 5 Photoelectric effect and Compton effect. Figure reprinted/adapted with permission from
Ref. [68]

3.2 Photo Fission of Nuclei

If high-energy photons collide with the CaF2 or fluorite, then gamma photons having
energy greater than 5 MeV can be generated. During these phenomena nuclei of the
thorium and uranium becomes unstable to an extent that they can produce fission
reaction. Energetic X-rays having energy greater than 8 MeV are produced by the
particle accelerators. In case of uranium and thorium, the values of threshold energies
do not differ from one nucleotide to the other nucleotide under the area of the mass
numbers. Gamma photon having energy greater than 16 MeV are unable to produce
fission in lead [69].

3.3 Compton Scatterings

Compton scattering is a major phenomenon in understanding the interaction of

gamma radiations with matter. In this process, a gamma ray photon strikes with
the free electron and elastically scatters. Momentum and the energy are not con-
served if the striking photon is completely absorbed by the electrons at rest. It is a
matter of fact that the electron in the matter is not free or at rest; however, if the
energy of incident photon is much greater than the binding energy of the electrons
then the state of electron is either at rest or is free. In Compton scattering gamma
radiations interact with the loosely bound electrons being scattered by an appropriate
loss in amount of energy [70].
Figure 6 illustrates the Compton scattering by gamma rays in the presence of
incident laser light. Laser photon strikes with the electron having an initial energy
of E e ,i at an angle θ p . As a result of Compton scattering photon energy is converted
into gamma energy (E γ ).
316 K. Ali et al.

Fig. 6 Laser Compton scattering schematically. Figure reprinted/adapted with permission from
Ref. [71]

3.4 Dose Rate Effects

Dose rate effects for silicon and germanium have been investigated by many
researchers. It involves the study of Cobalt-60 (60 Co) gamma irradiation of elec-
tronic devices with energy greater than 1.43 MeV. It was observed from this study
that the calculated dose rates greatly depend upon the primary source of the radiations
[72]. It has been found that the silicon and germanium negligibly depend upon the
dose rates [73]. Many experiments have been performed in calculating the dose rate
effects. In case of silicon and germanium, there is a gradual decrease in the value of
biased current at low voltage, up to the dose rate of 5-kilo rad (Si). On the other hand
increase in the value of biased current is observed for values of dose rates greater than
5-kilo rad (Si). Many physical methods are also adopted for optoelectronic devices to
understand the dose rate affects produced by the ionizing radiations. Previous studies
show that the emitter-based junctions in optoelectronic devices highly depend upon
the low dose rates [74].

4 Influence of Gamma Radiations on the Solar Cells,

LED’s and Photodiodes

4.1 Effect on Solar Cells

Most of the optoelectronic devices, such as solar cells, LED’s, photodiodes, etc., are
significantly influenced by gamma irradiations. This is due to the fact that the produc-
tion or absorption of light in a solid medium is greatly influenced by the presence of
defects inside the medium. Phototransistors are designed in such a way that the base
region absorbs maximum light when exposed to it. Solar cells are frequently used in
Solar Cells and Optoelectronic Devices in Space 317

most of the electronic systems and in satellites as power sources. Solar cells are highly
sensitive to the electromagnetic radiations having shorter wavelengths like gamma
rays and X-rays. These radiations are largely present in space and help in studying
the radiation-induced defects in different optoelectronic devices. These types of radi-
ations are highly energetic and can produce structural as well as electronic defects
in semiconductors.
These defects ultimately alter the output power and reduce the efficiency
of solar cells. The radiations produced by the gamma rays, neutrons or any
other charged particles may produce large number of energy levels in the band
gaps. Undesired energy levels are produced by these gamma radiations. These
unwanted energy levels significantly affect the electrical behavior of the solar
cells and produce electron-hole pairs near the mid gap. Generation of electron-hole
pairs increases the possibility of leakage current [75]. Figure 7 demonstrates the
output parameters of cadmium telluride (CdTe) solar cell. Output parameters such as
open-circuit voltage, fill factor and efficiency were observed as a function of absorber
layer thickness for various back surface recombination velocities. In addition gamma
radiation also affect the solar cell devices such as in the form of trapping of hole pairs,

Fig. 7 Output parameters of the CdTe solar cell after irradiation. Figure reprinted/adapted with
permission from Ref. [77]
318 K. Ali et al.

compensations, and tunneling of the charge carriers at the edges of the devices. These
defects ultimately become responsible for altering the desired output characteristics
of the solar cells [76].

4.1.1 Compton Scattering in Silicon Solar Cells

During the passage of gamma radiations through the matter, electrons and secondary
photons are emitted and the mechanism is termed as Compton scattering. A large
number of the electrons are generated as a result of this Compton scattering affect.
Other effects such as pair production and photoelectric affect are almost negligible
in this process. In the silicon solar cells, the photon collides with the cell and ejects
the primary electrons from the atoms. Each of these primary electrons generates the
secondary electrons which exhibit as kinetic energy greater than that of the primary
photon. The secondary electron then excites the atoms in the absorber region after the
dissipation of kinetic energy [78]. This kinetic energy is dissipated in the form of heat
and transferred to the atom. The remaining kinetic energy then relocates the atoms
from its normal position and thus generates the vacancies inside the solar cell. Under
the higher electric field, the presence of defects increases the thermal production of
the charge carriers by decreasing the potential barriers. This phenomenon is termed
as the Poole Frenkel effect [78]. So, increased kinetic energy is dissipated as heat
energy into the solar cell devices [79, 80].

4.2 Effect on Photodiodes and LED’s

Many optoelectronic devices such as LED’s and photodiodes are a course of major
discussion in the work. To study the radiation-resistant properties, photodiodes and
LED’s are exposed by 60 Co gamma rays at different angles. Dose rates are normally
chosen in connection with the available dose in space environment [81]. The results
of the earlier investigations show that there is a significant decrease in the output light
of LEDs and photodiodes. It was observed that non-radiative recombination centers
are mainly responsible for decreasing the output parameters. Due to an increase of the
density of the non-radiative recombination centers there is a reduction in the lifetime
of minority charge carriers. However, in case of the LEDs and photodiodes, the radia-
tive recombination is relatively smaller as compared to other electronic devices [82].
Before irradiation with gamma rays, LEDs and photodiodes show a short lifetime
of the minority charge carriers and higher current densities. In case of photodiodes,
the irradiation phenomena produce dark current in great extent [83]. Influence of
the gamma rays on the photodiodes has been analyzed by many researchers. It was
observed that after irradiation there is an increase in resistance and as a result voltage
is dropped across the photodiodes. Different types of radiation-induced defects in the
form of shunt resistance dark current has been observed [84]. Light-emitting diodes
Solar Cells and Optoelectronic Devices in Space 319

Fig. 8 Signal to noise ratio of photodiode with fluence of gamma radiations at different
temperatures. Figure reprinted/adapted with permission from Ref. [85]

made of gallium nitrides (GaN) endure considerable attraction from the past few
years owing to its wide energy band gap and radiation-resistant electrical properties.
Figure 8 shows the signal to noise ratio (SNR) of photodiode with fluence of
gamma radiations at different temperatures. The signal to noise ratio is calculated for
quantum efficiency against the fluence of gamma radiations at different temperatures.
Two curves are obtained at temperatures above 100 K. It is observed that the quantum
efficiency of photodiodes is decreased by increasing the temperature.

5 Conclusion and Future Prospectus

The purpose of the present work was to investigate the gamma radiation interac-
tion with optoelectronic devices. During gamma rays interaction with these devices,
atomic electrons are knocked out and kinetic energy is produced. This kinetic energy
eventually is dissipated in the medium as heat and imparted to the atom in order
to displace it from its normal site producing vacancy-interstitial pair. Ultimately,
lattice periodicity changes and give rise to additional energy levels and alter the
electrical properties of optoelectronic devices. A major challenge in the electronic
industry is to recognize the relationship among the characteristics and defects of the
optoelectronic devices. For successful operation and development of the aerospace
systems, radiation-resistant materials need to be employed. This study emphasizes
on the understanding of radiation tolerance of optoelectronic devices. This demands
a thorough and detailed study of the distribution of defects by using simulation and
laboratory tests. One of the most adopted techniques is the relocation of radiation-
induced defects in nanoscale structures. It is observed that output parameters of
irradiated optoelectronic devices are influenced by the increased value of resistance.
320 K. Ali et al.

This effect can be analyzed by using long-to-short range 3D models [86]. In some
cases, improvement is being carried out by increasing the n layer thickness of the
LED’s and photodiodes. This method is based on the principle that the given intensity
of light and wavelength changes with the reverse current. With increased thickness
of the layers, the total reverse currents in irradiated photodiodes can be made neg-
ligible. Si solar cells can be optimized with lithium (Li) incorporation. This can
improve the radiation tolerance and the minority carrier diffusion length. Li has the
ability to enhance radiation-resistant properties of solar cells by diffusing to and
combining with radiation-induced point defects. Radiation tolerance of integrated
electronic circuits is the main area of study for high-energy physics experiments. It is
observed that the radiation-resistant techniques are also useful in submicron technolo-
gies and have a significant role in the future research and development of aerospace
missions [87].

Acknowledgements This work was supported by the Higher Education Commission (HEC) of
Pakistan [Grant No: 8615/Punjab/NRPU/R&DHEC/2017]; and the National Centre for Physics
(NCP), Islamabad, Pakistan for providing assistance and Associate Membership to Dr. Khuram
Ali.

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Multi-junction (III–V) Solar Cells: From
Basics to Advanced Materials Choices
Khuram Ali, Afifa Khalid, Muhammad Raza Ahmad, Hasan M. Khan,
Irshad Ali and S. K. Sharma

Abstract Solar cell efficiency can be associated with the ability of the solar cell to
produce the maximum amount of electricity from a light energy source. There are
many uses of multi-junction solar cells based upon likewise in satellites and space
vehicles. Physically based two-dimensional methods under ultra-high concentration
above 1000 suns, the important limiting factors of multi-junction solar cells can be
investigated. The single-junction solar cells that are merged with silicon and GaAs
solar cells lead to the great importance due to 30% limit of intrinsic efficiency. In the
present chapter, we have discussed the basic physics and operation of solar cells with
multiple-junction cell designs of different types of materials, with a particular focus
on the GaInP/GaAs/Ge tandem cells. Further, their performance based on different
parameters will be discussed along with future consideration for developing most
advances in high efficiency III–V multi-junction solar cells.

Keywords Multi-junction · Anti-reflection coating · Conversion efficiency ·

Limiting factors · Concentrated photovoltaic · Tandem solar cells

K. Ali (B) · A. Khalid

Nano-Optoelectronics Research Laboratory, Department of Physics, University of Agriculture
Faisalabad, Faisalabad 38040, Pakistan
e-mail: [email protected]
M. R. Ahmad
Centre for Advanced Studies in Physics (CASP), GC University Lahore, Lahore, Pakistan
H. M. Khan
Department of Physics, The Islamia University of Bahawalpur, Bahawalpur, Pakistan
I. Ali
Department of Physics, Bahauddin Zakariya University, Multan, Pakistan
S. K. Sharma
Department of Physics, Faculty of Science and Technology, The University of the West Indies,
St. Augustine, Trinidad and Tobago

© Springer Nature Switzerland AG 2020 325

S. K. Sharma and K. Ali (eds.), Solar Cells,
https://doi.org/10.1007/978-3-030-36354-3_13
326 K. Ali et al.

1 Introduction

The solar cell is a device which converts the energy of light (photons) directly into
electricity. It is a form of photoelectric cell whose electrical characteristics vary when
exposed to light. The solar cell devices can be combined to form modules which
are also known as solar panels. The power conversion efficiency is an important
parameter which refers to the portion of energy in the form of sunlight that can be
converted into the electricity by the solar cell. It is the need of hour to new types of
solar cells which have better conversion efficiency. For this, there are new group of
solar cells known as multi-junction solar cells which are based on the combination of
multiple p–n junctions and made up of different semiconductor materials [1]. These
junctions are used for improving the solar cell conversion efficiency of sunlight into
electrical energy. In this new generation of solar cells, a large spectrum of lights
can be used for high efficiency. Multi-junction solar cell is composed of various
types of photovoltaic junctions that stack over each other to give better efficiency
[2]. Different individual solar cells having different band gaps of physical properties
and energies are held together that are able to catch and change a big range of photon
wavelengths into electrical energy with better efficiency. Multiple-junction solar cells
have the ability to give two times more energy as compared to conventional solar
cells [3]. By increasing the amount of multiple-junction solar cells, large amount of
energy with high efficiency can be generated. In this method, light is absorbed in the
panel through reflectors which lead to the idea of concentrated photovoltaic (CPV)
[4]. Generally, four regions are given to the solar cell concentration. Multi-junction
solar cells deal with thermal management and face tracking problems, by increasing
the solar concentration level. However, the strength of tunnel junction can be affected
by increasing the current densities [5].
The important purpose of photovoltaic studies is to enhance the ability of solar
cells. In August 2009, a press released by Spectrolab declared that a triple-junction
solar cell concentrator has an effectiveness of 41.6% [6]. In the light of this press
release, the triple-junction solar cells of III–V semiconductor materials are brought
under trial by Fraunhofer Institute of Solar Energy (ISE) and announced the effi-
ciency of 41.1% [7]. This efficiency is studied under spectral conditions such as under
AM1.5 direct and under 454 KW/m2 intensity of light. Thus, this cell is designed for
increasing the characteristics of solar concentrator set-up [8]. The concentrator pho-
tovoltaic devices exhibit 40% altering efficiencies in the solar cells of triple junction
derived from III–V semiconductor type materials, which is the present position of
proficiency [9].
There are many uses of multi-junction solar cells likewise in satellites and space
vehicles. These applications are studied under spectral conditions of one sun of
International Organization for Standardization (ISO) [10]. However, under the hard
environment, these applications cannot be studied, because protons and electrons
can destroy the solar cell in space due to high energy and rough environment [11].
Humans can obtain a significant amount of electrical power through solar energy
without developing nuclear fission reactions and fossil fuels such as oil, natural gas,
Multi-junction (III–V) Solar Cells … 327

and coal. Multiple-junction solar cells or photovoltaic have many benefits such as
they can produce broad range of electricity which can be used in many applications
[12]. These are also less costly, economically, and electrically suitable devices.
Conversion efficiencies in excess of 50% can be achieved by III–V semiconductor
multi-junction photovoltaic cells [13]. These types of photovoltaic cells have capa-
bilities of applications in terrestrial and space. From the past few years, MJ solar
cells have become important photovoltaic cells. Two-junction solar cells of gallium
arsenide (GaAs) and aluminum gallium arsenide (AlGaAs) had been investigated
by some researchers since 1982. The group related to this research also proved the
conversion efficiency of 20.2% in 1987, connected with a sub-cell of dual hetero
tunnel junction structure [14, 15]. In 1990, MJ solar cells with super high conver-
sion efficiency were investigated by research and development project in Japan to
obtain 40% of conversion efficiency and developed resourceful technologies sub-
jected by the support of New Energy and Industrial Technology Development Orga-
nization (NEDO) [16]. The concentrated photovoltaic CPV system depends on the
ratio of concentration which vividly enhances the MJ solar cell‘s production scale
and decreases its cost for terrestrial uses because this system corresponds to the
powerful device for multiple-junction solar cells [17]. In the fiscal year of 2001,
the multiple photovoltaic cells were achieved for the development of cost-effective
and great efficiency MJ concentrated cells and its modules, through the support of
research and development project under NEDO [18].

1.1 Limiting Factors Involved in Multi-junction Solar Cells

In the physically based two-dimensional methods under ultra-high concentration

above 1000 suns, the important limiting factors of multi-junction solar cells can
be investigated [19]. In the electrical activity of multi-junction solar cells, series
resistance is the main factor. This factor can be studied and examined in different
ways such as top solar cell’s window layer; the band dis-continuities are found at
multi-junctions and the electrical characteristics of the emitter [20]. The structure of
multi-junction solar cells can be formed under ultra-high concentration, i.e., >1000
suns, so the amount of concentrator photovoltaic (CPV) system can be decreased. The
process done under ultra-high concentration is also important for optical properties
of concentrators [21]. The structures of multi-junction solar cells that are formed
under ultra-high concentrations (>1000 suns) are attracting the great importance at
the present time with the increasing efficiency of 35%. The way to working of solar
cell and the release of heat are also important factors involved in the multi-junction
solar cell. The loss of the series resistance is the main disadvantage of ultra-high
concentrators [22, 23].
However, in physical operations, the solar rays having properties of light spectrum,
size, or quantity and the match of solar ray band gap with junction are the main factors
in which the conversion of energy of solar cell is based [24]. The air mass coefficient
is a common term which is used to characterize the performance of photovoltaic
328 K. Ali et al.

system under standardized conditions such as temperature, weatherly, surrounding

conditions, and geomorphology. It is referred to using the syntax “AM” followed by
a number. The photovoltaic multi-junction devices refer the suitable air conditions,
better efficiency with AM1.5 spectrum, and suitable micro-surroundings [25]. The
temperature and intensities can also be the factors of multi-junction solar cells. The
multi-junction solar cells are connected in series with tunnel junctions and contain
three sub-cells spreading through organic vapor phase [26]. These three sub-cells
that connect in series are able to work as a single diode to define the procedure of
multi-junction solar cell. This procedure is used under the factors of intensity and
temperature which leads to estimate the design of multi-junction solar cells [27].

2 Multi-junction Solar Cells Design

The multi-junction solar cell (MJSC) devices are the third generation solar cells which
exhibit better efficiency and have potential to overcome the Shockley–Queisser limit
(SQ limit) of 31–41% [28]. Mostly the MJSCs are based on multiple semiconducting
materials, and these semiconductors are stacked on top of each other having different
energy gaps, which is similar to that concept of sub-cells [29]. The MJSC due to these
sub-cells has different energy gaps for handling the spectral matching of single-
junction solar cell. The sub-cells of different energy gaps have ability to absorb the
photons from different segments of the solar spectrum. The more photons of light
can be absorbed by the upper part of the sub-cell so the upper level is produced
with high-energy band gaps [29]. The design framework of multiple-junction solar
cells should be perfectly chosen, to obtain the better efficiencies of solar cells. The
drift diffusion model defines the perfect combination of the design framework, with
all factors of semiconductor materials (III–V) likewise conduction band (CB) and
valence band (VB) density measured as factor of energy gap and effective mass [30].
The design of generic material set, with the explained model of non-radiative and
radiative losses, provides the basic information of multi-junction solar cell. In multi-
junction solar cells, the use of suitable anti-reflective coating is assumed for better
efficiency [31].
It is thoroughly difficult to calculate design of full spectrum. For the accurate
combination of multi-junction solar cell, there is a well-ordered method to describe
the design of a spectrum. This method is used to obtain better efficiency of spectrum
design under standard test condition (STC), at any location to maximize the energy
[32]. The multi-junction solar cell shown in Fig. 1 is used to increase the efficiency.
The conversion efficiency can be increased to discover the band gaps by using spectral
functions [33].
Multi-junction (III–V) Solar Cells … 329

Fig. 1 Schematic diagram of multi-junction solar cells. Figure reprinted/adapted with permission
from Ref. [34]

2.1 GaAs/Si Tandem Solar Cell

In the photovoltaic research, the multi-junction solar cells that consist of silicon
are very important. The single-junction solar cells that are merged with silicon and
GaAs solar cells lead to the great importance due to 30% limit of intrinsic efficiency
[35]. For non-concentrating solar cells, the Si-based multi-junction provides better
path to exceed the efficiency limit to 30%. The use of gallium arsenide (GaAs) and
germanium materials is going less. The Si-based method can be done with fewer
amounts and is less costly. This method has great importance due to the requirement
of better efficiencies for non-concentrating photovoltaic systems [36].
Silicon-based solar cells are less expensive due to the use of silicon at the lower
level of the cell. Thus, these cells have gained the novel status in their use. Solar cell,
with a lower silicon cell and two junctions have 1.7–1.8 eV band gap of its upper
cell and 45% efficiency limit, is described by method of explained balance limit
[37]. The merger of GaAs with silicon is still less and is considered non-suitable
because it has a 1.41 eV band gap. However, the efficiency of silicon-based GaAs
is greater as compared to single-junction solar cell. Thus, the efficiency of silicon-
based GaAs tandem solar cell with the arrangement of non-current matched four
terminals is 42% and for two terminals of current-matched arrangement is 39% [38].
The silicon-based gallium arsenide (GaAs) solar cells have been becoming developed
electronic components. Thus, in the laboratory conditions and suitable environment,
Si-based GaAs solar cells can be obtained with efficiency greater than 30% with four
terminals arrangement and have attained technologically importance [39].
The silicon-based multi-junction solar cells with appropriate band gap have been
achieving a significant importance in the present industry. These days, multi-junction
solar cell with silicon as a bottom cell is giving the contemporary structure in indus-
tries. The high efficiencies and great performance in multi-junction arrangements
330 K. Ali et al.

Fig. 2 Schematic diagram

of multi-junction tandem
solar cells. Figure
reprinted/adapted with
permission from Ref. [43]

are achieved by using III–V semiconductor materials [40]. The multi-junction solar
cells that are put together with current match two terminals and same band gaps are
considered to obtain the better efficiencies. The band gap of the upper cell should be
1.75–1.79 eV in the two-junction silicon-based solar cell which exhibits good com-
bination and can provide 29.79% efficiency with silicon bottom cell [41]. In III–V
semiconductor solar cells, the combination of gallium indium phosphorous (GaInP)
with gallium indium arsenide (GaInAs) has been used to obtain 31.5% efficiency.
The efficiency limit of 25.2% has been recognized for perovskite materials that are
now in the procedure of growth [42]. Figure 2 shows two- and four-terminal silicon-
based GaAs tandem solar cells. In two-terminal tandem cell with thickness of 200 nm
GaAs is placed at the top with Si bottom cell. In four-terminal solar cell, 1 µm GaAs
top cell is placed. The sub-cells are separated by zero-thickness insulation coating.

3 Multi-junction Solar Cell Performance

The multi-junction solar cell (MJSC) consists of multiple p–n junctions of differ-
ent semiconductor materials. These semiconductor materials absorb a wide range
of wavelengths and improve electrical energy conversion efficiency [44]. The multi-
junction solar cells (MJSCs) are instrumental in concentrated photovoltaic (CPV)
and space photovoltaic systems. The idea of CPV is used for optical light concen-
trators which increase the incident power on solar cells. The driving force for the
material and technological development of MJSCs is the need for higher conversion
efficiency. In CPV systems, the conversion efficiency is further increased owing to
the use of concentrated light and therefore any efficiency gain that can be made by
using more suitable materials and advanced design would lead to significant gain in
Multi-junction (III–V) Solar Cells … 331

overall system efficiency [45]. This CPV module uses four-junction III–V-based solar
cells. The record CPV efficiency for lattice-matched GaInP/GaAs/GaInNAsSb solar
cell is 44%. On the other hand, the best lattice-matched GaInP/GaAs/Ge exhibits a
peak efficiency of 43.3% under concentration and 34.1% at 1 sun. Efficiencies as
high as 50% have been predicted for cells with a larger number of junctions and
high concentration. To this end, a promising approach is to integrate dilute nitrides
and standard GaInP/GaAs/Ge. Yet, so far, such heterostructures have exhibited low
current generation [46].
In addition to these higher efficiencies, tracking that allows CPV systems can
produce a larger amount of energy throughout the day in sunny regions, notably
during the late part of the day when electricity demand is at the peak. At the same
time and in contrast to concentrated solar power (CSP), the size of the installations
can be scaled over a wide range, i.e., from kW to multi-MW. This way the local
demands are adapted. Some CPV systems also disturb a smaller land area, since
the trackers with relatively narrow pedestals are not closely packed [47]. In some
cases, this could allow for continued use of the land for other purposes, for example,
agriculture, although the relevant benefits of CPV versus flat plate PV in this case is
still an active area of research. Finally, heliostat concentrator photovoltaic (HCPV)
could provide an advantage over traditional c-Si technology in hot climates because
of the lower temperature coefficient.

3.1 Current Density–Voltage Curves

People are little impressed from the efficiency which is almost 25% for single-
junction record cells and more than 30% in the case of tandems. Nobody bothers to
ask this sort of question for the latest sports car even though the efficiency of typical
combustion engines in cars is probably not much higher. Cells made from multiple
materials layers can have multiple band gaps and will therefore respond to multiple
light wavelengths, capturing and converting some of the energy that would otherwise
be lost to relaxation as described above [48].
For instance, if one had a cell with two band gaps in it, one tuned to red light
and the other to green, then the extra energy in green, cyan, and blue light would be
lost only to the band gap of the green-sensitive material, while the energy of the red,
yellow, and orange would be lost only to the band gap of the red-sensitive material.
Following analysis similar to those performed for single-band gap devices, it can be
demonstrated that the perfect band gaps for a two-gap device are at 1.1 and 1.8 eV.
Traditional single-junction cells have a maximum theoretical efficiency of 33.16%.
Theoretically, an infinite number of junctions would have a limiting efficiency of
86.8% under highly concentrated sunlight [49].
Currently, the best laboratory tested results of traditional crystalline silicon (c-Si)
solar cells have efficiencies between 20 and 25%, while the best laboratory tested
results of multi-junction cells have demonstrated performance over 46% under con-
centrated sunlight. Commercial examples of tandem cells are widely available at 30%
332 K. Ali et al.

under one-sun illumination and improve to around 40% under concentrated sunlight.
However, this efficiency is gained at the cost of increased complexity and manufactur-
ing price [50]. To date, their higher price and higher price-to-performance ratio have
limited their use to special roles, notably in aerospace where their high power-to-
weight ratio is desirable. In terrestrial applications, these solar cells are emerging
in concentrator photovoltaics (CPVs), with a growing number of installations around
the world [51]. Tandem fabrication techniques have been used to improve the per-
formance of existing designs. In particular, the technique can be applied to lower
cost thin-film solar cells using amorphous silicon, as opposed to conventional crys-
talline silicon, to produce a cell with about 10% efficiency that is lightweight and
flexible. This approach has been used by several commercial vendors, but these
products are currently limited to certain niche roles, like roofing materials [52].
The current–voltage (I–V ) characteristics of single-junction GaInNAs SC, for
AM1.5G real-sun illumination, are shown in Fig. 3a. Measurements were done with
and without a 900-nm long-pass filter inserted before the solar cell. The filter was
used for simulating the light absorption into top junctions present in a multi-junction
device. The open-circuit voltage (V oc ) and short-circuit current (J sc ) values for the
GaInNAs solar cells were 0.416 V and approximately 40 mA/cm2 and 0.368 V and
approximately 10 mA/cm2 , without and with a long-pass filter, respectively. The
spectral behavior of PL and EQE is shown in Fig. 3b. The band gap of the GaInNAs
was estimated from the PL peak maximum wavelength to be approximately 1 eV
[53].
Examples of the measured PL spectra for GaInNAsSb structures with different
amounts of Sb are presented in Fig. 4a. As it can be seen, the band gap of GaIn-
NAsSb can be decreased down to 0.83 eV (1500 nm). The I–V characteristics of a
GaInNAsSb SC with E g = 0.9 eV measured under real-sun excitation at AM1.5G
are presented in Fig. 4b [56].
The data showed the calculated values of the W oc for selected GaInNAs and
GaInNAsSb single-junction solar cells (SCs). For GaInNAs solar cell with E g = 1 eV,

Fig. 3 I–V characteristics of single-junction GaInNAs solar cell (a) and EQE and PL spectra of
GaInNAs (b). Figure reprinted/adapted with permission from Ref. [54]
Multi-junction (III–V) Solar Cells … 333

Fig. 4 Measured photoluminescence spectra of GaInNAsSb SCs (a) and I–V characteristics of
0.9-eV GaInNAsSb SC (b)

the W oc was 0.58 V, and for GaInNAsSb with E g = 0.90 eV, the W oc was 0.59 V.
The best W oc achieved so far from GaInNAs single-junction SCs is 0.49 V. The
observations made here are in accordance with previously published reports which
indicate that the Sb-based solar cells have a slightly higher W oc values compared to
GaInNAs SCs [55].
The optimal band gap for GaInNAsSb junction of the triple- and four-junction
solar cells depends on the target spectrum and the performance of the sub-junctions.
In a four-junction cell, it would be beneficial to have slightly larger band gaps for
the top junctions, especially for the AM1.5G spectrum. The GaInP/GaAs top cells
have already been well optimized and that is the reason why the band gap shifting is
probably not the best practical step to start with, especially because the W oc values
of top junctions with larger band gaps increase easily [56].

3.2 Band Gap Conversion Efficiency

There are several reasons why III–V multi-junction solar cells reach the highest
efficiencies of any photovoltaic technology. The III–V solar cells are composed of
compounds of elements from group III and V of the periodic table. In the correspond-
ing multi-junction devices, several solar cells made of different III–V semiconductors
are stacked with decreasing band gaps from top to bottom [56]. This reduces ther-
malization losses as photons are mostly absorbed in layers with a band gap close
to the photon’s energy. Moreover, transmission losses are reduced as the absorption
range of the multi-junction solar cell is usually wider than for single-junction devices.
Finally, the use of direct band gap III–V semiconductors facilitates a high absorption
334 K. Ali et al.

of light even in comparably thin layers. In addition, the efficiency increases when
operated under concentrated illumination due to a linear increase of short-circuit
current and logarithmic increase of voltage [57].
The most common III–V multi-junction solar cell in space and terrestrial con-
centrator systems is a lattice-matched Ga0.50 In0.50 P/Ga0.99 In0.01 As/Ge triple-junction
solar cell. The device is typically grown with high throughput in commercial metal
organic vapor phase epitaxy (MOVPE) reactors. All semiconductors in this structure
have the same lattice constant as the Ge substrate, which facilitates crystal growth
with high material quality [58]. However, its band gap combination is not optimal
as the bottom cell receives significantly more light than the upper two cells resulting
in about twice the photocurrent of the upper two sub-cells. Nevertheless, a record
efficiency for this triple-junction concentrator solar cell 41.6% (AM1.5d, 364 suns)
was achieved in 2009. Various approaches are under investigation to further increase
in solar cell efficiencies. So far achieved record cell efficiencies are above 41%. This
uses different elements from the wide range of technology building blocks available
for III–V multi-junction solar cells [59].
The fill factor (FF) is essentially a measure of quality of the solar cell. It is
calculated by comparing the maximum power to the theoretical power (PT ) that
would be output at both the open-circuit voltage and short-circuit current together.
In practical terms, for two solar panels of the same physical size, if one has a 21%
efficiency rating and the other has a 14% efficiency rating, the 21% efficient panel
will produce 50% more kilowatt hours (kWh) of electricity under the same conditions
as the 14% efficient panel [60].

3.3 Spectral Distribution Effects

It is well known that triple-junction CPV cell performance depends on spectral con-
ditions, and therefore, atmospheric conditions such as aerosol optical depth (AOD),
perceptible water vapor (PWV), and optical air mass (AM) can have an impact on
cell and module performance. Although improved models are needed to accurately
predict energy production for CPV systems, it is not clear what, if any, spectral
parameters should be included in these models [61]. As spectral data is not read-
ily available, one must justify requiring this data by a significant increase in model
accuracy. To further compound this issue, CPV system technology varies signifi-
cantly, and it is probable that spectral data could improve energy predictions for one
technology but have little impact on alternate technology [62].
The part of this chapter explores the impact of AOD (at 500 nm) PWV, opti-
cal AM on module performance, in conjunction with the SMARTS spectral model,
cell quantum efficiency (QE) data (InGaP/InGaAs/Ge optimized for a G173/AM1.5
spectrum), and spectral measurements from a PG S-100 Direct Normal Spectral
Radiometer. Integrating the QE data with both modeled and measured spectra pro-
vides a means to predict changes in module current as AOD, PWV, and optical AM
changes [63].
Multi-junction (III–V) Solar Cells … 335

It is useful to begin an analysis of the spectral sensitivity of CPV modules by

briefly mentioning characteristics of an InGaP/InGaAs/Ge cell in relation to the
solar spectrum and key spectral parameters. The InGaP (top junction) is generally
responsive in the range of 350–700 nm, the InGaAs (middle junction) from 500 to
1000 nm, and the Ge (bottom junction) from 800 to 1800 nm. The three junctions are
wired in series, and therefore, the cell operates based on the junction that is generating
the least current. Manufactures typically design cells such that the top and middle
junctions alternate in the role of limiting current, while the bottom junction always
has surplus current. The top and middle junctions are grown to be current matched
for the G173/AM1.5 direct reference spectrum, a design point that is suggested for
optimum energy production at many CPV appropriate sites [64].
The spectrum is very dynamic, and changes in optical AM, PWV, and AOD all
impact CPV performance. Optical AM, the relative path length through the atmo-
sphere, varies from 1 to 5 when CPV produces the majority of its energy. As optical
AM increases, there is an increased Rayleigh scattering of blue light and the top
junction predominantly loses current. PWV, cm of condensed water vapor in the ver-
tical direction, absorbs solar radiation in bands around 720, 820, 940, 1100, 1380,
1870, and 3200 nm. Absorption bands corresponding to the bottom junction are the
strongest, but because the bottom junction does not limit this device’s performance,
PWV has little effect on cell performance [65]. However, absorption by water vapor
does decrease the measured direct normal irradiance (DNI). Consequently, as PWV
increases, DNI decreases more than power, resulting in an increase in efficiency. It
is interesting to note that changes in PWV have stronger impact in dry climates due
to the fact that an increase from 0 to 0.4 cm of PWV decreases solar radiation by
10%, while an increase from 0.4 to 4 cm is required to decrease radiation another
10%. AOD measurements quantify the number of particles/aerosols in the vertical
direction that results in radiation attenuation in the range of 400–2000 nm. The rate
of attenuation decreases with wavelength but is a complex function of quantity and
size distribution of particles. An increase in AOD typically results in the top junction
decreasing in current more than the middle junction [66].
The part of the chapter briefly explains the spectral sensitivity of CPV modules
with triple-junction cells on sun for multiple months in Golden, CO. The simple
model of the atmospheric radiative transfer of sunshine (SMARTS) model is used
with quantum efficiency (QE) data, optical air mass (AM), PWV, and AOD mea-
surements to predict variation in Isc/DNI over 9 months. Ultimately, this approach
provides a reasonable estimate of long-term variation in Isc/DNI. When SMARTS
is used in the same approach to predict intraday changes, the results are less use-
ful. This is likely due to small intraday changes in PWV and AOD being within
the measurement uncertainty of these parameters coupled with uncertainties and
assumptions made when applying the SMARTS model. At the same time, using
measured spectra rather than SMARTS spectra, intraday modeling indicated the
correct movements in Isc/DNI but with a reduced magnitude. In examining CPV
module performance, data show clearly defined AM response peaks for Isc/DNI and
efficiency while confirming that FF is minimized when Isc/DNI peaks. The mod-
ule metrics, Photovoltaics for Utility Scale Applications (PVUSA) power ratings,
336 K. Ali et al.

performance ratio, and DNI weighted efficiency, all show monthly variations on the
order of 5–10%, while Isc/DNI shows variation of 15%. In a simple approach, the
overall spectral sensitivity of three modules is quantified by fitting an AM correction
factor to nine months of data and then applying these correction factors in a yearly
energy prediction. Ultimately, the AM correction factor results in a 7% drop in annual
energy over a fixed efficiency module and 2% difference between CPV modules with
the differing spectral sensitivities [67].

3.4 Anti-reflection Coating in Multi-junction Solar Cells

An anti-reflection (AR) coating is a type of optical coating which is applied to

the surface of multi-junction solar cell for reducing the reflection of light which
improves the performance of the solar cell. This anti-reflective coating (ARC) is very
much needed as the reflection of bare silicon solar cells is over 30%. For the thin
AR Coating, silicon nitride or titanium oxide is generally used. The anti-reflecting
coatings are also used in various systems such as telescopes and microscopes for
improving the contrast of the image. In these systems, AR eliminates the stray light.

3.4.1 Principle of Anti-reflection Coating

Many coatings consist of transparent thin-film structures with alternating layers of

contrasting refractive index. Layer thicknesses are chosen to produce destructive
interference in the beams reflected from the interfaces and constructive interference in
the corresponding transmitted beams. This makes the structure’s performance change
with wavelength and incident angle, so that color effects often appear at oblique
angles. Figure 5 exhibits the experimental process of anti-reflection coating [68].

Fig. 5 Coating structure

diagram of quadruple
anti-reflection coating
structure. Figure
reprinted/adapted with
permission from Ref. [69]
Multi-junction (III–V) Solar Cells … 337

3.4.2 Mechanism

Anti-reflection coatings are used to reduce reflection from surfaces. Whenever a ray
of light moves from one medium to another (such as when light enters a sheet of glass
after traveling through air), some portion of the light is reflected from the surface
(known as the interface) between the two media [70]. A number of different effects
are used to reduce reflection. The simplest is to use a thin layer of material at the
interface, with an index of refraction between those of the two media. The reflection
is minimized when
√
n1 = n0ns (1)

where n 1 is the index of the thin layer, and n 0 and n s are the indices of the two media.
The optimum refractive indices for multiple coating layers at angles of incidence
other than 0° are given. Such coatings can reduce the reflection for ordinary glass
from about 4% per surface to around 2%. These were the first type of anti-reflection
coating known, having been discovered by Lord Rayleigh in 1886. He found that
old, slightly tarnished pieces of glass transmitted more light than new, clean pieces
due to this effect [71].
Practical anti-reflection coatings rely on an intermediate layer not only for its
direct reduction of reflection coefficient, but also use the interference effect of a thin
layer. If the layer’s thickness is controlled precisely such that it is exactly one-quarter
of the wavelength of the light in the layer (a quarter-wave coating), the reflections
from the front and back sides of the thin layer will destructively interfere and cancel
each other.
In practice, the performance of a simple one-layer interference coating is limited
by the fact that the reflections only exactly cancel for one wavelength of light at
one angle and by difficulties finding suitable materials. For ordinary glass (n ≈ 1.5),
the optimum coating index is n ≈ 1.23. Few useful substances have the required
refractive index. Magnesium fluoride (MgF2 ) is often used, since it is hard-wearing
and can be easily applied to substrates using physical vapor deposition, even though
its index is higher than desirable (n = 1.38). With such coatings, reflection as low as
1% can be achieved on common glass and better results can be obtained on higher
index media [72].
Further reduction is possible by using multiple coating layers, designed such that
reflections from the surfaces undergo maximum destructive interference. By using
two or more layers, broadband anti-reflection coatings which cover the visible range
(400–700 nm) with maximum reflectivities of less than 0.5% are commonly achiev-
able. Reflection in narrower wavelength bands can be as low as 0.1%. Alternatively,
a series of layers with small differences in refractive index can be used to create a
broadband anti-reflective coating by means of a refractive index gradient. The anti-
reflective coating on a solar cells helps to increase the amount of light absorbed into
the cell [73].
From the previous conception of photovoltaic systems, the anti-reflection layers
have been broadly studied. If there are no anti-reflection coatings, then it would result
338 K. Ali et al.

in unsuitable reduction into large refractive indexes of semiconductors (n nearly four).

The largest efficiency of about 43.49% is calculated for photovoltaic cells presented
by solar cells of multiple junctions. Multi-junction solar cells are generally affected
through a spectral bandwidth as compared to silicon [74]. However, these solar
cells are mostly demanding for semiconductors and exhibit anti-reflection coating
designs. Collectively, these types of solar cells exhibit series connection. However,
the anti-reflective coating (ARC) mechanism results into restricted current (photo-
generated) in a specific area of the spectrum for the related sub-cell, so this results
into decreased efficiency of the cell. The consideration of angular distribution is
important to properly design the concentrator solar cell with anti-reflection coating
[75].
According to the model of Henry, multi-junction solar cells exhibit particularly
greater limiting efficiencies. In comparison to the single-junction solar cells, in
multiple-junction solar cells, the conversion of the solar spectrum into electrical
energy is obtained at very large scale. Because of the larger range of solar spectrum,
this type of photovoltaic devices needs a very wide band anti-reflection coating [76].
The comparatively simple interference dual layer coatings are used to sufficiently
obtain control of reflection for customary single-junction solar cells, for example,
silicon, gallium arsenide, and indium phosphide, and also for double junction solar
cells, for example, GaAs/AlGaAs or gallium arsenide/InGaP [77]. This is probable
for these solar cells, because of the comparatively thin range of the solar spectrum.
The range of solar spectrum is almost doubled, with the development of multi-
junction solar cells consisting of photovoltaic germanium substrates. Because of the
requirement of current matching, multi-junction cells that are connected in series
have higher demands for the performance of anti-reflection coatings. For this pur-
pose, the reconsideration is required for the performance of anti-reflection coatings
and also the information of technologies required for the performance of these solar
cells is important [78].
To allow the greater conversion efficiencies in MJ solar cells, the factors that
include are costly materials, complex in design, and contain extra steps in processing.
The solar cells of these types are broadly used in space applications where cost of
device contains one component only of the total cost. These types of devices have
been enabling for worldly economical applications by integrated with concentrated
photovoltaic (CPV) systems, these systems concentrate the big area of sunlight on
the solar cell. CPV systems also give permission to the equivalent decrease in the
area of solar cell and usually generate nearly 500X rise in intensity. So by increasing
intensity, the efficiency of solar cell also increases which is the advantage also, until
the internal resistance restricts the device [79].
The design of multi-junction solar cell exhibits different band gaps in three sub-
cells which absorbs the solar spectrum of different parts. The sufficient efficiency
is obtained in this type of solar cell by refining the lattice match and current match
between the sub-cells. The design for anti-reflection coating in single-junction solar
cells is developing at large scale and widely studied in the literature. However, appro-
priate design of anti-reflection coating for multi-junction solar cell is extra challeng-
ing as compared to single-junction solar cells, because of some reasons. For example,
Multi-junction (III–V) Solar Cells … 339

firstly, as compared to single-junction solar cells, MJ solar cells can change more
solar spectrum bandwidth into electrical energy. So the more wideband anti-reflection
coating is required [80].
However, commonly the solar cell‘s bandwidth is probably increased, by adding
the more multiple junctions in the cell. Now secondly, the AR coating design for MJ
solar cells is challenging due to series connection between the sub-cells of multiple-
junction solar cells by which the performance of anti-reflection coating requires
for further demands [81]. The main objective of SJ solar cells is to provide the
considerable amount of light possible for the device. While the main objective in
case of MJ solar cells is to obtain matching current in relation to the light dispersion
among all sub parts of solar cell. However, thirdly, multiple junctions with series
inter-connection exhibit variations in the design of anti-reflecting coating, which
corresponds to the rise in mismatch current [82].

4 Material Choice and Growth

Photovoltaic effect occurred when the p–n junction solar cells of III–V type semi-
conductor materials transform the light rays into electrical energy. In 1954, the 6%
efficient silicon-based solar cells were invented. Photovoltaic systems have been uti-
lized in various applications such as electronic calculators, characteristics of remote
locations, and in space operations to supply power [83].
The occurrence of large amount of power from the sun to earth exists every day. It
is possible to calculate the power, because in photovoltaic device the area of device
and the energy produced are directly proportional to each other. The one approach
is occurred to estimate the percentage that can generate the use of energy in the
country, by supposing the photovoltaic devices of 15% efficiency that executed with
commercial tools. This research shows that the land area of Belgium is required 24%
that is the least felicitous country, the land area of UK is required almost 11% which
is the less felicitous country, while the land area of Australia is required 0.2% which
is the most felicitous country [84].
The more research on photovoltaic solar cells has shown that photovoltaic panels
can generate the power that is equivalent to the total usage of energy in UK. A number
of benefits that are investigated by building photovoltaic solar cells like the efficient
matching between use of power and power matching, land usage minimization, and
the photovoltaic panels used in built structure are less costly. The building integration
photovoltaic solar cells fabricate the Saturn modules used by Northumbria University
to show the appearance of 40 KW power of Northumberland building. Each module is
based on 36 silicon crystalline solar cells that are attached with each other [85]. These
cells are attached in series to extend the output voltage. The silicon-based solar cells
are the most progressed solar cells and have 1.1 electron-volt energy band gaps in
polycrystalline and crystalline form. However, the need of purity for semiconductor
grade is greater than grade of solar cell that carries the decrease of cost in feedstock
and beneficial for micro-electronics industry [86].
340 K. Ali et al.

To cover the broader region of wavelength in range of 300–1800 nano-meters

(nm), multiple-junction cells with various band gaps are stacked over each other in
a cycle. Different factors can play an important role in selecting the material for
solar cells such as band gap energies, impurity defects, lattice matching, thermal and
electrical properties [87].

4.1 Metal Organic Chemical Vapor Deposition

The triple p–n junction solar cells are used in worldly applications of concentrator
photovoltaic solar cells as well as in space and are the solar cells of greatest efficiency.
In commercial reactors of large scale, these cells are formed by utilizing metal organic
chemical vapor deposition. By increasing the growth rate of metal organic chemical
vapor, deposition can increase the throughput of reactor and decrease the process
time in the triple-junction solar cells. The process time of triple-junction solar cells
is largely directed by the growth of top cell (indium gallium phosphide) and middle
cell (indium gallium arsenide). By metal organic chemical vapor deposition growth
process, the higher growth processes are integrated and this also leads to the formation
of cheaper triple-junction solar cells and decrease in the time of process nearly 20%
[88].
In multi-junction solar cells, the method of metal organic chemical vapor depo-
sition (MOCVD) can also be used in combination with molecular beam epitaxy
(MBE). For example, highly efficient triple-junction solar cells of gallium indium
phosphide, gallium arsenide, and gallium indium nitride arsenide are fabricated by
these methods. By combining the MOCVD and MBE methods, the combined advan-
tages are obtained such as for III–V semiconductor materials rapid growth rate is
obtained by metal organic chemical deposition process and dilute nitrides are grown
by high quality of molecular beam epitaxy [89]. In this process, firstly, GaInNAs is
put as a bottom cell and grown by molecular beam epitaxy then MOCVD process
deposited the structure. Triple-junctions solar cells are displayed at 0AM and have
nearly 29% conversion efficiency. This tends to the production of less costly and
high-efficient concentrated multi-junction photovoltaic solar cells [90].
The progress of III–V compound semiconductor solar cells depends upon the
improvement in the innovative growth techniques. These technologies include such as
generally molecular epitaxy beam, MOCVD, and metal organic epitaxy vapor phase
and related technologies [91]. To achieve multiple-junction cells with high conversion
efficiency, highly accurate growth epitaxial technique is required. This corresponds
to the small difference between lattice match of the nearby cell layers. The atomic
level of semiconducting materials is uniquely controlled by growth technologies. So
the growth of new devices is possible such as compositions of multiple alloys and
pseudo-morphic alloys [92].
Multi-junction (III–V) Solar Cells … 341

Fig. 6 Schematic diagram

of GaAs based on Schottky
junction photovoltaic cells.
Figure reprinted/adapted
with permission from Ref.
[96]

4.2 Gallium Arsenide Solar Cells

In photovoltaic solar systems, gallium arsenide (GaAs) is the most frequently utilized
III–V semiconductor material. GaAs solar cells have efficient growth techniques
such as electron mobility as well as band gap [93]. The present investigation on
single p–n junction devices shows that gallium arsenide is almost 30% efficient. The
researchers at IRDEP observed the perfectly gained photoluminescence samples of
gallium arsenide photovoltaic solar cells from the ISE institute of Fraunhofer. In this
process, 532 nm ray was passed to irradiate the whole field of vision from microscope
and collected the photoluminescence signals from various points. The hyper-spectral
images were obtained, and the dimensions of these images can be increased a couple
of square meters [94].
The p–n junctions of GaAs were manufactured by molecular beam that is same as
substrate. The voltage–current properties were calculated under various conditions
such as in the dark and contain 1.5AM. It has 4.5% total efficiency. The emission
peak of electroluminescence calculated is about 1–4 electron-volt so these results
correspond in the photovoltaic applications of nanowires. Figure 6 shows Schottky
junction solar cell based on gallium arsenide [95].
In GaAs solar cells, the large amount of photons are absorbed in the device at
first 5µm. The thickness of gallium arsenide is more than 5 µm that gives a little bit
more output of power from device. The photons of energies are greatly absorbed by
gallium arsenide, because it is a semiconductor of direct band gap [97].

4.3 Gallium Indium Phosphide Solar Cells

In the industry of photovoltaic devices, the main objective is to obtain the less costly
solar cells. The efficiency of single junctions is reduced because the solar spectrum
of these cells can absorb only a certain wavelength. In contrast, the solar spectrum
of MJ solar cells is divided into smaller pieces, so they can absorb sunlight to the
matched solar spectrum pieces. MJ solar cells exhibit alloys of III–V semiconductor
materials [98]. These solar cells provide greater efficiencies than SJ solar cells.
Because, with greater optical sensitivity and by ideal grouping of band gaps, the
342 K. Ali et al.

concentration of photons increases, which gives rise to large number of electron hole
pairs and thus increases the device efficiency. Hence, many important organizations
of research spent their money to design the projects of III–IV semiconductor MJ
solar cells. The most prosperous sustainable root of energy is the sunlight, affecting
the surface of earth each day, having intensity of almost 0.1 W/cm2 and in excess
of 15,000 exajoules (EJ) [99]. This huge amount of energy is 10,000 times larger
than the energy used by the world daily, that is, 1.3 electron-joules. For the network
of electricity, the electricity produced by the photovoltaic system is still unsuitable.
This restriction has solutions such as increasing the efficiency of multiple-junction
III–V semiconductor materials with perfect band gaps choice and greater optical
sensitivity, so the total absorption of solar cell increases [100].
In solar cells of single junction, the replacement between the voltage and current
cannot give the greater conversion efficiency. Higher current is obtained by solar cell
which generates by using semiconductor of one material with small band gap. But in
such type of materials the light absorption is good in visible spectrum region, but the
production of open circuit high voltage is limited [101]. In small band gap materials,
the voltage of open circuit is restricted by higher dark currents. This problem has
a solution, by utilizing multiple band gap system having upper layer with larger
band gap, and solar spectral region is split to the sensitivity of matched spectrum.
The MJ solar cells were established and generated by utilizing III–V semiconductor
materials on silicon substrates and having interlayers of silicon germanium. Without
adjusting the design of solar cell, the open-circuit voltage greater than 2 V is obtained
to increase the performance of double junction [102].
The positions and lattice parameters of upper and lower cells should be carefully
matched in the material to decrease the mismatch dislocations in lattice-matched solar
cells. It is significant to study the connection between lattice material performance
and band gap to obtain higher performance. The maximum efficiency can be achieved
by energies of ideal band gap in lattice-matched solar cells. Although in III–IV
semiconductor compounds, there is no substrate material with lattice-matched lower
cell, which is cost-effective and available at commercial scale. The three-junction
lattice-matched system includes examples such as GaAs/InGaP/germanium and two-
junction lattice-matched materials are GaAs/AlGaAs, InGaAs/InP, and GaAs/InGaP
[103].
Sharp organizations have obtained the highest conversion efficiency of solar cell
which is 36.8% approximately by utilizing triple-junction solar cell compounds. This
structure of cell exhibits three stacked layers. The solar cell compounds using layers
of photo-absorption is prepared from compounds containing two or more components
such as gallium and indium. These solar cell compounds are used in space satellites
due to their higher conversion efficiencies [104].
Multi-junction (III–V) Solar Cells … 343

4.4 Germanium Solar Cells

In space for potential characteristics, the multi p–n junction solar cells that stacked
mechanically have been growing at IMEC. In these mechanically layered solar cells,
the germanium solar cells are being used in hybrid lighting devices as stand-alone
solar cells and developed in mechanical stack cells as a bottom cell. The general
spectrum is applicable in germanium solar cells for absorbance, so these solar cells
can also be used in thermo-photovoltaic systems. The use of less costly method and
substrates is necessary for cheaper and efficient thermo-photovoltaic system. The
use of germanium solar cells is important in these systems because of its low cost
and low band gap [105].
In the past decades, the remarkable researches have been started on photovoltaic
germanium solar cells. In initial researches, the monolithically layered multi-junction
solar cells have been studied, where the junction of germanium is achieved by diffu-
sion of arsenide by layer produced by metal organic chemical vapor deposition from
gallium arsenide. The single-junction solar cells have been investigated recently in
various researches at spectrum 1.5AM with efficiency 6% and at concentration of
light presented with 13% efficiency [106].
The surface passivation is a valuable characteristic of single-junction solar cells
with greater efficiency. The germanium oxide attracts the water that it is a hygro-
scopic, because of this reason it devalued the electrical characteristics and became
the difficult element in past. The materials such as amorphous silicon, silicon diox-
ide, silicon nitride, and gallium arsenide have been investigated for the characteris-
tics of surface passivation. The surface passivation characteristics of these materials
were not contained much data at that time. It is significant to use materials that can
accumulate by less cost in future [107].
The schematic Fig. 7 shows amorphous intrinsic silicon germanium (i-a-SiGe:H)

Fig. 7 Schematic diagram

of MJ solar cells with silicon
germanium cell. Figure
reprinted/adapted with
permission from Ref. [108]
344 K. Ali et al.

films with U-type coated glass substrate for amorphous silicon germanium (a-
SiGe:H) multijunction solar cells. The performance of photovoltaic cell is depre-
ciated, through the production of misfit dislocations in dense gallium arsenide and
lattice mismatch of 0.079% between germanium and gallium arsenide [109]. For the
better performance of solar cell with germanium substrate, all layers of cell can be
exactly lattice-matched by almost 0.99% addition of indium in GaAs/GaInP layers
of solar cell. Through this addition of indium, the lattice mismatch and dislocations
disappeared as presented by above figure. The factors including open-circuit volt-
age and short-circuit current were improved by addition of almost 0.99% indium. In
addition, longer wavelength of absorption edge is also obtained [110].

5 Future Consideration for Developing Advanced

Multi-junction Solar Cells

Multi-junction III–V compound tandem semiconductor solar cells have capability

for obtaining higher conversion efficiencies, that is, in excess of 40%. These solar
cells are also capable for terrestrial and space applications.
The above schematic plot is the example of chronological progress in space solar
cells target with conversion efficiency of 0AM. Figure 8 shows the significance and
development of multi-junction solar cells with greater efficiency. As compared to
single-junction silicon solar cells, the MJ solar cells with two and three junctions
such as InGaP/gallium arsenide/germanium solar cells have been established newly
in space applications due to their conversion higher efficiencies and higher resis-
tance radiation [112]. The R&D project of superb high-efficient solar cell has been
developed in Japan in 1990 fiscal year; this project was the long-term goal to the
initial twenty-first century. The progress in solar cells technologies with super high
efficiency is carried out and determined in this project, and the main objective is to
achieve 40% conversion efficiency and generating innovative technologies [113].
MJ solar cell technology manufacturing programs include some struggles on this
type of solar cells for the use in space into profitable production through Spectro-
lab and TEC-STAR. In August 1997, the commercial production of satellite was
launched based on two-junction solar cells of InGaP/GaAs on germanium solar cell
substrate. However, indium gallium phosphide single junction and GaInP/gallium
arsenide multiple-junction cells were originated to become radiation resistant as
compared to silicon and gallium arsenide SJ cells. Thus, MJ solar cells are broadly
used in space applications [109].
For the use of solar cells at large scale with higher efficiency, it is important
to make them cost-effective and develop their conversion efficiencies. The above
schematic plot shows the estimated accurately and theoretically single- and multi-
junction solar cell’s conversion efficiencies versus experimentally measured conver-
sion efficiencies. Thus, concentrator photovoltaic three- and four-junction solar cells
have greater capability to achieve 40% super high conversion efficiency [114]. The
Multi-junction (III–V) Solar Cells … 345

Fig. 8 Conversion efficiencies plotted for different types of solar cells per year. Figure
reprinted/adapted with permission from Ref. [111]

already established system of InGaP/GaInAs/Ge solar cell on a germanium cell sub-

strate three-junction arrangement will become broadly used system. There is also a
system with four-junction arrangement which theoretically exhibits 42% conversion
efficiency under condition of one-sun 0AM. This system exhibits arrangement of
germanium substrate as a bottom cell, the upper cell with energy band gap E g is
equal to 2.0 eV, the second layer of solar cell is gallium arsenide, and third layer
of cell exhibits energy band gap of 1.05 eV. Under condition of 1.5AM five hun-
dred suns, this system has the capability to generate in excess of 52% conversion
efficiency [115].
The solar concentrator cells are looking to correspond to reduce the electricity
cost in the future. From one of the future consideration applications, there also
exist three-junction solar cells on metal or silicon substrates. For terrestrial uses, the
concentration process of multiple-junction cells is important. The CPV systems have
also ability to reduce the cost. Thus, for general photovoltaic applications and cost-
effective production of electricity, crystalline silicon and multi-junction concentrator
solar cells are probably used [116].
346 K. Ali et al.

Acknowledgements This work was supported by the Higher Education Commission (HEC) of
Pakistan, [Grant No: 8615/Punjab/NRPU/R&D/HEC/2017] and the National Centre for Physics
(NCP), Islamabad, Pakistan, for providing Associate Membership to Dr. Khuram Ali.

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