Materials Science and Engineering B 307 (2024) 117504

Contents lists available at ScienceDirect

Materials Science & Engineering B

journal homepage: www.elsevier.com/locate/mseb

Solar cell performance enhancement using nanostructures

Priya V. Tumram a, * , Renuka Nafdey b , Pranay R. Kautkar c , S.V. Agnihotri a ,
Rohini A. Khaparde e , S.P. Wankhede d , S.V. Moharil e
a
Department of Physics, Amolakchand Mahavidyalaya, Yavatmal 445001, India
b
Shri Ramdeobaba College of Engineering and Management, Nagpur 440013, India
c
VMV Commerce, JMT Arts and JJP Science College, Nagpur 440008, India
d
Department of Physics, K.D.K. College of Engineering, Nagpur 440009, India
e
Department of Physics, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033, India

A R T I C L E I N F O A B S T R A C T

Keywords: The review focuses on the recent developments in nanostructure based solar cell technology. Apart from suc­
Nanostructure cessfully commercialized crystalline silicon (c-Si) solar cells, various other solar cells have been a topic of
Quantum dots research since last few decades because limitations of c-Si solar cells such as cost and low efficiency. Though
Nanowires
theoretically predicted solar cells efficiencies by Shockley and Queisser for various solar cells are high, real-world
Solar cells
Semiconductor
solar cell efficiencies are low due to various factors like spectral mismatch, reflection losses, recombination
losses, incomplete absorption, etc. The efforts to enhance solar cell performance by using nanotechnology has
facilitated development of altogether new types of devices such as quantum dot and nanowire solar cells.
Quantum dot solar cells (QDSC) make use of Quantum dots for absorption of incident solar radiation. Optical
properties of the quantum dots can be manipulated through adjustment of the bandgap which depends on the
size. The bandgap tuning makes QDSC adequate for multi-junction solar cells. QD of numerous semiconductors
have been investigated for improving solar cell efficiency by exploiting various regions of the solar spectrum. Use
of QDs for absorption of the solar light theoretical efficiency limit of mono-junction, as well as tandem cells can
be improved. First principle calculations led to the prediction that the encasing QDs in the intrinsic region can
significantly enhance the performance of p–i–n structures. The same logic can be used for the tandem cells as
well.
Apart from QDs, use of nanowires to attain similar improvement but through increasing the short-circuit
current (Isc) has also been explored. On the other hand, the problem of optimizing the open-circuit voltage
(Voc) is not yet satisfactorily solved in photovoltaic devices based on nanowires. One of the approaches had been
to incorporate nanophotonics in the design of a solar cell. This concept could be applied to almost all types of
cells. Even today, the limiting factor for the implementation of c-Si for harvesting solar energy is the high cost.
The use of nanostructures in designing the solar cells is expected to address this issue as well.

1. Introduction the help of selenium and a gold foil [3]. The efficiency of this primitive
cell was less than 1 %. Several researchers [4–6] continued work on Se
Observation of light induced voltages in 1839 by Edmond Becquerel and Cu2O cells which forms the basis of photovoltaic conversion of solar
can be said to mark the beginning of photovoltaics [1]. He performed the energy. Almost for a century, these types of devices remained in the
experiment on conventional two electrode arrangement with liquid reckoning for conversion of light into electricity. Later, Audobert and
electrolyte and noticed a voltage across these electrodes when light was Stora observed the photovoltaic conversion in CdSe semiconductor, in
allowed to fall on this arrangement. Almost after 40 years similar effect 1932. Modern solar photovoltaics had its seeds in the c-Si p-n junction
was observed for solid. by Adams and Day in 1877 [2]. He noticed solar cell fabricated in 1954 at Bell Telephone Laboratories by Chapin
variations in electrical characteristics of selenium subjected to irradia­ et al. [7] This device had efficiency of 6 %. Around the same time,
tion by visible light. In 1883, a photovoltaic device was designed with prototype heterojunction cell based on Cu2S/CdS was reported [8]

* Corresponding author.
E-mail address: [email protected] (P.V. Tumram).

https://doi.org/10.1016/j.mseb.2024.117504
Received 14 April 2023; Received in revised form 6 June 2024; Accepted 10 June 2024
Available online 20 June 2024
0921-5107/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
P.V. Tumram et al. Materials Science & Engineering B 307 (2024) 117504

which had equal efficiency. In 1956, Jenny et al. [9] reported the first
GaAs photovoltaic cell based on III-V semiconductor, with efficiency
more than 6 %. Russian scientist Zhores Alferov [10] in 1970 con­
structed solar cells based on the same material with much better per­
formance. In contrast to these single crystal cells, one based on thin film
with efficiency above 10 % was fabricated a decade later at “The Insti­
tute of Energy Conversion, University of Delaware”. This was based on
heterojunction sulfide, same as that used in 1954, technology. Alto­
gether new concept was used by Graztel in 1988, in which light was
absorbed by a dye and charge carriers were injected in the semi­
conductor. These are some of the landmarks in the early history of
photovoltaics progress.
Solar energy is distributed over a broad spectral region and it is
necessary to note this spectral distribution for understanding and
developing the solar photovoltaics. Solar surface is at around 6000 K,
and thus the spectral distribution of solar radiations is equivalent to that
of a black body at this temperature. Solar radiation entering the earth’s
atmosphere, gets attenuated due to scattering by air molecules, aerosols
and dust particles, as well as by oxygen, ozone, water vapour, CO2, etc.
This absorption spectrum is thus superposed over the solar spectrum
falling at the earth’s surface [11] as shown in Fig. 1. The magnitude of
Fig. 2. Solar energy distribution. (https://www.lmd.polytechnique.fr/sirta/tp/
this effect is a function of the path traversed through the atmosphere and
radiometrie.html).
is conveniently stated in terms of air mass (AM). “The ratio of the path
length of direct solar.
and non-solar sources of light (such as photons from incandescent bulbs)
radiation through the atmosphere at any time to that when the Sun is
is termed a photovoltaic cell”. The working of a photovoltaic (PV) cell
at the zenith defines AM. This value is considered as zero for the radi­
basically involves three steps (Fig. 3):
ations above atmospheric heights. AM 1 signifies the spectrum received
1 > The absorption of light, creating electron-hole pairs either free or
on Earth when Sun subtends right angle with the horizon. Customarily
bound (excitons).
conversion efficiencies of various devices are compared under AM 1.5
2 > The separation of charge carriers.
[12]. As can be seen in Fig. 2, solar spectrum at the surface of the earth is
3 > The separate extraction of these carriers to an external circuit.
distributed over a broad range of about 280 nm to 2500 nm. Of this
about 52–––55 % is in infrared (above 700 nm), 43 % visible (400 to
2. Development of various kinds of solar cells
700 nm), and 3–––5 % ultraviolet [13] (below 400 nm). An ideal
photovoltaic device should be capable of converting the entire spectrum
2.1. Solar cell classification
into electrical energy. This has not been achieved. Various materials
have been used in designing solar cells. None of these can convert entire
Solar cells are categorized on the following criteria.
spectrum, but a given material is effective over a small part of it.
1 > Thickness of active material.
Bulk solar cells, which do not need a substrate and thin film cell in
1.1. Solar cells basics which a thin film of active material is deposited on a substrate.
2 > Type of junction structure.
A photovoltaic cell “is a device that converts photons from the sun There are several types of junctions and solar cells are classified
(solar light) into electricity. In general, a cell that works on both solar accordingly, e.g. p-n homojunction cell, p-n heterojunction cell, p-n

Fig. 1. Spectral distribution of Solar radiations reaching earth. (https://en.wiki Fig. 3. Solar Cell Working Principle. (https://en.wikipedia.org/wiki/File:Sola
pedia.org/wiki/File:Solar_spectrum_en.svg). rgif1.gif).

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P.V. Tumram et al. Materials Science & Engineering B 307 (2024) 117504

multijunction cell, Metal semiconductor Schottkey junction, p-i-n Table 1

semiconductor junction. Shockley–Queisser limits for various solar cells.
3 > Type of material used in fabrication. Solar cell S.Q. limit (%)
Single crystal Silicon, Multicrystalline silicon, Amorphous silicon(a-
c-Si 33.2
Si) cell, Gallium arsenide (GaAS) cell, Copper Indium diselenide cell pc-Si 33.2
(CIS), Cadmium telluride cell (CdTe) and Organic PV cell including dye a-Si 28.9
sensitized cell [14,15]. CdTe 32.8
Another way of classifying the solar cells is based on the evolution GaAs 33.2
CIS 31.5
period, apart from the constituent material. CIGS 33.4
First generations solar cells were designed using c-silicon. These are CGS 28.9
also known by different terms like conventional, traditional, wafer- GaSb 23.9
based solar cells. They come in different varieties like monocrystalline Ge 22.5
(mono-Si) and polycrystalline (multi-Si) semiconducting materials.
Solar cells or panels based on thin-film technology make up the
Moreover, owing to the direct nature of the bandgap, the absorption
Second generation. These are important for technology development as
coefficient is high. By virtue of these properties thin layers of few mi­
well as commercial significance. CdTe, CIGS and amorphous silicon are
crons are enough for absorbing almost all the incident light. Conse­
the main members of this category.
quently, only a small amount of material is required for constructing the
In contrast, the third-generation solar cells have little market sig­
solar cell at reduced cost. Again, as most of the incident radiation is
nificance as their technology is still evolving. The constituent materials
absorbed in the depletion region, short minority carrier diffusion length
include a large range of substances, mostly organic, organometallic or
is adequate. This eliminates need to grow single crystals; polycrystalline
hybrid compounds.
layers suffice for fabrication of cells with desired output. Methods for
Fig. 4 shows spectral response for various types of solar cell.
deposition of polycrystallites are much more economic as compared to
Upper limits for conversion efficiencies of various solar cells have
the single crystal growth.
been estimated theoretically and referred to as Shockley–Queisser limits
The above arguments indicate that devices based on II-VI compound
[16,17]. These are listed in Table 1.
semiconductors are possible alternatives to c-Si photovoltaic cells. There
is one hitch. Conductivity type (p or n) can be manipulated for the
2.2. Heterojunction solar cells traditional materials Silicon and Germanium by doping with group III or
group V impurities. Such doped materials can be used for forming p-n
c-Si solar cells are most widely marketed. One of the reasons why junctions. This is not possible for II-VI materials. e.g. CdS is intrinsically
they cannot completely replace the conventional energy sources is the n- type and cannot be converted to p-type by any doping, and n-type
high cost. Notwithstanding the natural abundance of silicon, the device CdTe is impossible to engineer. This is because of the vacancy related
grade semiconductor material is still expensive. Comparatively, II-VI defects which are unavoidable. For these reasons, homojunctions cannot
semiconductors are economic. In fact, CdS [8,18] and CdTe [19] as be formed with II-VI materials. For obtaining p-n junctions we have to
photovoltaic converters were actively considered as early as 1954, resort to heterojunctions. Such heterojunctions were serendipitously
almost coinciding with the time when c-Si solar cells were demonstrated discovered while attempting CdS with holes as majority carriers or CdTe
by Bell laboratories [20]. with electrons. For a brief period, p-type CdS [23] and n-type CdTe
Actually, CdTe possesses several properties desired of a solar cell [24,25] were claimed and homojunction solar cells even demonstrated
material. From theoretical considerations, Loferski, explained that for during early sixties. These claims could not be substantiated and found
the optimum photovoltaic solar energy conversion the material should misleading when it was pointed out that in these devices, CuxS/CdS and
have bandgap close to 1.5 eV [21]. Based on these predictions, he found CuxTe/CdTe heterojunctions were formed [26]. Moreover, the perfor­
that CdTe, with a direct bandgap of 1.45 eV, [22] is most appropriate. mance of the resulting devises was marred by the questionable stability.
For fabrication of a heterojunction Cadmium telluride and sulfide
form an ideal pair. CdS is intrinsically n-type. Its bandgap of 2.4 eV is
adequate for a window material. A major part of solar spectrum can be
transmitted to the absorber. p-type CdTe is perfect in the role of
absorber. A direct bandgap of 1.45 eV matches very well with the peak
of the solar spectrum (1.43 eV). A thickness of 1–2 μm is found to be
adequate for absorption of solar photons. This can be conveniently
interfaced with the window material. Lattice mismatch between CdTe
and CdS is as low as 10 %. notwithstanding this mismatch, the CdTe-CdS
heterojunction has an excellent photovoltaic performance, with a typi­
cally high fill factor of 0.77 [27]. A prototype CdTe based cell with ef­
ficiency worth mentioning was announced in 1972. Bonnet and
Rabnehorst [28] used a thin film, graded gap CdTe-CdS p-n hetero­
junction for the construction of this device. Next milestone was achieved
after a gap of nearly 20 years when a cell with double digit efficiency
[29] was achieved at Kodak. For forming heterojunction, Monosolar
[30] and Ametek [31] used simple electrodeposition, while Kodak
employed close spaced sublimation (CSS). Subsequent significant step
was scaling up size and fabricate modules with larger area. The currents
drawn by modules are higher as compared to small cells. This could be
achieved by depositing one more transparent and yet conducting layer.
This layer of TCO facilitates the flow of current across upper part of the
cell. Several reviews are available which describe progress on CdS-CdTe
Fig. 4. Response curves of various Solar Cells. (https://pvpmc.sandia.gov/wp- solar cells [32–34]. For multi-kilowatt systems, the only technology
content/uploads/2012/04/Spectral_Response_PV.jpg.

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available as a substitute for the conventional c-Si industries is the thin semiconductor. The name is derived from a mineral of the same name
film technology based on Cadmium telluride PV [35]. Moreover, it has which is close to chalcopyrite. The structure can be obtained by various
lower cost. However, even the best commercial panels have efficiency of substitutions in CIGS. In and Ga are substituted by Zn and Sn [45].
approximately only 10––11 % [36] which is short of the theoretical However, the difficulties in the deposition of CZTS thin films has
value (28–30 %) by a huge margin [37]. slowed down the progress of CZTSSe solar cells [8]. Thus, solar cells
with compatible efficiencies, using thin-film technology that could be
2.3. Thin film solar cells commercialized are built upon Cu(In,Ga)Se2 (CIGS) and CdTe [46].
Hahn was the first to prepare the Chalcopyrite-type material, CulnSe2, in
The strategies used for cost reduction are based on i > using different 1953 [47]. Along with CdS, it possesses remarkable characteristics for
material and ii > using less amount of material. Due to indirect bandgap formation of heterojunction devices. The favorable features include, not
that leads to low light absorption, use of quite thick Si crystals (200–250 so demanding minority-carrier diffusion lengths owing to direct nature
µm) is mandatory for efficient photovoltaic conversion. Growing single of the bandgap [48,49], almost same lattice parameters for CuInSe2 and
crystals is also a costly and resource-hungry process. Efforts were thus hexagonal CdS; mismatch being ~ 1.2 %. Type of conductivity of thin
made to use non-crystalline/thin film materials for photovoltaic gener­ films can be manipulated [50]. CulnSe2 and CdS have nearly same
ation [38]. electron affinities and thus potential barriers for the photoinduced car­
Though cost reduction was the initial driving force behind thin film riers is minimum. CuInSe2, (CIS) as a PV material has been thoroughly
solar cell research, the other advantages were subsequently realized. investigated [51]. Devices with efficiencies of the order of 17 % have
Thin films could be deposited on flexible substrates leading to flexible been designed as early as 1993 [52,53]. Better devices could be pro­
solar cells. If an absorbing layer is constructed such that UV and/or NIR duced with the addition of Ga and S which enabled enhancing the effi­
bands are absorbed and subsequently used for photovoltaic conversion, ciency [54]. Bandgap of CulnSe2 is rather low, this can be remedied by
without obstructing the visible light the outcome is a transparent solar increasing Ga contents [55,56]. Bandgap of CulnSe2 − CuGaSe2 system
cell. Partial transmission of the incident light leads to the formation of a can be manipulated over the range1.04 to 1.70 eV. Conversion efficiency
partial transparent or semitransparent solar cell. When this solar cell is also enhances with increasing Ga content up to 30 % [57]. Survey of the
implanted in window or building glasses, these will generate solar power available literature leads to the conclusion that for CuIn1-xGaxSe2 the
without obstructing the illumination by the day light [38]. maximum performance is achieved in the composition range, 0.88 <
Sterling and Swann introduced the amorphous silicon (a-Si) layer Cu/(In + Ga) < 0.95 and x < 0.3 [58].
derived from silane in 1965. They achieved this by employing chemical CIGS has high absorption coefficient and thus a layer of only 1–2 µm
vapor deposition CVD [39]. As compared to c- Si, a-Si passivated by suffices to absorb most of the sunlight. This can be compared with
hydrogen (Si:H) has much higher absorption coefficient in visible region 160–190 µm that is required for c-Si. The developments at laboratory
by virtue of its direct bandgap. 1 µm thick a-Si is sufficient for absorption scale continued over a long period before the first CIGS hit the market in
of 90 % light. Processing of a-Si:H is also much easier. “Chemical vapor 1998 [54].
deposition” at moderate temperature (up to 400 ◦ C) yields large surfaces
coated with a-Si:H. The disordered material a-Si:H could be doped [40] 3. Nanostructured materials for solar cells
was an unexpected discovery. This enables formation of p-n junction.
Soon after the discovery, the initial a-Si:H solar cells [41] were fabri­ In recent years researchers focused their attention on ‘Multiple
cated. Such devices were put on the production line using monolithic exciton generation’ and ‘hot carriers in quantum confined nano­
interconnection [42] and integrated into miniature modules. These low structures’ [59]. These studies are expected to provide a solution to the
power devices were used for manufacturing products like calculators by problem of finding economic, efficient photovoltaic devices for the
several companies Royal, Sharp, Casio, and Teal [43]. A drawback of a- future. In nanostructures low defect densities lead to reduced re­
Si:H is its high band gap of 1.7 eV making it transparent to NIR spec­ combinations, and in turn, increased open circuit voltages and short-
trum. The long-range disorder limits the mobility of charge carriers and circuit currents [60].
diffusion length. These factors, in turn, affect the charge collection ef­ Fundamental studies on the preparation of nanostructures with
ficiency. Maximum photovoltaic conversion efficiency achieved with various morphologies opened up the new strategies to design solar cells
such devices did not exceed 13.6 %. for future. QD based solar cells have become quite attractive in recent
a-Si is not the only alternative considered to c-Si. Thin films of times as they can enable more efficient photovoltaic conversion going
various compound semiconductors have also been envisaged to this beyond the conventional Shockley and Queisser limit of 32 % for c-Si
purpose. For most of these materials, grain boundaries are the hindering solar cells. “Three major ways to utilize semiconductor dots in solar cell
factors. These lead to increased recombinations which impede the include (i) metal–semiconductor or Schottkey junction photovoltaic cell
photovoltaic conversion. Among various materials considered CuInSe2, (ii) polymer-semiconductor hybrid solar cell, and (iii) quantum dot
by virtue of its chemical structure exhibit minimum such effects. The sensitized solar cell. QD have been used in dye sensitized solar cells
added advantage was that devices with adequate efficiencies could be (DSSC) as photo-sensitizer instead of organic dyes to form quantum dot
produced even with polycrystalline materials, eliminating the need for sensitized solar cells (QDSSC) [61]”. Tuning the bandgap through size
crystal growth. This opened up entirely new field of “polycrystalline thin control leads to novel methods to control photo response and photo­
film solar cells”. conversion efficiency of the solar cell. The concept of the nanostructured
Though CIGS thin film solar cells use less material, the basic purpose semiconductor-based solar cells was demonstrated some thirty years
of cost reduction is not served as the constituent Indium, Gallium and back [62]. Some of the remarkable advantages are “tunable bandgap”
Selenium are costly. In an effort to replace these expensive ingredients, [63], “multiple exciton generation” (MEG) [64], and high “molar
kesterite materials were suggested as absorber of solar radiations. extinction coefficient” [65]. Moreover, semiconductor nanostructures
Kesterite based solar cells, including Cu2ZnSnS4 (CZTS), Cu2ZnSnSe4 become vital for light absorption as they can be turned into flexible
(CZTSe), and their alloys Cu2ZnSn(S,Se)4 (CZTSSe), are made up of non- panels [66]. Some excellent reviews on this topic can be found in recent
toxic and easily available chemicals. CZTS is a direct energy gap, p literature [67].
− type semiconductor. Consequently, it has large absorption coefficient
(~104 cm− 1). By allowing with Se the bandgap can be tuned from 1.0 to 3.1. Improving the efficiency of solar cells by using semiconductor
1.5 eV. The absorption curve excellently overlaps the solar spectrum quantum dots (QD)
[44]. The theoretical limit for the CZTS solar cell efficiency is 32 %,
almost same as that of CIGS and CdTe. Kesterite is a p-type Strategies to improve the performance of QDSCs include [68] (i)

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increasing solar radiation absorption and effective surface area by co- 3.2. Nanotechnology for designing portable solar power
sensitization method (ii) minimising recombination with help of
passivation barrier (iii) reducing traps by incorporating QD (iv) using As the name suggests, portable solar panels are compact solar panels
dopant for optimizing optoelectronic characteristics of QD and (v) use of which can be installed with ease, and that can be moved anywhere. They
core/shell nanostructures and alloying QDs for quick diffusion of serve the purpose of converting sunlight into electricity or heat. They are
carriers. made up of arrays of photovoltaic cells. An individual panel can be
The performance of QDSC depends to a large extent on the capability dismantled into smaller parts, where each part is made up of thin silicon
of photoinduced charge separation within semiconductor QDs and the layers. These are available in various sizes, but even the biggest portable
transport of these charges across the interface [69]. Lifetime of the solar panel can be accommodated inside a car. Depending on the size,
carriers can be increased if photogenerated electrons can be quickly they can generate up to 320 W of power.
transferred to an acceptor or if holes can be cleared with a redox couple. Portable solar cells are used for charging batteries of small electronic
This facilitates effective delivery of the photocurrent. The recombina­ devices such as smart phones, cell phones, iPads, small projectors, etc.
tion losses across the grains need to be minimized, so that electrons and These can also be used for automatic charging batteries of vehicles.
holes can efficiently migrate to the respective electrodes. This can make Nanotechnology facilitates fabrications of portable solar cells by
the solar cells to function efficiently. using nanomaterials in form of flexible thin films.
At present investigations on QD photovoltaics can be mainly found
on two types of solar cell configurations, (i) ‘solid-state semiconductor 3.3. Reduction of the cost of solar cells by Nanotechnology
heterojunction solar cells (SHJSC)’ and (ii) ‘liquid junction solar cells’ or
‘QD-sensitized solar cells (QDSC)’. These can be manufactured on large Synthesis of nanostructured materials involves much higher costs
scale without specific requirements using the available technologies. than the conventional bulk or thin films. The advantages of improved
Most of the journal literature on SHJSC is related to lead chalco­ performances must not be offset by the increased cost. Efforts are
genides [70]. As photoanode, PbS and PbSe QDs coated on mesoscopic continuously made to synthesize the nanomaterials with economic
TiO2 or ZnO film have been employed. Semiconductors like CdSe, Sb2S3, routes. e.g. manufacturing of PbS quantum dot (PbS QD) solar cells on
CIGS, have also been considered for harvesting photons. Photocurrent is commercial scale is affected by the high cost of some of the ingredients.
generated by light driven motion of electrons toward the oxide layer and These are required at the ligand exchange step. By using the recycled
that of hole toward the metal contact. ligand, PCEs of 10.36 and 10.05 % were attained [77]. This recycling
The lead chalcogenide based BHJSC are getting replaced by a new ligand method can be applied to other nanomaterials. This strategy can
class of halide perovskite semiconductors [71–73]. QDSC designed with lead to decreased costs, production times, and green production
such semiconductors are exhibiting much superior conversion effi­ methods through recycling.
ciencies. Emphasis is on the Cesium lead halides (X = Cl,Br or I) which Notwithstanding the steady improvements in the conventional
evolved from Methylammonium lead iodide chloride. Anticipating ob­ technologies and cost reduction, there is huge scope for exploring new
jection to lead containing materials for the toxicity, efforts have also designs and concepts that can prove useful for achieving this goal.
been made to prepare lead-free perovskites [74]. Increased light absorption in nanomaterials implies that significantly
The working of “QD sensitized solar cells (QDSSC)” is derived from less quantity is required for constructing a solar cell. Bottom-up
the “semiconductor − liquid junction photoelectrochemistry” [75]. approach enables processing as much lower temperatures and with
Majority of the work on fabrication of QDSSC has been carried out on simple, low-cost assemblies, as compared to that required for production
mesoscopic oxide films. These films have been prepared with CdSe and of solar cells based on conventional bulk semiconductors. Ability to use
CdS QDs. For transporting holes the sulfide/polysulfide electrolyte had flexible and/or transparent substrates could result in further cost
been used. FTO surface is first coated with a thin buffer layer (10 − 20 reduction. production on mass scale will make it easier to materialize.
nm) of close packed TiO2. Mesoscopic TiO2 is then deposited. This en­ All these efforts if restricted to laboratory scale preparations will not
ables isolation of the FTO surface with the redox electrolyte. This is show true cost reduction. Real reduction will take place when the lab­
crucial for achieving higher photovoltage. oratory experiments will be converted to manufacturing at industrial
The prompt migration of electrons and holes towards the corre­ scale.
sponding electrodes is the most important step during operation of
QDSC over the extended period. Such migrations are the primary pro­ 4. Recent advancements in synthesis of nanostructured
cesses which govern the “photon conversion efficiency”. On the other materials for solar cells
hand, loss of charge carriers due to recombination and their discharge at
the counter electrode adversely influences the “overall power conver­ Nanostructured materials in various forms and morphologies such as
sion efficiency”. thin films, quantum dots, nanowires, etc. have been suggested for
“Plasmonic Solar Cells” make use of plasmon resonances of silver and designing high efficiency, low-cost solar cells. In recent years, novel
gold nanoparticles. The “photovoltaic conversion efficiency” can be techniques were used obtain these structures.
enhanced by coupling semiconductor nanostructures with metal nano­ QD thin films can be deposited using methods like electrophoretic,
particles. The improved photoconversion efficiencies can be explained drop cast/spin coating, SILAR, CBD, bifunctional linker, etc.
in terms of the effective charge separation induced by the localized In drop casting method, a measured quantity of the colloidal QD
surface plasmon (SP) resonance near the photoactive molecules and/or suspension is placed onto the electrode surface, and the film is dried
near the semiconductor particles. Other possibilities are “(i) increased gently so as to prevent agglomeration.
absorption due to SPs and light trapping effects, (ii) creation of a The chemical bath deposition (CBD) [78], or chemical solution
localized electric field, (iii) direct participation of electron transfer from deposition (CSD) [79], has been described as early as 1869 for preparing
metal nanoparticles and (iv) electron storage effects that can drive the thin films. This method is applicable for producing films over large
Fermi level to more negative potentials” [76]. surface in a batch mode. CBD is a simple method for obtaining homo­
Although work in this area has yielded promising results, there is still geneous, robust and durable films. An attractive feature is that it can be
a long way to go to reach the commercial production stage. The syn­ performed with a simple set up consisting of solution holders and sub­
thesis of high-quality and uniform quantum dots is a complex process. strates placed appropriately. The process progresses through a couple of
Achieving consistent properties across a large quantity of quantum dots steps, viz. nucleation and growth. The quality of the grown films de­
can be challenging, which may impact the overall performance and pends on several factors like, growth temperature, dilution and pH of the
reliability of QDSCs. solvent, solute quantity, etc.

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Surface ionic layer adsorption and reaction (SILAR) was introduced problem of finding NPs specific catalyst is eliminated. This process can
by Nicolau in the mid-1980 s [80]. SILAR makes use of reactions taking be performed at easily achievable temperatures. These are often less
place at the surface of the electrode. The growth is governed by the time than those required for SLS growth.
and the frequency of the SILAR reaction. In 1995, Trentler et al reported an alternative solution–liquid–solid
Electrophoretic deposition is carried out by applying a DC electric (SLS) growth mechanism [88]. Using this they could obtain crystalline
field between two electrodes immersed in a QD suspension [81]. In this whiskers of a semiconductor at temperatures as low as 200 ◦ C. The
method QD are negatively charged by a liquid mixture of polar/ underlying mechanism was described by Wang et al [89]. Constituents
nonpolar solvents. By virtue of the negative charge, QDs are attracted in liquid form upon adequate thermal treatment leads to formation of
towards anode. The process enables uniform, dense layers of QD with small particles of semiconductor. These get dissolved in the molten
narrow distribution of size on anode which could be in form of a catalyst in a quantity decided by the supersaturation. Eventually nano­
mesoscopic film. Deposit thickness can be controlled by the duration of particles are formed and heterogeneous nucleation results in formation
deposition and the amount of QD suspended in a given volume of the of NW. Surfactants present in the solution facilitates the unidirectional
solvents. growth. The diameter of the NW is decided by the size of the catalyst
particle.
5. Nanowire synthesis and nanowire solar cells Another recently used technique is aerotaxy. Mass production of
functional nanowire-based devices needs an effective process which
5.1. Nanowire synthesis facilitates the synthesis of NW on commercial scale and low cost.
Moreover, the NW so prepared must have defect free structure, repro­
A number of approaches such as template mediated growth, VLS ducibility, size control, homogenous composition, etc. No method that
growth, supercritical–fluid–liquid synthesis and solution–liquid–solid can satisfy all these requirements exists as of now. For growing nano­
growth, etc. have been used for synthesizing NWs. wires with specified diameter and length, good crystallinity and prac­
Discovery of vapor–liquid–solid (VLS) is credited to Wagner and Ellis ticable speed, aerotaxy is used. The method makes use of aerosol. The
at Bell Labs [82]. Most commonly, preparation of nanowires is assisted method relies on formation and alignment of NP and NW in a flowing
by nanocluster-catalyzed VLS growth [83]. A commonly agreed upon gas. Thus, there is no requirement of single crystal substrates; nucleation
mechanism of this process is based on getting the constituent semi­ takes place continuously in a gas flow overcoming drawbacks of pro­
conductor dissolved at high temperature within a droplet. Other con­ duction in batches. The method can be applied at various scales, even for
stituents combine till supersaturation is reached. This is followed by the applications involving large area to be covered by NW [90].
nucleation and subsequent precipitation of the product. This takes place
at the interface between the liquid droplet and the solid substrate. 5.2. Nanowire solar cells
Axial as well as radial p-i-n Si-nanowires have been prepared by the
“gold-nanoparticle catalyzed VLS growth method”. In this silane (SiH4) Core–shell NW with high packing density can act as highly absorbing
is most commonly used source for silicon. and as silicon source, For p- elements which can lead to solar cells with high efficiency. Solar cells
type doping diborane (B2H6) is often employed while phosphine (PH3) incorporating inclined and core–shell NW can benefit from effective
serves as a n-type dopant. In the first step nanosized liquid droplets of a light confinement [91]. Apart from inclining and using core/shell
catalyst metal dissolve the reactant gases up to saturation limit is structures, the third factor for optimizing the performance is to manip­
attained. Subsequently, Nucleation is initiated. It culminates into ulate the design parameters like inclination angle, core diameter,
growth of single-crystalline nanowires. nanowire length, and the fill factor. GaAs shell has been used to cover Si
“Template-based growth” is another popular technique among the core. With these strategies current density of 58.59 mA/cm2 and a power
most commonly used methods for producing nanowires (NWs). It in­ conversion efficiency (PCE) of 33.52 % has been attained.
volves a cylindrical pore, track etch membranes or templates fabricated GaAs near-band-edge absorption properties of free-standing
from anodized alumina [84]. The underlying mechanism is the crystal­ GaAs–AlGaAs core–shell nanowires have been reported recently [92].
lization of the desired composition with the boundaries defined by the Prototype NWSC have attained an efficiency of 17.8 %. This could be
pore size. In template-based growth, solutions of the precursors of the achieved through nanophotonic engineering by size and shape control of
desired material in proper solvents are prepared. A working electrode is NW which allows enhanced solar light absorption [93]. Mechanism of
made by plating metal at the end of the template. For electrodeposition light Absorption by NWs is significantly distinct from that for the bulk.
of the desired material, the entire assembly is immersed in the growth Several investigators have observed that subwavelength size, high-
solution; electrodes are inserted and adequate potentials are applied. refractive index NWs have remarkably higher light absorption as
Dimensions of the nanowires are decided by the pore dimensions. The compared to the bulk materials occupying the same volume. Oriented-
host is removed by washing with a suitable etchant and the synthesized NW arrays with appropriately chosen pitch size have been shown [94]
NWs are extracted. to possess antireflection over wide spectral range and effective light-
Pioneering work on preparation of semiconductor NWs using liquid scattering. For certain wavelengths a-Si NW can absorb light more
phase methods (supercritical–fluid–liquid–solid growth (SFLS)) was than its physical size. This had been termed as the ‘optical antenna ef­
presented around year 2000 [85]. This method utilizes supercritical fect’. In association with distinct resonant modes this effect can result in
fluid for attaining desired elevated temperatures. The method could be much higher light absorption compared to that by the bulk material.
exploited for using catalyst NPs like gold for growth of semiconductor EQE is nearly unity even for wavelengths in the range of 400–500 nm
NWs. The factors which govern good yield of NW are solubility of pre­ where the solar cell made from a bulk material shows sharp decline in
cursors, surface binding ligands and ligand passivated NPs. efficiency. This increase is attributable to the “optical antenna effect”.
Another interesting mechanism for the solution phase growth of NWs This effect is purely classical and associated with the sub-wavelength
is known as an ‘‘oriented attachment’’ mechanism. This was postulated diameter of the NW. Light absorption in NWs is determined by the
way back in 1998 [86]. It consists of two steps. First NPs crystallize via following: (i) absorption coefficient of the NW material, (ii) spatial
alignment. In the second step various NPs join along common orienta­ profile of NW cavity modes, (iii) optical antenna effect and (iv) wave­
tion. The process is favoured due to decrease in free energy at surface length matching between NW cavity modes and irradiance of the solar
owing to removal of interfaces and unsaturated bonds. Joining of spectrum.
different NPs is facilitated by dipole–dipole attraction between unpas­ Recently, a numerical analysis of the I-V characteristics quad-
sivated NC faces [87]. What makes the approach attractive is it is not crescent-shaped Si NWSC has been carried out. Based on this analysis
specific to a particular material but pertains to practically all NCs. The the structure was designed for the optimum performance [95,96]. The

6
P.V. Tumram et al. Materials Science & Engineering B 307 (2024) 117504

architecture is made up of four crescents thus enclosing a cavity which (1 0 0) surface of QDs results in poor passivation which adversely affects
facilitates multiple scattering and trapping within NWs. Absorption of the photovoltaic generation. Recently,
light over a wide spectral range takes place from the generation of new mixed halide ions ligand passivation strategy was used for passiv­
modes along NWs. Owing to increased absorption PCE gets enhanced. ating the (1 1 1) and (1 0 0) faces of QDs [102]. This leads to enhanced
The enhancement is as much as 80 %. Use of thin radial shell reduced the carrier mobility, increased carrier lifetime, and reduced defect density.
recombination at the sidewalls of NW. All these factors were shown to boost the IR efficiency by 1.25 %. Huang
The PCE and short circuit current were 18.5 % and 33.8 mA/cm2, et al. obtained similar improvement through passivation [103]. They
respectively for the suggested design of axial junction. The corre­ report that using the PbS-OA QD solution in the concentration 30 mg/ml
sponding numbers for the core–shell junction are 19 % and 34.9 mA/ resulted in the complete elimination of surface OA. Consequently, the
cm2. The proposed crescent design claims an increase of 23 % over the devices so fabricated displayed a higher PCE of 12.53 %. Mukai et al.
conventional NW, for both junctions. For a practical surface recombi­ [104] observed that by substituting ligands of PbS QDs with iodine and
nation velocity of 102 cm/s, the PCE of the proposed design, in the axial preparing QD films by the sedimentation method, PCE was increased. To
junction, has been reduced to 16.6 %, with a reduction of 11 %. How­ achieve this effect Maleki et al. [105] used tetrabutylammonium iodide
ever, the core–shell junction achieves PCE of 18.7 %, with a slight (PbS-TBAI) as active layer (AL). Magnesium Zinc Oxide and PbS etha­
reduction of 1.6 %. nedithiol acted as electron transport layer (ETL) and hole transport layer
Improvement achieved by NW solar cells is not limited to increased (HTL), respectively. For extending the absorption over infrared spec­
light absorption. The other issues like enhancing the Isc and Voc have also trum, Molybdenum Ditelluride was employed to serve as the additional
been considered. These factors are governed by ‘carrier lifetime’, ‘radi­ absorbing layer. In this design nanostructure-oriented core–shell was
ative recombination lifetime’ and ‘recombination current’. For keeping used. Both PCE and Voc increased considerably.
the losses to minimum, the external radiative recombination rate should In devices based on PbS QD, electron transport layer (ETL) is usually
be almost same as the solar generation rate. These basic principles prepared from ZnO. For avoiding band gap reduction of PbS QDs it is
decide the Voc value of a solar cell. Attaining high Voc depends on important that ZnO ETL is suitably accommodated so that carriers are
effective management of the ‘external radiative efficiency [97]’. efficiently extracted. Wang et al. [106] successfully demonstrated the
In principle, open circuit voltage, Voc, of a solar cell should be equal process for this. Postannealing of ZnO is crucial for this. This led to
to the bandgap. However, in practical solar cells, it is always small than proper energy level alignment and reduced trap states. Consequently,
the bandgap. This phenomenon has been called as “Voc-deficit”. The the nonradiative recombinations were suppressed and the electron in­
difference between the actual Voc and the bandgap is “Voc-deficit”. It is jection from the QD layer to ETL got facilitated.
totally influenced by the (nano) photonic design of the solar cell. Xiao et al. noted [107] that the reduction of surface traps is a chal­
Nanowire solar cells provide a way to minimize Voc-deficit and thus lenging process. The hydroxyl group (–OH) is mainly responsible for
increase Voc. producing such traps when PbS QDs are prepared by oleic acid route.
Nanowire solar cells is a new concept and as such there is lot of scope They claimed that use of acetonitrile (ACN) as precipitant for washing
for improving the photonic structure as compared to that for a con­ QDs reduced the trap state density considerably.
ventional solar cell. Apart from maximizing the utilization of solar ra­ Doping of PbS QDs with Ag was shown to boost photovoltaic per­
diation by the nanowire array and optimizing the Isc of the solar cell, formance. Incorporation of Ag releases compressive stress improving
nanophotonic engineering holds a great potential for optimizing the thereby compactness and homogeneity which helps in reducing leakage
external radiative efficiency, which is a vital factor for optimizing Voc of currents. Ag doping increases hole concentration, which aligns energy
the solar cell. Systematic efforts in this direction are lacking. It appears levels and increases hole mobility to boost hole collection. Increased
obvious that a nanowire solar cell could in principle should have higher hole concentration also broadens the depletion region of the active
internal radiative efficiency than its planar counterparts. By optimizing layer, decreasing interface charge accumulation and promoting carrier
the photon escape probability, a higher external radiative efficiency extraction efficiency [108].
than a planar solar cell should be attainable. The anticipated superior PbSe QDSC were improved by changing ETL. PbSe QDSC are up­
performance of a nanowire solar cell is owing to the fact that a large part coming photovoltaic devices acclaimed for solution processing.
of the emission is guided into a confined optical mode which can adia­ Currently, ZnO is used for ETL in these QDSC. However, surface defects
batically expand into the air with only negligible reflection loss. A in ZnO are the deterents for its widespread use. Liu et al. [109] devel­
nanowire solar cell, however, needs a highly reflective back mirror to oped a modified ETL based on Ti3C2Tx and ZnO for producing solar cells
avoid radiation losses in the underlying substrate. responsive to IR. Combining with Ti3C2Tx resulted in reduction of de­
As the NW dimensions shrink the photocurrent density increases fects in ZnO. The reduction is achieved by improved crystallinity.
monotonously. The increase is very rapid for NW with diameters smaller Consequently, transport and collection of photo-generated carriers got
than 200 nm. This is manifestation of the changes in the ratio of ‘ab­ improved by this procedure.
sorption cross-section to physical cross-section [98]’. Improvements are also sought in QDSC based on hybrid FAPbI3 pe­
From the initial days of growing nanowires with tailored architec­ rovskites. Passivation was achieved with help of methylamine thiocya­
ture, the field of nanowire solar cells has come a long way. The recent nate layer. In this process 6.2 nm thick MAPbI3 layer is formed.
years witnessed lot of progress in this context. The notable achievements Formation of the heterostructure results in reduction of trap states, band
are InP nanowire solar cell with the 13.8 % efficiency [99], GaAs gap and increased charge carrier movements [110].
nanowire solar cell with even better efficiency of 15.3 % claimed by Sol In an innovative experiment, two different energy production tech­
Voltaics [100]. The best figure achieved to date is the 17.8 % efficiency niques were combined in a single device. This was achieved by inte­
InP nanowire solar cell reported by Van Dam et al [101]. grating triboelectric nanogenerator and PbS QDSC. Such strategies will
lead to new methods of constructing renewable energy devices [111].
6. Recent developments
6.2. Modification of NWSC Geometries
6.1. Improved QDSC architecture
Recently, Rautela et al [112] studied effect of plasmonic Al NPs on
One of the ways of overcoming Shockley–Queisser limit is to use InP NWSC. The localized surface plasmon resonance (LSPR) character­
tandem architecture. In this respect, PbS QDs are remarkable for istic of Al NPs results into a profound increase in optical edge absorp­
absorbing low-energy IR photons. Moreover, they have tunable bandg­ tion. They reported that, a 37.07 % increase in PCE) for an aspect ratio of
aps and can generate multiple excitons. A drawback is that the exposed 0.3.

7
P.V. Tumram et al. Materials Science & Engineering B 307 (2024) 117504

Performance enhancement was also observed by optimizing the ge­ solving the energy problem. At present some of the ideas of integrating
ometry of NWSC. From thermodynamic considerations it is clear that Voc nanostructures with solar cell design appear futuristic, in context of cost
depends on the external radiative efficiency. Planar SC have small reduction. Cost of nanostructured materials is rather prohibitive to
probability for photon recycling and the said efficiency is about 2 % attain this goal at this moment. With standardization of new technolo­
because of the reflection losses. As a result Voc decreases by 0.1 eV than gies of production of nanostructures the situation will improve.
the maximum attainable value. Tapered NWSC permits an adiabatic
expansion of the optical mode which reduces reflection losses. Conse­ CRediT authorship contribution statement
quently, photon escape probabilities increase by 47 % for the tapered
geometry. The probability almost doubles for inversely tapered NW. Priya V. Tumram: . Renuka Nafdey: Conceptualization, Method­
Using this strategy Bochicchio et al [113] observed optimum increase in ology. Pranay R. Kautkar: Investigation. S.V. Agnihotri: Writing –
Voc for tapering angle of 2.46 . review & editing. Rohini A. Khaparde: Investigation. S.P. Wankhede:
◦

Concept of tandem photovoltaics for high efficiency was also Writing – review & editing. S.V. Moharil: Conceptualization, Writing –
extended to NWSC [114]. The GaInP and InP subcells and the Esaki original draft, Writing – review & editing.
tunnel diode linking them were packed in the same NW. These results
are of importance for designing high efficiency NWSC. In another work, Declaration of competing interest
core–shell structure was used for constructing NWSC [115]. The cell
based on GaAs0.99Bi0.01/ZnO/ITO core–shell had core dimensions of 1 The authors declare that they have no known competing financial
µm x 100 nm and shell 10 nm thick with 280 nm period. The core–shell interests or personal relationships that could have appeared to influence
structure facilitates the charge carrier separation and consequently in­ the work reported in this paper.
creases Voc as well as PCE.
Geometries have also been used to increase the bandgap of tradi­ Data availability
tional semiconductor NW. It was demonstrated that GaN and Ag nano­
plasmons modulate the bandgap of the Si NWs [116]. As a result, charge No data was used for the research described in the article.
carrier density, photocurrent, and optical hole mobility increase. Ag
nano particles are more effective for reducting the ‘nonlinear optical References
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