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SOLAR CELLS AND
LIGHT MANAGEMENT
Materials, Strategies
and Sustainability

Edited by

FRANCESCO ENRICHI
Research Fellow
Department of Molecular Sciences and Nanosystems
Ca’ Foscari University of Venice
Venice, Italy

GIANCARLO C. RIGHINI
Emeritus Research Director
Museo Storico della Fisica e Centro Studi e Ricerche Enrico Fermi
Rome, Italy
Elsevier
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To my wife Valentina and my children Marco, Davide, and Elena,
for their endless love, trust, and support
Francesco Enrichi

To my Dearest Ones, Marta and Nicoletta

Giancarlo C. Righini
Contributors


Hugo Aguas
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal

Mario Enrique Alvarez-Ramos
Posgrado en Nanotecnología, Departamento de Física, Universidad de Sonora, Hermosillo,
Sonora, México
Arturo Ay on
MEMS Research Lab, Department of Physics and Astronomy, University of Texas at San
Antonio, San Antonio, TX, United States
Jérémy Barbé
SPECIFIC, College of Engineering, Swansea University, Swansea, United Kingdom
Antonino Bartolotta
CNR-IPCF, Istituto per i Processi Chimico-Fisici, Messina, Italy
Brigitte Boulard
IMMM UMR CNRS 6283, Le Mans Université, Le Mans, France
Giuseppe Calogero
CNR-IPCF, Istituto per i Processi Chimico-Fisici, Messina, Italy
Andrea Chiappini
IFN-CNR CSMFO Lab. and FBK Photonics Unit, Povo-Trento, Italy
Isabella Concina
Division of Materials Science, Department of Engineering Sciences and Mathematics,
Luleå, Sweden
Isodiana Crupi
Engineering Department, University of Palermo, Palermo, Italy
Paola Delli Veneri
Italian National Agency for New Technologies, Energy and Sustainable Economic
Development (ENEA), Portici Research Centre, Portici, NA, Italy
Aldo Di Carlo
Centre for Hybrid and Organic Solar Energy, University of Rome Tor Vergata, Rome,
Italy; Laboratory for Advanced Solar Energy, National University of Science and
Technology ‘‘MISiS’’, Moscow, Russia
Francesco Enrichi
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice,
Venice, Italy

xiii j
xiv Contributors

Maurizio Ferrari
IFN-CNR CSMFO Lab. and FBK Photonics Unit, Povo-Trento, Italy; Museo Storico
della Fisica e Centro Studi e Ricerche Enrico Fermi, Rome, Italy
Alvaro Flores-Pacheco
Posgrado en Nanotecnología, Departamento de Física, Universidad de Sonora, Hermosillo,
Sonora, México; MEMS Research Lab, Department of Physics and Astronomy, University
of Texas at San Antonio, San Antonio, TX, United States
Elvira Fortunato
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Mojtaba Gilzad Kohan
Division of Materials Science, Department of Engineering Sciences and Mathematics,
Luleå, Sweden
Francesco Gonella
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice,
Mestre-Venezia, Italy
Sirazul Haque
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Harrison Ka Hin Lee
SPECIFIC, College of Engineering, Swansea University, Swansea, United Kingdom
Yumiko Katayama
Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan
Anna Lukowiak
Institute of Low Temperature and Structure Research, PAS, Wroclaw, Poland
Xiaoling Ma
Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing
Jiaotong University, Beijing, China
Rodrigo Martins
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Tiago Mateus
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Manuel J. Mendes
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Contributors xv

Lucia V. Mercaldo
Italian National Agency for New Technologies, Energy and Sustainable Economic
Development (ENEA), Portici Research Centre, Portici, NA, Italy
Itumeleng Mokgosi
School of Physics, Centre of Excellence in Strong Materials and Materials for Energy
Research Group, University of the Witwatersrand, Johannesburg, South Africa
Seweryn Morawiec
Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus
University, Torun, Poland
Dustin R. Mulvaney
Department of Environmental Studies, San Jose State University, San Jose, CA, United
States
Alessandro Lorenzo Palma
Centre for Hybrid and Organic Solar Energy, University of Rome Tor Vergata, Rome,
Italy; Italian National Agency for New Technologies, Energy and Sustainable Economic
Development (ENEA), Energy Efficiency Unit Department, Rome, Italy
Alexander Quandt
School of Physics, Centre of Excellence in Strong Materials and Materials for Energy
Research Group, University of the Witwatersrand, Johannesburg, South Africa
Giancarlo C. Righini
Museo Storico della Fisica e Centro Studi e Ricerche Enrico Fermi, Rome, Italy
Olalla Sanchez-Sobrado
i3N/CENIMAT, Department of Materials Science, Faculty of Science and Technology,
Universidade NOVA de Lisboa and CEMOP/UNINOVA, Campus de Caparica,
Caparica, Portugal
Danila Saranin
Laboratory for Advanced Solar Energy, National University of Science and Technology
‘‘MISiS’’, Moscow, Russia
Sofia Spagnolo
Department of Environmental Sciences, Informatics and Statistics, Ca’ Foscari University of
Venice, Mestre-Venezia, Italy
Setsuhisa Tanabe
Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku,
Kyoto, Japan
Wing Chung Tsoi
SPECIFIC, College of Engineering, Swansea University, Swansea, United Kingdom
Alberto Vomiero
Division of Materials Science, Department of Engineering Sciences and Mathematics,
Luleå, Sweden; Department of Molecular Sciences and Nanosystems, Ca’ Foscari
University of Venice, Italy
xvi Contributors

Robert Warmbier
Department of Physics, University of Johannesburg, Auckland Park, South Africa
Narges Yaghoobi Nia
Centre for Hybrid and Organic Solar Energy, University of Rome Tor Vergata, Rome,
Italy
Fujun Zhang
Key Laboratory of Luminescence and Optical Information, Ministry of Education, Beijing
Jiaotong University, Beijing, China
Lidia Zur
IFN-CNR CSMFO Lab. and FBK Photonics Unit, Povo-Trento, Italy
Preface

The growth of global population and the ever-increasing energy consump-

tion put serious questions on the sustainability of our society. In this context,
the transition from fossil fuels to renewable energies is recognized as a funda-
mental strategy to pursue, driven by strong investments and strict regula-
tions. Among renewables, a key role is played by photovoltaics (PV),
since sunlight is widespread all over the world and can be exploited at any
level, from cheap portable devices up to large industrial installations.
In the last few decades, the evolution of solar cells developed incredibly
fast, thanks to both a multiplication of different technologies driven by the
synthesis and optimization of novel materials and a continuous increase of
efficiency, made possible by proper structure design and light management
strategies. The aim of this book is to provide the state of the art of the most
recent progresses in the field of PV solar cells, with the attempt of shining
light on emerging technologies, latest results, and potential perspectives. It
is intended both for the expert in the field, and for the newcomer, being
a valuable reference tool with updated literature and envisioned develop-
ments in the field. It also aims at being an instructive and stimulating text
for undergraduate and postgraduate students, allowing a growth of their
knowledge about novel materials for solar cells and light management.
This book is organized in four sections. After a general introduction, the
first section provides a detailed overview on different concepts and materials
for solar PV devices, starting from the standard silicon cells to the organic-
based, dye-sensitized perovskite and all-oxide solar cells. This panorama al-
lows the reader to get up to date with the standard traditional approach as
well as the new and more promising concepts for the evolution of the field.
The second and third sections are focused on light manipulation and solar
spectrum modification, as tools to further increase the photon-to-current ef-
ficiency. This field, too, is in rapid evolution, and the latest results on optical
strategies and materials for light trapping, plasmonic scattering, spectral up-
and downconversion (mainly based on rare earth doped oxides and com-
plexes) are reported.
Finally, in the last section, a critical approach on the sustainability of PV
technologies is given. An eMergy (spelled with “m”) analysis, which is an
extension of the life cycle analysis (LCA), is applied to the study of solar
PV systems. Furthermore, the limits of LCA metrics into questions of

xvii j
xviii Preface

environmental justice, human rights, and other nonquantifiable impacts of

production systems are discussed. Nowadays, the attention to issues such
as sustainability and social responsibilities cannot be neglected and, instead,
should be carefully considered in the development of new technologies
and their use.
In details, this book starts with an introduction, Chapter 1, which gives
an overview of the concepts and a summary of the main results of the PV
sector. After a general description of the global scenario and the historical
evolution of PV, the different families of solar cells are presented, with their
latest efficiency achievements and perspectives of further research develop-
ment. Furthermore, the main optical strategies for increasing the efficiency
of these devices are illustrated with updated results and future potential.
Chapter 2 is focused on silicon solar cells from a device-engineering
perspective, encompassing both the crystalline and the thin film (based on
amorphous and microcrystalline silicon) technologies. Properties and fabri-
cation methods of the photoactive materials are considered, as well as
different device architectures and promising new trends for this technology.
Organic solar cells (OSCs) are the subject of Chapter 3, with particular
attention to the recent advances in ternary structures. The development
of ternary OSCs based on different system is summarized; the main working
mechanisms and the potential research directions are outlined, together with
the challenges and perspectives for future development.
An original journey into the field of dye-sensitized solar cells (DSSCs),
starting from the colors of chemical dyes to the natural ones, is presented
in Chapter 4. The state of the art, design, and fabrication of solar devices
based on the appealing family of natural sensitizers are shown, reviewing
their lights and shadows. The working principles and the main components
of DSSC are described, with a specific focus on the photoanode; a systematic
review of the many dyes employed as sensitizers for solar energy application
is also provided.
In Chapter 5, the emerging field of perovskite solar cells is examined.
The chapter summarizes the unique properties of halide perovskite, such
as crystal structure, energy band properties, charge transport, recombination,
and ferroelectric properties. A detailed discussion is devoted to perovskite
crystallization (from liquid phase) and the use of different deposition
methods. Furthermore, examples of possible device architectures and mod-
ule fabrication are discussed.
Solar cells based on oxide materials are described in Chapter 6. These ox-
ides, composed of Earth-abundant harmless materials, are more stable than
Preface xix

most of the other materials alternative to silicon and are therefore ideal can-
didates for realizing cheap, stable, and safe solar cells. Their major efficiency-
limitation factor is the low hole mobility in the p-type oxide. This chapter
illustrates the latest results in the field, including the integration of nanowire
geometries as a viable solution toward fast charge transport and collection.
Chapter 7 illustrates simulation approaches for the modeling of PV ma-
terials and devices. The calculation of material parameters by ab initio
methods based on density functional theory opens the very exciting possibil-
ity to develop new types of solar cells entirely in silico. Furthermore, the
chapter gives some insights in the augmentation of commercial types of solar
cells by using frequency conversion layers.
Metallic nanoparticles sustaining localized surface plasmon resonances are
the subject of Chapter 8. The correlation between structural and optical
properties of self-assembled silver nanostructures, the optimization of the
fabrication process, and their potential for enhancing light trapping in thin
film PV are discussed. Furthermore, a novel optoelectronic spectroscopic
method for the quantification of absorption enhancement and of parasitic
losses in thin photovoltaic absorbers due to plasmonic light trapping is
described.
Chapter 9 is focused on the development of photonic structures for
improving light trapping in thin film solar cells, enabling high-efficiency,
low-cost and mechanically flexible devices, in particular for silicon and
perovskite PV technologies. In this chapter, colloidal lithography methods
are shown to be suitable for surface nanopatterning, allowing compatibility
with industrial scalability and low-cost requirements.
The field of indoor light harvesting is presented in Chapter 10, in rela-
tion to the significant increase of electronic devices for Internet-of-Things
(IoT) applications. IoT can be crucial in developing smart homes, offices,
and buildings. Compared to silicon, the cheaper organic and perovskite
PV cells have much better performance under indoor lighting conditions.
The aim of this chapter is to introduce this exciting and emerging applica-
tion of organic and perovskite PV devices.
Chapter 11 discusses transparent glass ceramics activated by rare earth
ions as spectral converters to improve the efficiency of solar cells. After a
brief presentation of transparent glass ceramics, the basics of spectral conver-
sion are summarized, and some specific examples, mainly based on glass ce-
ramics fabricated by sol-gel route, are reported.
In analogy with the previous chapter, Chapter 12 is focused on quantum
cutting by lanthanides and Yb3þ co-doped phosphors. After absorption in
xx Preface

the UV or visible spectral region, two or more photons at about 1 mm wave-

length can be emitted, which are better matched to commercial polycrystal-
line or single crystal silicon absorption. Recent results and updated literature
on this field are presented.
The use of quantum dots as broadband spectral down-shifters is
illustrated in Chapter 13. The experimental observations indicate that higher
power conversion efficiency values can be achieved by exploiting this
down-shifting effect, due to the absorption of the UV photons by the
QDs involved and the subsequent emission at longer wavelengths.
In Chapter 14, an eMergy (spelled with “m”) analysis approach is pre-
sented, applied to the study of solar PV systems. Emergy analysis is a
thermodynamic-based method used for the assessment of systemic sustain-
ability, based on the upstream energy investment necessary for creating a
product or a service. This analysis, which is an extension of Life Cycle
Assessment (LCA) methodology, allows to determine effective integrated
indicators for the evaluation of the global efficiency and the sustainability
of the systems at issue.
Finally, Chapter 15 draws on several LCA and environmental justice case
studies related to PV commodity chains. It aims at improving our under-
standing of the socio-ecological impacts of global production systems.
LCA could be an important tool to explore the roots of environmental
inequality, and it brings a way to look at risks in a more comprehensive
way, but also poses some challenges. This chapter attempts to provide
both the rationale, methodology, and instances of integrating LCA and
commodity chain analysis in the assessment of systems of production.
This book would not have been possible without the collaboration and
the scientific-technical expertise of the authors of the different chapters; we
are deeply indebted to them for their excellent and timely work. We are also
grateful to our editorial project manager, Isabella Conti Silva, and all the
Elsevier editorial staff for the precious and continuous support.

Francesco Enrichi
Giancarlo C. Righini
 CHAPTER ONE

Solar cells’ evolution and

perspectives: a short review
Giancarlo C. Righini1, Francesco Enrichi2
1
Museo Storico della Fisica e Centro Studi e Ricerche Enrico Fermi, Rome, Italy
2
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice, Venice, Italy

1.1 An introduction: economics, energy, and

sustainability
The growth in world population and industrialization that started to
accelerate in the second half of the 20th century had an obvious effect on
the growth of the global economic activities, hence of the world gross prod-
uct (WGP). In turn, energy consumption has also continuously increased
and so did the impact of all these factors on the environment. Doubts
were then rising about the possible consequences of continuing to equate
growth with progress. The concept of sustainability, “which encompasses
the idea of pursuing societal structures and activities that are resilient and
enduring, for both human beings and the geobiosphere that supports their
life” [1], is relatively recent. A first warning of unlimited material growth
and unrestrained consumption in a world which has limited resources
came from the work of “Club of Rome,” founded in 1968 [2], and from
the publication, in 1972, of the report “The Limits to Growth” [3], that first
introduced the idea that environmental and economic issues cannot be
treated separately. The idea of assessing the quality of energy necessary to
make a product or service and of doing so by taking into account all the rele-
vant parameters (primary energy, economic investment, labor, environ-
mental loading, etc.) led to the introduction of the emergy methodology,
largely based on the seminal work by H. T. Odum [4]. An emergy analysis
of a sustainable photovoltaic solar exploitation is presented in the Chapter 14
of this book [1].
Fig. 1.1 presents the growth rates of population, WGP, global energy
consumption, and electricity consumption in the present decade

Solar Cells and Light Management

© 2020 Elsevier Ltd.
j
ISBN: 978-0-08-102762-2
https://doi.org/10.1016/B978-0-08-102762-2.00001-X All rights reserved. 1
2 Giancarlo C. Righini and Francesco Enrichi

Figure 1.1 Growth rates in the present decade of the population (blue), world gross
product (orange), global energy consumption (yellow), and global electricity consump-
tion (gray).

(2010e19). Despite the fact that the population growth slowed in the last
years (1.07% growth rate estimated in 2019, with respect to 1.23 in
2010), it reached a count of over 7.7 billions of persons [5]; the GDP annual
growth rate fluctuated but was always higher than 3%, reaching 3.6% in
2017 and 2018 (values calculated by adjusting for purchasing power parities,
i.e., for differences in the cost of living across countries) [6].
The energy consumption increased at a lower rate than GDP, thanks to a
better efficiency of the technologies and industrial processes; in 2017 and
2018; however, there was a faster rise, with a global energy demand
increased by 2.1% in 2017, compared with 0.9% the previous year and
0.9% on average over the previous 5 years. More than 40% of the growth
in 2017 was driven by China and India. Global energy demand in 2017
reached an estimated 14,050 million tonnes of oil equivalent (Mtoe),
compared with 10,035 Mtoe in 2000, according to the “Global Energy
and CO2 Status Report 2017,” released by the International Energy Agency
(IEA) in March 2018 [7]. The global trend of consumption of electricity, in
particular, after a continuous strong increase from 2000 to 2010, slowed
down, with a minimum growth rate in 2015, corresponding to minimum
growth rate of GDP [8]; then, started again to rise, with an increase of
2.6% in 2017. Global power generation is forecast to increase by some
60% between 2017 and 2040 to cover a quarter of primary energy demand,
the IEA said in its World Energy Outlook 2018 [9].
Solar cells’ evolution and perspectives: a short review 3

Correspondingly, the measurements of the natural concentration of car-

bon dioxide in our atmosphere have shown that the annual increase rate
over the past 50 years has been about 100 times faster than previous natural
increases, which were due to thermal fluctuations in geological eras. Fig. 1.2
shows the historical fluctuations of the atmospheric carbon dioxide concen-
tration, as reconstructed from ice cores [10]. Global energyerelated CO2
emissions grew by 1.4% in 2017, reaching a historic high of 32.5 gigatonnes
(Gt), a resumption of growth after 3 years of global emissions remaining flat
[7]; the average concentration of CO2 in the atmosphere also hit a new re-
cord high in 2017: 405.0 parts per million (ppm). Fig. 1.3 reports the atmo-
spheric CO2 levels measured at the altitude of 3400 m, at Mauna Loa
Observatory, Hawaii, from 2005 to present; the latest data, expressed as
dry mole fraction of the number of molecules of carbon dioxide divided
by the number of molecules of dry air multiplied by one million ppm, are
obtained from direct measurements of the infrared absorption, showed in
January 2019 a level of 411 ppm.
Despite some debates, there is scientific consensus on two facts, namely
that the greenhouse gases are causing a climate change (even if still there is

Figure 1.2 Atmospheric concentration of carbon dioxide during the last three glacial
cycles, as reconstructed from ice cores, and current level. Credit: NOAA. Reproduced
from NASA, Global Climate Change. Facts. https://climate.nasa.gov/evidence/.
4 Giancarlo C. Righini and Francesco Enrichi

Figure 1.3 Atmospheric concentration of carbon dioxide from 2005 to present, as

obtained by monthly averaged measurements of infrared absorption at the Mauna
Loa Observatory, Hawaii. The fluctuations due to the average seasonal cycle were
removed from the plot. Credit: NOAA. Reproduced from NASA, Global Climate Change.
Carbondioxide. https://climate.nasa.gov/vital-signs/carbon-dioxide/.

no universal agreement about the quantitative magnitude of anthropogenic

global warming and on its consequences) and that the CO2 emissions from
the combustion of fossil fuels give the largest contribution to the greenhouse
gases. Accordingly, policies’ choices made by most governments are aimed at
reducing air pollution, ensuring universal energy access, and achieving long-
term climate goals, with the central aim to keep a global temperature rise this
century well below 2 C above preindustrial levels and to make all efforts to
limit the temperature increase even further to 1.5 C. This was the target of
the Paris Agreement, entered into force in November 2016 and currently
ratified by 185 Parties of 197 Parties to the UNFCCC (United Nations
Framework Convention on Climate Change) [11].
The goal of reducing CO2 emissions while still providing the energy ser-
vices necessary to accommodate the global economic growth may be
reached only by reducing substantially the impact of the energy sources,
which provide the highest CO2 emissions, namely coal and, more generally,
fossil fuels. Electricity is increasing its share among worldwide end uses of
energy; industrial electric motor systems, electric mobility, electric heating,
and electricity access could lead to a 90% rise in power demand from today
to 2040, according to the IEA forecast [9]. It is here that renewable sources
of energy can play a substantial role. Fig. 1.4 shows that in 2017, the fraction
of electricity generated by renewables reached a record high of 25% (and
constituted nearly half of the global additional generation of 380 TWh
required to meet the increasing demand); moreover, IEA forecasts that
Solar cells’ evolution and perspectives: a short review 5

Figure 1.4 Electricity generation in 2017, for a total of 25,570 TWh, by different energy
sources. PV, photovoltaics. Credit: IEA. Reproduced with modifications from Global Energy
& CO2 Status Report 2017. https://www.iea.org/geco/.

the share of generation from renewables could rise from 25% today up to
around 40% in 2040 [7].
Today, wind, hydropower, and solar photovoltaics (PV) represent a major
source of low-emissions electricity; IEA expects that the increasing compet-
itiveness of solar PV could lead its installed capacity to overcome that of wind
before 2025, of hydropower around 2030, and of coal before 2040. Other
problems, however, have to be considered; for instance, the wider distribu-
tion of PV-generated electricity may create additional requirements for the
reliable operation of power systems. Moreover, if electrification certainly re-
duces local pollution, additional measures may be necessary to control its
generation as well as the operation and the decommissioning of the power
supply systems from the environmental point of view; otherwise, the risk is
that pollution and CO2 emissions simply move upstream from the end-use
sectors to power generation, systems’ decommissioning, and recycling.
In the present chapter, a brief overview of the status of the research on
the fundamental bricks of the solar PV, namely the PV cells, is outlined,
without entering into considerations on solar panels and concentrated pho-
tovoltaics (CPV).

1.2 Solar photovoltaics: historical notes

Solar radiation at the earth’s upper atmosphere totals some 174 PW;
the average annual solar radiation is roughly 1.36 kW/m2 and, since about
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