(SpringerBriefs in Applied Sciences and Technology) Girtan, Mihaela - Future Solar Energy Devices-Springer (2018)

SPRINGER BRIEFS IN
APPLIED SCIENCES AND TECHNOLOGY
Mihaela Girtan
Future Solar
Energy Devices
123
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Mihaela Girtan
Future Solar Energy Devices
123
Mihaela Girtan
University of Angers
Angers
France
ISSN 2191-530X ISSN 2191-5318 (electronic)

SpringerBriefs in Applied Sciences and Technology
ISBN 978-3-319-67336-3 ISBN 978-3-319-67337-0 (eBook)
https://doi.org/10.1007/978-3-319-67337-0
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To my lovely daughter Oana
Preface
Archimedes said, “Give me a place to stand and I will move the world”. The future
technologies based maybe all on light will let as perhaps say: “Give me the light
and the world will turn”.
This book gives a personal view on materials science, electronics, photonics and
future solar energy devices. Based on the similarities between electronics and
photonics and on the new advancements on solar energy and photonics devices, this
book tries to expose the new trends in science and future research axis.
If we have materials, light, life and intelligence, we can construct a world.
Looking back on the achievements of the last hundred years we remark that on the
basis one material: “sand” or “silicon dioxide” the common efforts of human beings
led to a huge and unimaginable development. All electronics, informatics and
communication networks are based on electronic devices made with silicon which
is extracted from sand and optical fibre networks which are fabricated from silicon
dioxide.
Materials are constructed from unit building blocks, atoms and molecules,
arranged in a periodic structure. In the same way, new artificial unit building blocks,
with completely new properties, can be created and new materials called meta-
materials or photonics crystals open a huge area of applications and research. The
understanding of the basis of solid-state physics allows the understanding of
electrons and photons transport phenomena in different 1D, 2D or 3D classical or
new periodic structures.
The first chapter of this book presents a parallel between electronics and pho-
tonics and the introduction to data transmission.
The second chapter is devoted to theoretical aspects of materials physics
including the band energies formation, the charge carrier transport, the photon–
electron interactions, quantum wells, quantum dots, photonic crystals and meta-
materials. The understanding of band energy formation and charge carriers transport
could be subsequently extrapolated for the theories related to photonic crystals,
plasmonics, photons interactions and “transport” in periodically optic structures.
As a consequence of photon–electron interactions, the energy of photons can be
converted into electrical energy. Chapter 3 describes the fundamentals of solar cells
vii
viii Preface
functioning principles and the new trends in solar cells research giving a
non-exhaustive list of examples and strategies developed recently in this research
area, in order to increase the energy conversion efficiency.
Chapter 4 is dedicated to the advancements in photonics and photonic devices,
including the new materials, the new carriers information vectors (plasmons and
surface plasmons polaritons), optical and plasmonics waveguides, lasers, spasers,
electro-optical modulators, optical transistors, integrated photonics circuits, etc.
Chapter 5 gives some general considerations on energy and perspectives of a
direct use of the solar energy.
This book is dedicated to all physics passionate students and scientists with the
hope to give a useful overview on some hot topics at the interface of many research
fields such as data transmission, materials physics, nanotechnologies, electronics,
photonics and solar energy devices.
The author is grateful to Oana, Manuel, Maria, Bogdan, Dumitru and Mayra for
English corrections and for moral and technical support for this work.
The author also would like to thank the exceptional professors: Liliana
Alexandru, Margareta Ignat, Mihaela Rusu, Dumitru Alexandru, Stefan Antohe,
Gheorghe Rusu and Michael Graetzel.
Angers, France Mihaela Girtan

Contents
1 A Parallel Between Electronics and Photonics . . . . . . . . . . . . . . . . . . 1

1.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Carrier Vectors and Transport Cables . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Pulse Generators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Data Transmission by Analog and Digital Signals . . . . . . . . . . . . 5
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2 Theoretical Aspects of Materials Physics . . . . . . . . . . . . . . . . . . . . . . . 15
2.1 Bands Energies Formation in Solids Crystalline Materials . . . . . . 15
2.2 Charge Carriers Transport in Bulk Semiconductors . . . . . . . . . . . 16
2.3 Transport Coefficients in Thin Films. Semi-classical Theory . . . . 24
2.4 Quantum Effects in Charge Transport. Quantum Well,
Quantum Wires, Quantum Dots . . . . . . . . . . . . . . . . . . . . . . .... 28
2.5 Linear Conjugated Systems. Organic Semiconductors.
Charge Transport in Organic Materials . . . . . . . . . . . . . . . . . . . . . 30
2.6 Photon—Electron Interactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.7 Superlattices. Photonic Crystals and Metamaterials . . . . . . . . . . . . 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3 New Trends in Solar Cells Research . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.1 Functioning Principles and Current Status . . . . . . . . . . . . . . . . . . 45
3.2 Plastic and Paper Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3 New Transparent Electrodes (IMI and Graphene) . . . . . . . . . . . . . 53
3.4 Strategies for Increasing the Absorption . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4 Trends in Photonics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 77
4.1 New Materials (Metamaterials and Graphene) . . . . . . . . . . . .... 77
4.2 New Carrier Information Vectors (Plasmons and Surface
Plasmons Polaritons) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 78
4.3 Optical and Plasmonic Waveguides . . . . . . . . . . . . . . . . . . . .... 80
ix
x Contents
4.4 New Generators (Spasers) . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 83

4.5 Modulators (Electro-Optic, Electro-Plasmonic
or Opto-Plasmonic) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 87
4.6 Electronic and Optical Transistors . . . . . . . . . . . . . . . . . . . . .... 89
4.7 Electronic Integrated Circuits and Photonics Integrated
Circuits (PIC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 89
4.8 Optical Data Transmission (LIFI and VLC) . . . . . . . . . . . . . .... 90
4.9 Optical Manipulation (Optical Antennas, Optical Tweezers,
Photonic Motors) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 92
4.10 Laser Propulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 93
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 93
5 Energy Conversion or Direct Use? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Chapter 1
A Parallel Between Electronics
and Photonics
Analysing the basic materials and continuing with the information carrier vectors,
the carriers transport ways, the generators, etc., these two sciences “Electronics”
and “Photonics” have a lot of elements in common.
Historically, we can consider that Electronics derived as new technological and
research field from Electricity and that Photonics derived from Optics.
Electronics starts with the invention of vacuum tubes in 1904, but the real date of
birth of modern electronics is that one at which was invented the transistor based on
semiconductor materials (1947).
Electronics is defined as branch of Physics and Electrical Engineering, which
deals with electrons displacements in a circuit that involve passive and active
electrical components such as resistors, capacitors, vacuum tubes, transistors,
diodes, integrated circuits, etc.
Today, most electronic components use semiconductor elements to achieve the
control of electrons. The study of semiconductor devices and associated technology
corresponds to the solid-state physics area, whereas the design and construction of
electronic circuits in order to solve practical problems correspond to electronics
engineering area.
Electronic circuits can be divided into two groups: analog and digital. Analog
circuits use a continuous range of voltage or current, whereas digital circuits are
electronic circuits are based on a number of discrete voltage levels. Most digital
circuits use a binary system with two voltage levels “low” and “high” labelled with
“0” and “1”, respectively and this represents the most common physical application
of Boolean algebra which led to the development of all digital computers.
With the development of lasers and data transmission by optical fibers, the term
of “Photonics” was introduced in the 1980s, from the necessity to describe a
research field, different from the Optics, whose aim was to use light to perform
functions that usually fell within the domain of electronics, such as telecommuni-
cations, information processing, etc.
Hence, Photonics can be defined as the science of generation, transmission,
amplification, detection, modulation and manipulation of photons [1].
© The Author(s) 2018 1
M. Girtan, Future Solar Energy Devices, SpringerBriefs in Applied
Sciences and Technology, https://doi.org/10.1007/978-3-319-67337-0_1
2 1 A Parallel Between Electronics and Photonics
1.1 Materials
The first element in common of electronics and photonics is their raw material: sand
or silicon dioxide (SiO2) also known as silica. SiO2 is one of the most abundant
chemical compounds on earth and can be commonly found in nature in the form of
sand, quartz or opals (Fig. 1.1).
The applications of SiO2 are numerous and since more than 4000 years old,
starting with buildings construction domain, as a basic material for cement and
glass windows, and continuing with all the glass applications uses in food industry,
aeronautics, marine industry, medicine, etc.
For optics and photonics, silicon dioxide is the basic material for optical ele-
ments such as optical waveguides, optical fibers, lens, mirrors, etc.
Beside, silicon is extracted from silicon dioxide by the reaction of
high-purity silica with wood, charcoal, or coal at high temperatures (over 1900 °C)
on the basis of the following chemical reaction SiO2 + 2C ! Si + 2CO and silicon
is today the main material for all integrated electronic circuits and almost all
photovoltaic industrial systems (Fig. 1.2).
Fig. 1.1 a Silicon Dioxide chemical structure and Silicon Dioxide in its different naturals forms
b Opals—ones of the most beautiful examples of natural photonic crystals c Quartz crystals d Sand
1.2 Carrier Vectors and Transport Cables 3
Fig. 1.2 Silicon in different forms a Bulk crystalline material b Silicon wafers c Electronic
integrated circuits on silicon wafers d Monocrystalline silicon solar cells
1.2 Carrier Vectors and Transport Cables
Electronics is based on the transport phenomena of electrons and photonics on the

transport phenomena of photons. Electrons and photons are both elementary par-
ticles, electrons have mass, photons have not, electrons have electric charge and
photons have not. Photons have the speed of light, while electrons can never attain
this speed. Electrons can emit photons but photons cannot emit electrons. Electrons
moves inside electrical cables due to an electrical potential difference (Fig. 1.3a).
Photons moves in optical fibers (wave guides) by multiple reflections (Fig. 1.3b).
Fig. 1.3 a Electrical metallic cables acts as transport cables for electrons b Optical wave guides
and optical fibers act as transport cables or optical circuits for photons
Fig. 1.4 A parallel between the electricity networks and optical fibers networks
Today the electrical networks are everywhere in the Earth and soon, will be the
same for the optical fibers networks (Fig. 1.4).
1.3 Pulse Generators
In electronics we can generate packages of electrical pulses (low and high voltages),
this packages can contain a codified information. In photonics by using lasers we
can generate light pulses (light on/light off) packages. The performances at present
of electrical signal pulse generators correspond to 100 kHz in frequency, duration
pulses of 100 ps and transitions times of 45 ps. For ultrafast lasers or ultrashort
pulse lasers, the performances are at present of 10–100 MHz repetition rates and
duration pulses of 10–50 fs. For pulsed LED Light generators the performances are
of 20–100 ns pulse duration and 100–1000 Hz pulse repetition rate [2] (Fig. 1.5).
Fig. 1.5 Electrical pulses versus optical pulses a Electrical pulses generated by electronic circuits
b Optical signal pulses generated by lasers
1.3 Pulse Generators 5
The development of electronics and of photonics have led to a lot of applications

that becomes indispensable for our modern life today such as computers and
communications.
1.4 Data Transmission by Analog and Digital Signals
The necessity to communicate is an ancestral need. The necessity to express an

action or to transmit a think, an achievement, the knowledge, an information to the
other people around, or to the next generation descendants exists from the begging
of our life. The simple fact to express an action, or a thought pass by many
encoding processes.
First encoding process was the “language”: from think to speak. The second
encoding process was to transform the speech, the language, in “writing”. Then the
need to transmit this information at greater distances made that speech and writing
were not sufficient and hence, we assisted to a new encoding of the information by
the “analog transmission” and then by the “digital transmission” (Fig. 1.6).
After sound, image and touch, the full human senses long distance communi-
cation will be achieved when the way to transmit the taste and olfactory sensations
will be found.
We call “data” an entity that has meaning or conveys information. The “signal”
is a wave representation of data. “Transmission” represent the displacement of data
from source to destination through the use of signals. A communication (transport)
channel is any pathway over which data can be transmitted. Electromagnetic
radiation is used for all data transmission today. The electromagnetic radiation can
propagate in different media (air, vacuum, copper cables, optical fibers etc.) and can
have different frequencies from: microwaves and radio waves (3 kHz–300 GHz),
Fig. 1.6 Communication evolution

infrared radiation (300 GHz–200 THz), visible and extreme ultraviolet (200 THz–
20 PHz), to gamma rays (20 PHz–300 EHz).
That means that any path, wired or wireless, consisting in an electrical or optical
cable, air or vacuum can be exploited to transport the information. The frequencies
used today for data transmission range from radio and microwaves frequency to
visible.
An “analog signal” (Fig. 1.7a) is a continuous signal which represents physical
measurements, denoted by sine waves which use a continuous range of values to
represent an information (example: the human voice in air). A “digital signal”
(Fig. 1.7b) is a discrete time signal, denoted by square waves which use discrete or
discontinuous values to represent the information (example: a sound message
transmitted in “Morse code”).
The encoding evolution up to nowadays in function of type of information,
communication channel, time to reach the receiver, wave frequency, maximum
distance emitter—receiver and the quantity of transported information in function
of time is given in Table 1.1.
Alexander Graham Bell was the first inventor who succeed to transmit an
information at long distance, in 1874, by transforming satisfactorily the sound
waves into electrical signals (in a transmitter) and then to re-transform these signals
into audible speech in a receiver. The transmitter and receiver convertors: sound
waves/analog electrical signal (microphone and speaker) were constructed on the
basis of the same principle (Fig. 1.8).
The mechanical vibration produced by sound was transmitted to a magnetized
hips which induce an undulating current that would be transmitted by wire. Then
the transmitted current was converted again via an electromagnet into a mechanical
vibration that would reverberate on a diaphragm, thus reproducing the original
sound.
Since that time, in the last century, the communications by analog signals
progress a lot and they can be described in a simple way by the scheme depicted in
Fig. 1.9.
Another idea of Bell was the “photophone” (1880), which work function scheme
is depicted in Fig. 1.10. This idea reposes also on an analog transmission of signals
Fig. 1.7 Analog versus

digital signal
Table 1.1 Encoding evolution
Encoding Type of Communication channel Time to reach Waves Maximum distance Quantity of transported
information the receiver frequency emitter—receiver information in time
Thinking Not known Not known Not known <100 Hz Not known Not known
Mimics Visual Visual instantaneous – Many meters Many images/s
Language Sound Sound waves in air ms 20 Hz– Many meters Many words/min
20 kHz
Written Visual Terrestrial or aerial transport Minutes, hours, – Many km Many words/days or
days or weeks weeks
Analog Sound and Electromagnetic waves air or Seconds 3 kHz– Many km Many words/min
Visual electrical cables 300 THz Many images/s
Digital Sound and Electromagnetic waves air, Seconds 3 kHz– Many km Huge quantity of words
Visual electrical cables or optical fibers 300 THz and images/s
7
Fig. 1.8 The schematic work functioning principle of the microphone and speaker. The sound
waves hit the diaphragm which set up vibrations that are transferred to the coil. The movement of
the coil in the magnetic field induces a signal voltage that is proportional to the incident sound and
vice versa: the electrical signal induce a movement of the coil and this movement set vibrations on
the diaphragm which recreate the input sound. Left image reused with kindly permission from
http://www.holmco.de
Fig. 1.9 Nowadays analog signal transmission. At the transmitter the microphone converts the
sound wave signal into an electrical signal. The electrical signal is modulated by a carrier wave of
different frequencies and then transported by metallic electrical cables or SiO2 optical fibers, or by
air or vacuum. When the signal arrives at the receiver it is demodulated and then retransformed in
sound signal by the speaker
Fig. 1.10 Schematic work principle of the photophone by modulating the audio input signal by
light. Adapted from A.G. Bell and S. Tainter, Photophone patent 235, 496 granted 14th December
1880
1.4 Data Transmission by Analog and Digital Signals 9
and use for the first time the optical modulation. At that time this idea wasn’t more
exploited, even if Bell considered at that time, that this was one of his more
interesting inventions. The difficulties of this way of transport of the information at
long distances, arises from the fact that light propagates in air and many obstacles
parasite the signal transmission.
The oldest way to transmit the information in a binary way, via “short” and
“long” pulses, was the Morse code created in 1832 (Table 1.2). The advantage of
the Morse code lies in its simplicity and its universality. Every way that allow to
produce recognizable pulses, sound signals, electrical or optical signals, etc., can be
used to transmit an information.
The transistors by their on/off function enabled the realization of logic circuits in
the binary system (0/1) which made possible the digitization of any type of infor-
mation: sound, image, video, text computation and increasingly, the transmission of
analog signals has been replaced by the transmission of signals in digital form.
The “digitization” of the information by the binary code codification allowed a
huge development of communications in recent decades. The process of sound
transmission is schematically represented in Fig. 1.11.
Table 1.2 Alphabet and Arabic numerals in Morse code
Fig. 1.11 Analog (A) to digital (D) and digital to analog signal conversion
Today, electronics, photonics and informatics are three technical and scientific
domains with strong interconnections. The transmission of the digitized information
was first possible by using the electrical cables of the telephone network and
specific Local Area Networks (LAN Ethernet), then by using the electrical cables
for television transmission and radio electromagnetic waves networks and now by
new optical fiber networks.
In electronics the carriers information vectors are the electrons. The information
carrier vectors in photonics can be photons but also solitons, light balls, or
plasmons.
The information transmission speed by using electrical, optical cables or wireless
media is quite the same and is close to the velocity of light. The frequency of the
carrier electromagnetic wave used for the signal modulation can have different
values and allow to establish individual recognized communication channels. The
difference in transmission efficiency between data transmission by electrical and
optical cables is given by the data rate: the carried information quantity per second.
The data rate is much higher when data are transmitted by optical fiber rather by
electrical cables. In binary encoding the amount of the transported information is
measured in bits (binary digit). A bit is the smallest unit of data in the binary
encoding and has a single binary value, either 0 or 1.
The bit rate indicates the amount of information transferred on a channel wired
(by electrical cables or optical fibers) or wireless (by air, vacuum or other medium),
and is measured in bits per second b/s or bps. One Byte per second (1 B/s) cor-
responds to 8 bit/s, 1 kb/s = 1000 bit/s 1 Mb/s = 1000 kb/s, 1 Gb/s = 1000 Mb/s
and 1 Tb/s = 1000 Gb/s. Morse code data transmission rate for a skilled operator in
1844, could be estimated nowadays at 21 bit/s.
Through the human/machine interface, Internet allows today, by putting in
common the whole world knowledge to achieve the most powerful collective
inteligence.
In a very simplified view, data transmission and Internet networks could be seen
as a “fluid”, circulating in many interconnected “tubes” (channels) having different
“diameters”. The quantity of the carried fluid and the carried quantity by second
depend on the transport channel.
Table 1.3 gives the data rates for different digital transmission systems [3]. The
given values are approximative, depend on the distance between the emitter and the
receiver and evolve continuously with the progress of the technology.
Hence, today different ways to transport the digital information are employed
and different switches to transform the electrical signals into electromagnetic sig-
nals and vice versa are often employed. Figure 1.12 presents the informational data
signal transmission by electrical and optical cables. The carrier waves are in both
cases electromagnetic waves. In first case the signal is in electric form, in the second
case in optical form. To pass from electrical cables to optical cables electrical/
optical convertors are necessary.
Both electronics and photonics are based on materials science and the under-
standing of materials physics is the key point for the development of new electronic
and photonic devices.
Table 1.3 Electrical and optical wired guided and wireless unguided omnidirectional transmission data
Data carrier Digital data transmission system Wave bandwidth Bit rate Distance
vector
Guided medium—wired (twisted pair, coaxial cable, optical fiber) data transmission channel
Electrons Analog telephone (twisted pair) 3–4 kHz 33.6–56 kb/s Many km
ADSL (twisted pair coexist with phone) Hundreds of kHz 64–640 kb/s in 1.5–6.2 Mb/s out Many km
Cable Modem—CATV cable (co axial cable) Hundreds of kHz to 500 Kb/s–150 Mb/s Many km
MHz
Wide Area Networks 30–50 MHz 10–150 Gb/s Many km
(WAN) Ethernet/OC-3072-STM-1024
Local Area Networks (LAN) Ethernet IEEE 802.11 g-n 30–250 MHz 100–600 Mb/s Hundreds of meters
Photons Optical fiber using single or multiple wavelengths NIR/IR 10 Tb/s–1 Pb/s Many km
200–350 THz
Unguided medium—wireless (air, water, vacuum)—data transmission channel
Photons Wireless Wide Area Networks (WWAN)
Satellite Radio 10–50 Mb/s Many km

Microwaves
3–30 GHz
Terrestrial Radio 10–300 Mb/s Many km
100 MHz
Cell phone Radio/Microwaves 14 kb–300 Mb/s Many km
800–1900 MHz
Wireless Personal Area Networks (WPA-N)
Bluetooth Microwaves 1–5 Mb/s Many meters
2402–2480 MHz
IrDa (Infrared Data Association) Microwaves/IR Up to 100 Mb/s Many meters
Wireless LAN IEE802.11b 2.4 GHz
LIFI Visible light Up to 100 Mb/s Many meters
11
300–600 THz
Fig. 1.12 Data transmission in electrical and optical cables and the conversion of electrical
signals in optical signals and vice versa
Therefore, the (Chap. 2) present some of the basic theoretical aspects of mate-
rials physics which could help the lecturer to understand the following chapters
(Chaps. 3 and 4) of this book. Hence, Chap. 2 describes the fundamentals of band
energy formation in solids, electrons transport in solid state materials and the
photon-electron interactions in solids. As a consequence of photons-electrons
interactions, the energy of photons can be converted into electrical energy. The
devices which convert the energy of solar photons in electricity were called “solar
cells”. The work principles of solar cells derived from the basic principle of elec-
tronic devices based on p-n semiconductors junctions. Chapter 3 describe the
current status and the trends in solar cells research area. Chapter 4 is devoted to
photonics devices and trends in photonics research area (Fig. 1.13). General con-
siderations on energy and future solar energy devices are presented in Chap. 5.
Fig. 1.13 World achievements based on one main material: sand. Reprinted with the permission
from [4] Girtan Materials Today 17 (2014) 100. © 2014 Elsevier
References 13
References
1. C. Roychoudhuri, Fundamentals of Photonics (SPIE Press Book, 2008)

2. T. Yoshizawa (ed.), Handbook of Optical Metrology: Principles and Applications, 2nd edn.
(2015)
3. A. Leon-Garcia, I. Widjaja, Communication Networks, 2nd edn. (McGraw-Hill Education,
2003)
4. M. Girtan, Is photonics the new electronics? Mater. Today 17, 100 (2014)
Chapter 2
Theoretical Aspects of Materials Physics
2.1 Bands Energies Formation in Solids Crystalline

Materials
The properties of solids materials, especially the electrons dynamics are determined
by the characteristics of the crystalline lattice.
In an isolated atom the electrons orbit around the nucleus and occupied discrete
energy levels. The two levels with the highest energy can be labelled E1 and E2.
The electrons on highest energy levels can be easily delocalized from the neigh-
bourhood of the nucleus and move. When two identical atoms are brought closer
together, the quantized energy levels hybridize and split into two different levels
because of the reciprocal interaction of the two atoms. More generally, when N
atoms are moved closer, until they reach the equilibrium at inter-atomic distance d,
the energy levels split into N levels. If N is very large as is the case in a crystal,
these N levels are very close to each other so that they eventually form a continuous
energy band (see Fig. 2.1). Hence the energy levels E1 and E2 split and form two
continuous bands called as: conduction band (CB) and the valence band
(VB) separated by a forbidden band, which is not accessible for electrons, called
the «gap». The lowest energy level of the conduction band is denoted EC and the
highest energy level of the valence band is called EV so that we have the rela-
tionship Eg = EC − EV. The electrons can move in the crystal if their energy is
equal or higher to Ec, that means, when there are located (from energetic point of
view) in the conduction band. For a semiconductor material at T = 0 K all electrons
are situated in the valence band. At temperature T 6¼ 0 K the electrons can pass
from the valence band into the conduction band by thermal activation. The place
remained unoccupied in the valence band is call a “hole”. The more the temperature
increases the more the electrical conductivity of semiconductors increases. The
charge carriers (electrons and holes) can flow through the semiconductor material
(at T 6¼ 0 K) when electric, magnetic or temperature gradients are applied.

16 2 Theoretical Aspects of Materials Physics
Fig. 2.1 The formation of the band energies in a crystalline material as a function of the
inter-atomic distance
The understanding of charge transport in low dimensional systems (thin films,

quantum wires, quantum dots or organic materials) is a key point in the develop-
ment of future devices.
Due to the fact that in thin films one of the dimensions is much reduced com-
paring to the other two, often the physical properties and consequently the charge
carriers transport are different from the bulk material. Different models were pro-
posed to describe the transport phenomena in thin films.
For monocrystalline films, in the limits of semi-classical mechanics (assuming
that the thickness of films is greater than the mean free path of carriers) the most
known are the models of Fuchs [1], Sonheimer [2] and Schrieffer [3].
For polycrystalline films, also remaining in the limits of semi-classical
mechanics, the most known model to calculate the transport coefficients (electri-
cal conductivity, Seebeck coefficient, Hall coefficient, etc.) is the model of Petritz
[4]. More sophisticated theories taking into account the energy band bending at the
surface and the inhomogeneity of carrier concentration in the volume and at the
surface were developed by Anderson [5].
The transport phenomena in thin films can be understood easier by particular-
izing Boltzmann’s equation for the bulk materials in the case in which, one of the
dimensions is much reduced compared to the other two.
2.2 Charge Carriers Transport in Bulk Semiconductors
The calculus of transport coefficients in bulk materials (electrical conductivity,

Seebeck coefficient, Hall coefficient, etc.) is generally given in literature for par-
ticular cases. Here we preferred to present a general calculus method, starting from
the considerations of Kireev [6], by considering the most general case of a material
in the presence of an electric field (E 6¼ 0), a magnetic field (B 6¼ 0) and temper-
ature gradient (∇T 6¼ 0). After establishing the expression of non-equilibrium
function in the most general case, this one could be simplified, depending on the
2.2 Charge Carriers Transport in Bulk Semiconductors 17
analysed situation by combining one, two or the three parameters (E, B, ∇T) and
different transport coefficients for different type of effects can be calculated:
• Electrical conductivity (E 6¼ 0, B = 0, ∇T = 0)
• Galvanomagnetics effects (E 6¼ 0, B 6¼ 0, ∇T = 0)
• Thermoelectrics effects (E 6¼ 0, B = 0, ∇T 6¼ 0)
• Thermomagnetics effects (E = 0, B 6¼ 0, ∇T 6¼ 0).
In the absence of external actions, the carriers charge (electrons and holes) are in
thermodynamically equilibrium and their behaviour is described by Fermi-Dirac
equilibrium distribution functions, fF − D. These distribution functions are usually
noted with f0 and they depend only on temperature and charge carriers energy.
1 1
For electrons: fon ¼ EEF while for holes fop ¼ 1 fon ¼ EE ð2:1Þ
e KT þ1 e KT F þ1
If an external perturbation is applied to the solid, such as: an electric field, a

magnetic field, or temperature gradient, etc. the system (in our situation the bulk or
the thin film) will no longer be in an equilibrium state.
The charge carriers movement get a directional character and their distribution
will be given by non-equilibrium distribution functions.
In the following we will present the calculation method for the non-equilibrium
distribution function for electrons and fn and f0n will be simply denoted by f and f0,
respectively. The calculus for holes non-equilibrium distribution function is similar.
The charge carrier’s non-equilibrium distribution function is the Boltzmann
distribution function f (r, k, t) and the variation in time of this function is given with
enough precision by Boltzmann’s kinetic equation [6–11]. The function f (r, k, t)
depend on the electron position r, the wavevector k and the time t.
The electron in crystal differs from a free electron because it is submitted to
different interactions with other electrons and ions in the crystal. To resume the
influence of these electrostatic interactions the mass of electron in vacuum is
replaced by the effective mass me .
Hence the momentum of the electron is expresses by:
p ¼ h~
~ k = me~
v ð2:2Þ
where
1
~
v ¼ r~k E ð2:3Þ
h
is the velocity of electron in the crystal and E—the energy.

We consider an n-type semiconductor crystalline solid with isoenergetic
spherical surfaces in the presence of an electric field, a magnetic field and of a
temperature gradient. The Boltzmann’s kinetic equation for the stationary case, in
the relaxation time approximation, is given by [6]:
~
F f f0
~
vr~r f þ r~k f ¼ ð2:4Þ
h s
where F is the force acting on charges, s is the relaxation time, s = s(E), f the
non-equilibrium function in the presence of external fields for the electrons and f0
the equilibrium distribution function (in the absence of external fields), which is
replaced with the Boltzmann distribution for non-degenerate semiconductors and
the Fermi-Dirac distribution function for degenerate semiconductors.
In the approximation of first order it is considered that f is close to f0 and in the
two first terms of the Eq. (2.4) we can replace f by f0, and then calculate the
non-equilibrium distribution function f:
f ¼ f0 þ f1 þ f2 þ f3 þ ; ð2:5Þ
Hence, in the approximation of first order:
f ¼ f0 þ f1 ð2:6Þ
with f1:
@f0
f1 ¼ vðEÞ ~
~ k; ð2:7Þ
@E
Here, ~vðEÞ being an unknown vector function, which depends on energy. By cal-
culating ~vðEÞ we can determine f0 and then the non-equilibrium distribution
function: f.
The force F acting on charges subjected at electrical and magnetic fields (the
most complex situation) will be expressed by:

~
F ¼ e ~ v~
E þ~ B ð2:8Þ
The equilibrium distribution function of electrons for degenerate semiconductors is

given by Fermi-Dirac distribution function:
1
f0 ¼ EEF ð2:9Þ
e KT þ1
and for non-degenerate semiconductors, by Boltzmann distribution function:
fo ¼ eð Þ
EEF
KT ð2:10Þ
Taking into account the relations from (2.5) to (2.8), the relation (2.4) becomes:
e e f1
vr~r f0 ~
~ Er~k f0 ~ v~
B r~k f ¼ ð2:11Þ
h h sn
and more
e e 1 @f0
vr~r f0 ~
~ Er~k f0 ~ v ~
B r~k f ¼ vðEÞ ~
~ k ð2:12Þ
h h sn @E
We consider the case of non-degenerate semiconductors and we replace f0 with

Boltzmann distribution function (2.10).
Calculating each term on the left member of the Eq. (2.12) in the hypothesis that
the semiconductors are monocrystalline, with spherical isoenergetic surfaces, we
obtain:

@f0 EF E h~
k @f0 EF E
~vr~r f0 ¼ ~
v r~r T r~r EF ¼ r~r T r~r EF ð2:13Þ
@E T mn @E T
e e @f o h2 k
~ Er~k fo ¼ ~E ; ð2:14Þ
h h @E mn
mn being the effective mass of the electron, in the crystal,

e e e e
v~
~ B r~k f ¼ ~ v ~
B r~k ðf0 þ f1 Þ ¼ ~ v~
B r~k f0 ~ v ~
B r~k f1
h h h
h
ð2:15Þ
It is easy to show that r~k f0 ¼ 0 and the relation (2.15) becomes:
e e
v~
~ B r~k f ¼ ~ v ~
B r~k f1 ð2:16Þ
h h
Considering the expression (2.7) for f1 we deduce:
@f0 e e @f0
r~k f1 ¼ ~
vðEÞ and finally ~ v ~
B r~k f ¼ ~ v ~
B ~
vðEÞ ð2:17Þ
@E h h @E
Now introducing (2.13), (2.14) and (2.17) into (2.12) we obtain:

2
h~
k @f0 EF E e ~ @f0 hk e ~
@f0
r~r T r~ E
r F E þ ~v B ~
vðEÞ
mn @E T h @E mn
h @E

@f0
vðEÞ ~
1
¼ ~ k
sn @E
ð2:18Þ
and after simplification:

h~
k EF E ehk e
r~r T r~r EF ~ v~ vðEÞ ~
1

Eþ ~ B ~
vðEÞ ¼ ~ k ð2:19Þ
mn T mn h sn
Here
k
h
~v ~
B ~ v ~
vðEÞ ¼ ~ vðEÞ ¼ ~
B ~ B ~
vðEÞ ð2:20Þ
mn
So rel. (2.19) becomes:

h EF E eh ~ e ~ 1

r~r T r~r F Eþ
E
B ~
vðEÞ ¼ ~ vðEÞ ð2:21Þ
mn T mn mn sn
and we obtain the vector equation:

sn h EF E ~ e ~
~
vðEÞ ¼ r~r T r~r E F e E þ B ~
vðEÞ ð2:22Þ
mn T
h
The equation is of type: ~ a þ~

v ¼~ b ~
v and the solution is:

aþ ~
~ a þ~
b ~ b ~b ~
a
~
v¼ ð2:23Þ
1 þ b2
This means that we can find the final solution ~

vðEÞ and determine the
non-equilibrium function:
@f0
f ¼ f0 vðEÞ ~
~ k ð2:24Þ
@E
The problem could be reduced now at different particular cases in order to cal-
culate different needed transport coefficients.
The Electrical Conductivity in the Relaxation Time Approximation for Bulk
Materials
Considering now that we apply only an electric field ~
E¼~EðEx ; 0; 0Þ, the tem-
perature gradient and the magnetic field being zero, the expression of ~ vðEÞ
becomes:
sn h ~
~
vðEÞ ¼ e E ð2:25Þ
mn
The electron current density is given by:

Z
~jn ¼ e vn f ð~
~ kÞdsk ð2:26Þ
4p3
V ðk Þ
where dsk = dkxdkydkz is the elementary volume in the space k.

As we chose ~
E¼~ EðEx ; 0; 0Þ, we have only the component of the vector~jn in the
direction x:
Z
e @f0 ~
jnx ¼ 3 vnx f0 ~
vðEÞ k dsk
4p @E
V ðk Þ
Z
e @f0 sn
h ~
¼ 3 vnx f0 þ e ~ E k dsk ð2:27Þ
4p @E mn
V ðk Þ
Taking into account that f0 is an even function, vnx an odd function and V
(k) implies an integration between symmetric limits (Brillouin zone) the first term in
the expression (2.27) is zero and jnx could be expressed as:
Z
e @f0 sn h ~
jnx ¼ 3 vnx e Ex kx dsk ð2:28Þ
4p @E mn
V ðk Þ
By changing the variable k to E (the energy) we have:

12
2mn mn 2mn 1=2 1=2
k¼ 1=2
E and dsk ¼ 4p 2 E dE ð2:29Þ
h2 h
h2
By calculus and taking into account that:
Z1 1
m axn 1 C mþ pffiffiffi
IðaÞ ¼ x e ¼ n
and Cðn þ 1Þ ¼ nCðnÞ; Cð1Þ ¼ 1; Cð1=2Þ ¼ p
n am þn 1
0
ð2:30Þ
we can expresses jnx as:
R1
3
sn ðEÞ @f
@E E dE
0 2
e\s [ 0
jnx ¼ enln Ex ; with ln ¼ and h si ¼ R1
@f0 3 ð2:31Þ
mn
@E E2 dE
0
Here n is the charge carriers concentration (electrons), ln—electrons mobil-

ity, <s> the mean relaxation time.
To calculate the mean values hsi or s2 precisely, it is necessary to express the
relaxation time s as function of energy s = s(E). This function depends on the
nature of scattering mechanism dominating in the studied sample.
Accepting that, this dependence is given by:
sn ¼ s0 Ep ð2:32Þ
where, s0 is a parameter depending on material nature and sometimes on temper-

ature, and the exponent p characterizes the scattering mechanism nature (p = −3/2
scattering on ionized impurities, p = 1/2 scattering on longitudinal acoustics pho-
nons [6]).
Taking into account the relations (2.31), (2.32), and the distribution function we
can express the mean relaxation time as:
R1 f0 3 R1
E E 3
s0 Ep KT E2 dE s0 Ep eKT eKT E2 dE
F
1 5=2
0 0 Cð5=2 pÞ
h si ¼ R1 ¼ R1
E EF 3 ¼ s0 5=2p KT
3 1 Cð5=2Þ
KT
f0
E dE
2 e KT eKT E2 dE KT
0 0
ð2:33Þ
and finally
Cð5=2 pÞ
\s [ ¼ s0 ðKTÞp ð2:34Þ
Cð5=2Þ
Hence, the electrons mobility for non-degenerate semiconductors can be expressed

as:
R1
3
sn ðEÞ @f
@E E dE
0 2
e\s [ e e Cð5=2 pÞ
l¼ ¼ 0
R1
@f0 3 ¼ s0 ðKTÞp ð2:35Þ
mn mn mn Cð5=2Þ
@E E2 dE
0
According to (2.29), the electrical conductivity for n-type non-degenerate

semiconductors is expressed by the well know formula:
r ¼ enl ð2:36Þ
The different charge transport mechanisms are comprised into the expression of the
mobility which depends on the different type of scattering processes.
In a similar mode one could calculate other coefficients, e.g., Hall coefficient,
Seebeck coefficient, etc.
Hall Coefficient in the Relaxation Time Approximation

The calculus of Hall coefficient, for electrons in a n-type non degenerate semi-
conductor conducts to [6, 7]:
r
Rn ¼ ð2:37Þ
ne
For a p type non-degenerate semiconductor, the Hall coefficient of holes is:

r
Rp ¼ ð2:38Þ
pe
and for mixed conduction:
r p b2 n le
Rm ¼ ; where b ¼ ð2:39Þ
jej ðp þ nbÞ2 lh
r is called Hall factor and for low magnetic fields it could be expressed by:
2
s
r¼ ð2:40Þ
hsi2
In the hypothesis s ¼ s0 E p using the formulae of average value we deduce:

C 52 2p C 52
r¼ 2 ð2:41Þ
C 52 p
Seebeck Coefficient in the Relaxation Time Approximation

The calculus for Seebeck coefficient conducts to [6, 7]:

1 \sE [
aðTÞ ¼ EF ð2:42Þ
eT \s [
and in the assumption s ¼ s0 Ep
R1 f0 3 R1
E E 3
s0 Ep E KT s0 E1p eKT eKT E2 dE
F
E2 dE
0 0
hsEi ¼ R1 ¼ R1
3
E EF
eKT eKT E2 dE
3
KT
f0
E dE
2
0 0
1p Cð7=2 pÞ
¼ s0 ðKTÞ ð2:43Þ
Cð5=2Þ
and taking into account the expression of <s> from (2.34) results as:
2 3
1p Cð7=2pÞ
1 4s0 ðKTÞ Cð5=2Þ 5 1 5
aðTÞ ¼ EF ¼ KT p EF ð2:44Þ
eT s0 ðKTÞp Cð5=2pÞ eT 2
Cð5=2Þ
2.3 Transport Coefficients in Thin Films. Semi-classical

Theory
In addition to the carriers scattering mechanisms presented in the bulk single

crystals materials, in thin films, due to the large diminution of one of the three
dimensions and due to the fact that films are usually polycrystalline, we should
consider also the scattering on the surfaces and the scattering at the limits of grain
boundaries.
For thin films the scattering mechanisms inside the crystallites corresponds to the
scattering mechanisms in monocrystalline bulk materials, and that’s why are
designed as “bulk scattering mechanisms”.
A direct consequence to the fact that the thickness is much reduced and becomes
comparable to the mean free path is that the non-equilibrium distribution function
and obviously the transport coefficients will depend on the films thickness. We call
this “dimensional effect”.
The dimensional effect for the electrical conductivity could be explained equally
on the basis of Boltzmann transport equation, the difference comparing to bulk
analysis consists in the dependence of non-equilibrium distribution function on the
position variable.
Thin Films Electrical Conductivity
Considering the geometry of the thin films in the coordinates (x, y, z) as is
presented in Fig. 2.2 the kinetic equation of Boltzmann for homogenous and
monocrystalline thin films in the absence of magnetic fields is given by [7, 12]:
Fig. 2.2 We consider that the thin film has infinite surface with the inferior surface in the plane
z = 0 and the superior surface in the plane z = d. The electric field E (E, 0, 0) is oriented along the
surfaces planes
2.3 Transport Coefficients in Thin Films … 25

@f ~
k; z e @f ~
k; z f f0
vz ~ E ¼ ð2:45Þ
@z h @kx sn
The distribution function on the spatial coordinates will depend only on z variable
and could be expressed by:
f ¼ f0 E þ f1 ðv; zÞ ð2:46Þ
The electrical conductivity is obtained in a similar way as in the case of bulk

material, with the difference that in this situation due to the dependence of current
density jx on the position variable z, the current density will be expressed as an
average of jx values along the direction z [7, 12, 13]:
Zd Zd Z
1 1 e
jn ¼ jx ðzÞdz ¼ 3 vx f1 ð~
v; zÞdsk dz ¼ rn E ð2:47Þ
d d 4p
0 0
rn, represents the electrical conductivity of the thin film considered as semicon-
ductor of n type.
The scattering mechanisms on the surface were characterized by a parameter
p call scattering factor, having the values 1 or 0 for the limit situations: (a) elastic
scattering; (b) inelastic scattering.
The electrical conductivity r in thin films is determined by calculus in con-
nection with the value corresponding to bulk material r0, for different situations,
such as degenerate and non-degenerated semiconductors, thick and thin films.
For degenerated semiconductors [7, 12]:
c
r¼ r0 ð2:48Þ
uðcÞ
u (c) being a function depending on film thickness and the free mean path of charge
carriers:
Z1
1 1 3ð1 pÞ 1 1 1 eca
¼ da ð2:49Þ
/ðcÞ c 2c2 a3 a5 1 peca
1
a = 1/cosh is the integration variable, h the angle between the direction of velocity
vector and Oz axis, c = d/l, is the ratio between the thickness of the film d, and the
free mean path, l.
This relation could be simplified for some limit cases: very thin films (c 1),
very thick films (c 1), and for pure diffuse scattering (p = 0) or pure elastic
scattering (p = 1) [1–3, 13].
r 3 1þp 1
¼ c ln ; c 1; ð2:50Þ
r0 4 1 p c
r 3
¼ 1 ð1 pÞ; c 1: ð2:51Þ
r0 8c
For Non-degenerated Semiconductors [12]
r
¼ 1 ð1 pÞð2=cÞ þ ð1 2pÞð2=cÞC1 ð2=cÞ þ ð2p=cÞC1 ð1=cÞ ð2:52Þ
r0
with C1(1/c) and C1(2/c) given by:
Z1 h i
C1 ðc=cÞ ¼ exp e ðc=cÞðpeÞ1=2 de; c ¼ 1 and c ¼ 2 respectively: ð2:53Þ
0
The presented formulas correspond to the Fuchs-Sondheimer and Schrieffer theo-

ries [1–3] for n-type semiconducting thin films, in the hypothesis of spherical
isoenergetic surfaces and flat bands (the concentration of carrier charge is the same
at the surface as in the bulk). The case of ellipsoidal isoenergetic surfaces was
studied by Ham and Mattis [14].
As, in general, the concentration on the surface of films is different from that in
the volume due to the existence of donors or acceptors states at the semiconductor
surface, different authors elaborated later, more sophisticated theories [5, 15, 16],
taking into account the energy band bending at the surface (Anderson model).
Another scattering mechanism, specific to thin films is the scattering on grain
boundaries. This problem is rather complicated due to the fact that it is difficult to
control and reproduce films having exactly the same polycrystalline morphology.
To explain the electrical and optical properties of polycrystalline films various
models were proposed (Volger [17], Petritz [4], Seto [18], Berger and Mankarious
[19]).
Most of analysis and simulating techniques are based on the consideration that
the boundaries between crystallites presented a spatial charge, which corresponds in
terms of energy bands to a band bending and existence of potentials barriers.
One of the most employed models is the model of Petritz [4] in which it is
considered that the polycrystalline semiconductor films are constituted by
homogenous separated (structural and electrical) domains with very low electrical
resistivities q1 (corresponding to the crystalline grains) and very high resistivities
q2, (corresponding to the boundary grains), connected in series.
The thickness of high resistivity domains is neglected, as compared with the
thickness of low resistivity domains. For a big number of grains, the characteristic
parameters are described by mean values.
2.3 Transport Coefficients in Thin Films … 27
Petritz deduced the electrical conductivity of a polycrystalline film as following

[4]:
rb ¼ el1 n exp( q/b =KT) ð2:54Þ
with l1 the mobility inside the crystalline grains, n the concentration of charge
carriers and /b the barrier height.
Since q2 q1 Petritz consider that the exponential factor is not due to the
concentration changes but to carriers mobility changes.
So that all charge carriers participate to the conduction but with a reduced
mobility due to the presence of barriers:
lg ¼ l1 exp( q/b =KT) ð2:55Þ
The barrier height at the grain boundaries is determined by the concentration of

charge carrier in grains and grain boundaries.
q/b = KT ln(n1 =n2 Þ ð2:56Þ
where n1 and n2 are the concentrations in the grain and grain boundary,
respectively.
Berger and then Mankarious [18] extended Petritz model. Mankarious and
co-workers made the observation that the electrical conductivity in a polycrystalline
thin film could be expressed in a more general way as:
rg expðEa =KT) ð2:57Þ
here Ea is the thermal activation energy.

For degenerated semiconductors, the effect of potential barriers at the grain
boundaries is not very significant [19], furthermore it should be mentioned that for
strong degeneration, the grain boundaries scattering does not depend on tempera-
ture and it is not possible to distinguish it from the scattering on the ionized
impurities.
Besides, if the mean free path of carriers is 4–5 times smaller than the size of
crystallites, the boundaries inter-crystallite scattering mechanisms can be consid-
ered negligible.
Hall Coefficient in Thin Films
The calculus of the other kinetics coefficients is even more complicated. From
Sondheimer model [2] the Hall coefficient R, is given by:
41 p 1
Rfilm ¼ Rbulk
2 ð2:58Þ
3 1þp
c ln 1c
p being the scattering factor, and c = d/l, the ratio between the thickness of the film
d, and the free mean path, l and c 1.
Seebeck Coefficient in Thin Films
The relations for Seebeck coefficient in thin films, considered as monocrystalline
are expressed as [2]:

cu0 ðcÞ U
afilm ¼ abulk 1 0 ; ð2:59Þ
u ð cÞ 1 þ U
with
(
0 duðcÞ EF @c 1 3ð1pÞ
8c ; c1
u ð cÞ ¼ ;U ¼ ; /ðcÞ ¼ 3 1þp
ð2:60Þ
dc c @E 4 1p c ln 1c c1
p being the scattering factor, and c = d/l, the ratio between the thickness of the
film—d, and the free mean path—l, EF is the Fermi energy.
These mechanisms explain the behaviour of charge carriers when crosses the
solid semiconductor material under the action of different fields.
2.4 Quantum Effects in Charge Transport. Quantum

Well, Quantum Wires, Quantum Dots
The development of molecular beam epitaxy since the late 1960s, made possible to
grow ultrathin layers ( 20 Å) of different materials with atomically sharp inter-
faces. On such small length scales the semi-classical distribution function is no
longer a valid concept, due to the uncertainty relation between r and k.
To analyse and design devices on a sub 100 nm scale it will be necessary to go
beyond the Boltzmann equation and develop simulation techniques based on
quantum kinetic equations. The development of an appropriate kinetic equation is
an active topic of theoretical research [20]. The last twenty years have seen the
emergence of new research areas, such as: nanostructure physics and
nano-electronics.
Quantum effects in electron transport can broadly be divided into two categories:
those involving devices whose transverse dimensions are either much longer or
either much shorter than the phase coherence length.
For the devices belonging to the first category, the sub-band energies are nearly
continuous and one can describe electron transport in terms of plane waves. For
those belonging to the second category it is more appropriate to view transport in
terms of discrete waveguide modes [20].
We define as quantum well a zone in which the electrons are situated in a
one-dimensional potential well. We suppose that the thickness “a” of the layer
2.4 Quantum Effects in Charge Transport … 29
Fig. 2.3 Quantum well, quantum wires, quantum dots
which represent the quantum wall is large enough (a > 20 Å), as the layer keeps the
characteristic of macroscopic crystal and small enough (a < 400 Å) to suppose that
the electron crosses the wall without suffering collisions (a < the mean free path).
Hence the electrons are confined (2D electronic gas) in this zone, which is a
uni-dimensional potential well.
In a quantum well structure, the electrons confinement occurs perpendicular to
the interface (Fig. 2.3a).
The structures in which the electrons are confined along two directions
(bi-dimensional potential well) and along the three spatial directions
(tri-dimensional potential well) were called quantum wires (Fig. 2.3b) and
respectively quantum dots (Fig. 2.3c). In these structures we consider that we have
a 1D and respectively 0D electronic gas.
The simplest way to create a quantum well is by designing hetero-structures or
MOS-type structures (Fig. 2.4).
After putting in contact the metal and the semiconductor through an oxide
interface, an electron transfer occurs since the two Fermi levels become equal. This
conducts to a bending of semiconductor energy bands, and consequently to a
potential barrier.
From Fig. 2.4c. one can remark that such a structure in terms of quantum
mechanics could be approximated with a triangular one-dimensional quantum well.
(a) (b) (c)
Fig. 2.4 a MOS structure b Energy band diagram of metal and semiconductor before contact
c Energy band diagram of metal and semiconductor after contact
The wave function and the energy associated to the electrons could be deter-
mined using the Schrödinger equation [21], in the one-dimensional case.

h2 d 2
2 þ VðxÞ uðxÞ ¼ EuðxÞ ð2:61Þ
2m dx
V(x) is the electric potential function, which describes the barrier height as a
function of the coordinate x.
The equation of Schrödinger for uni-dimensional problems is generally quite
easy to solve, much more complicated being the equation of Schrödinger in three
dimensions (the case of quantum dots):

h2
D þ Vð~
rÞ uð~
rÞ ¼ Euð~
rÞ ð2:62Þ
2m
By creating multilayer structures of very thin films we obtain complex devices with
multiple quantum wells called superlattices.
2.5 Linear Conjugated Systems. Organic Semiconductors.

Charge Transport in Organic Materials
A conjugated system is defined as a system presenting a simple-double carbon

chemical bonding alternance.
We can distinguish two categories of linear conjugated systems: small molecules
and polymers. Some examples of such conjugated system are given in Fig. 2.5.
Despite the saturated polymers which are insulators and less interesting from the
point of view of electronics materials, in conjugated polymers, the chemical
bonding leads to one unpaired electron (the p electron per carbon atom) in a
delocalized state, with the results that such polymers can exhibit semiconductor or
even metallic properties.
The electronic structure in conducting polymers is determined by the chain
symmetry and the electronic delocalization provides a “highway” (as Heeger calls
it) for charge mobility along the backbone of the polymer chain [22].
To understand in a simple way the electronic band structure formation in organic
semiconductors, we can start from the example of polyacetylene (–CH)n Fig. 2.6.
At molecular level the p electrons could be ejected from the Highest Occupied
Molecular Orbital (HOMO) level (p) or captured on the Lowest Unoccupied
Molecular Orbital (LUMO) level (p*). With the increase of molecular length, by
analogy with inorganic crystals, the energetic levels split and the degeneration
increases with the number of atoms, conducting to continuous energetic bands for
an infinite chain (Fig. 2.7).
2.5 Linear Conjugated Systems. Organic Semiconductors … 31
Fig. 2.5 Examples of a few conjugated polymers, note the bond-alternated structure
Fig. 2.6 Polyacetylene chain
Fig. 2.7 Energy diagram

evolution for molecular
orbitals with the increase of
conjugation, Ip is the
ionization energy, Ae the
electron affinity and Eg the
gap of the material
Even if the terms HOMO and LUMO characterize an isolated molecule, they
were extended to the solid phase and are the equivalents of the maximum of
Valence Band (VB) and minimum of Conduction Band (CB) in the physics of
semiconductor materials.
By the relative positions of HOMO and LUMO of materials putted in contact it

is possible to define them as Donor or Acceptor, but this is not an intrinsic char-
acteristic of the material.
The band gap is the difference between these two positions in the energetic
diagram and since there are no partially filled bands, conjugated polymers are
typically semiconductors. Because Eg depends upon the molecular structure of the
repeat unit, this gave rise to the idea that the energy gap could be controlled by
design at molecular level.
In the assumption of electron gas model, the problem of p electron travelling
along the molecular chain, is equivalent, from quantum point of view, to the motion
of an electron in a periodic potential (Fig. 2.8).
Hence the Schrödinger equation in the one-dimensional case for the motion of
electron in a periodic potential can be solved. This potential can be approximated
with a rectangular potential, as shown in Fig. 2.9.
The equation to solve is:
8h i
>
< 2mh2 d 2
dx2 þ VðxÞ uðxÞ ¼ EuðxÞ
ð2:63Þ
> 0; x 2 ð0; aÞ
: with VðxÞ ¼
V0 ; x 2 ða; a þ bÞ
Fig. 2.8 Approximate potential curve V(x) created by the atoms of polymer chain
Fig. 2.9 Simplified periodic potential (as in crystals)

2.5 Linear Conjugated Systems. Organic Semiconductors … 33
From solid state physics, we remember that this situation corresponds exactly to the
Kroning-Penny model, which lead by calculus to the explanation of energy struc-
ture bands formation in crystals.
In this simplest way, on the basis of quantum mechanics and condensed matter
physics, the formation of bands energy in organic semiconductors, can be
explained. However, the discovery of nonlinear excitations (solitons, polarons and
bi-polarons) indicated that the physics of organic materials is much more complex
and entirely new concepts were developed in the last twenty years.
A soliton type excitation (or radical) results from the separation of the chain into
two domains which differ by the simple-double bonding alternance. In the presence
of an acceptor or donor electrons, the soliton (neutral defect) is positive or negative
charged and becomes a positive or negative mobile polaron (charge defect)
responsible of the conduction along the chain [22].
The studies on polyacetylene contributed to the development of important
models concerning the non-linear excitations such as: soliton, polaron, bipolaron.
The first model was the SSH model (Su, Schrieffer, Heeger). This model is built,
assuming the alternance single-double bonding along the polymer chain, by con-
sidering that the two configurationally equivalent chains of polyacetylene
(Fig. 2.10) are weak-coupled (quasi one-dimensional character). The formation of
soliton excitations is studied along an infinite chain and in the one-electron
approximation. The band structure is calculated by expressing the total Hamiltonian
of the system.
The electrical conduction and charge transport in organic semiconductors need
the creation of free charge carriers. A conjugated system could become conductive
by doping.
The electrical conductivity results from the existence of charge carriers (trough
doping) and from the ability of those charge carriers to move along the p bonded
“highway”. Thus doped conjugated systems (polymers) are good conductors for
two reasons [22]:
Fig. 2.10 a The two configurationally equivalent structures, from energetic point of view in
polyacetylene b Band structure for a dimerised polyacetylene chain calculated from the SSH
Hamiltonian
(i) Doping introduce carriers into the electronic structure. Since every repeat unit
is a potential redox site, conjugated systems can be doped n-type (reduced,
creation of a negative charge) or p-type (oxidized, creation of a positive
charge) to a relatively high density of charge carriers.
(ii) The attraction of an electron in one repeat unit to the nuclei in the neigh-
bouring units, leads to the carrier delocalization along the polymer chain and
to the increase of charge carrier mobility which is extended into three
dimensions through inter-chain electron transfer. However, disorder limits the
carrier mobility.
Mobile charged defects in lightly doped one-dimensional chains and
disorder-induced charge localization in heavily doped systems have attracted much
attention. The knowledge of the electrical conduction process in organic solids is of
great importance because it conducts to the explanation of organic electronics and
optoelectronic devices operation. On the other hand, the understanding of the
complex physical processes in conduction mechanisms, leads to the understanding
of charge and energy transfer in biological systems.
A common problem in charge transport in organic materials is a lack of detailed
knowledge of the organisation of the material. Today we know, both theoretically
and experimentally, that for disordered electronic systems, even in the weak dis-
order limit, the Boltzmann transport equation for metals could not be applied.
Instead new concepts which treated the disorder from the beginning were
introduced.
A unified theory of the electrical conduction in conducting polymers and organic
materials in general, doesn’t exist yet.
Transport models for three-dimensional amorphous semiconductors have been
used often to describe the charge delocalization phenomena in conducting polymers
despite fundamentals differences. Covalent bonding along polymers chains and
weak bonding between them result in a quasi-one dimensional morphology which
has an important role in the charge delocalization of these systems. A central issue
is whether the metallic states are predominately one dimensional (1D) or three
dimensional (3D). For example the 1D random dimmer model has been proposed to
explain charge delocalization [23]. On the other hand, both theoretical and exper-
imental studies emphasized the importance of inter-chain interaction. Another
controversy is whether charge transport is due to variable range hopping
(VRH) with emphasis on inter-chain hopping in disordered regions or charge
energy-limited tunnelling based on granular metallic model. More details on the
different charge transport mechanism proposed for describing organic solids
behaviour are given in [22, 24, 25].
All these controversial issues originate from the complex morphology associated
with organic materials.
2.6 Photon—Electron Interactions 35
2.6 Photon—Electron Interactions
• Plasmons. Absorption of light in a metallic material with a dielectric interface.

Surface plasmon polaritons.
• Absorption of light in semiconductor materials.
• Absorption of light in a semiconductor material with a metallic interface.
• Absorption of light in organic semiconductors
• Plasmons. Absorption of light in a metallic material with a dielectric
interface. Surface plasmon polaritons.
The energy of photons is given by: Eph = hm, where h = 6.62606957 10−34 Js
is the Planck constant and m is the photon frequency. Photons (electromagnetic
radiation) can interact with the matter and transfer their energy in different ways.
If the frequency of the electromagnetic radiation corresponds to the microwave
domain (300 MHz–300 GHz) the interaction with the matter conducts to molecular
rotations and torsion, if the radiation frequency is in the infrared domain
(3–300 THz) it conducts to molecular vibrations. For frequencies in the visible and
ultraviolet domain (300 THz–3 PHz) the interaction of photons with atoms conduct
to an increase of the electrons energies, hence the photon energy is transferred to an
electron, and the electron moves to a higher energy level. For higher energies of
photons, corresponding to X ray domain, (300 PHz–30 EHz) the electrons can even
be extracted from the atoms (photoionization and Compton scattering).
A crystalline solid can be imagined as a “plasma” of electrons and ions in which
the electrons can move (oscillate) in a collective organized way with respect to the
fixed positive ions.
The plasma oscillations of the free electron gas density can be quantized and a
particle can be associated to these waves.
The particle associated to the free electron density oscillations with respect to the
fixed positive ions in a metal or semiconductor is called plasmon.
Surface plasmons (SPs) are those plasmons that are confined in surfaces for
example at the interface between a metal and a dielectric, such as a metal sheet in
air. SPs have lower energy than bulk (or volume) plasmons which quantise the
longitudinal electron oscillations about positive ion cores within the bulk of an
electron gas (or plasma).
In a bulk material (metal or semiconductor) the plasma oscillations cannot be
produced by usual thermal excitations, that is why at normal temperatures plasmons
are in their fundamental state and do not participate at the most electronic processes
and their contribution can be neglected.
The plasmons can be excited by passing the electrons with high energies through
thin metallic films or by interactions with light in the visible range of the electro-
magnetic spectrum.
Fig. 2.11 Absorption of light in a metallic material with a dielectric interface. a Schematic
representation of a SPP as a collective excitation propagating along a metal—dielectric interface.
b The perpendicular electromagnetic field intensity Ez decays exponentially with the distance
away from the interface with a characteristic length dd in the dielectric and dm in the metal.
Adapted with permission from Benson [26], © 2011 Macmillan Publishers Limited, part of
Springer Nature
Figure 2.11a gives the schematic representation of an electron density wave

propagating along a metal—dielectric interface. The dependence of the electro-
magnetic field intensity on the distance away from the interface is shown in
Fig. 2.11b.
These waves can be excited very efficiently with light in the visible range. The
interaction (coupling) of a surface plasmon with a photon give rise to a new particle
called “Surface Plasmon Polariton” (SSP).
• Absorption of light in semiconductor materials.
– Intrinsic Absorption (fundamental). Optical Transition between Bands.
– Factors Determining the Shift of Fundamental Absorption Edge.
– Extrinsic Absorption.
– Free Carriers Absorption.
For the absorption of electromagnetic radiation in semiconductors, generally,
two mechanisms are responsible. The first one, referring to the excitation of elec-
trons from Valence Band (VB) to Conduction Band (CB), or in an electron-hole
bounded state (exciton), is defined as an inter-band absorption process and it is
treated in quantum physics manner. The second one consisting in the acceleration
of free carriers by the oscillating electrical field, is referred to as absorption on free
carriers and could be discussed in the limits of classical electrodynamics [27–31]. In
the domain of low wavelength the strong absorption is determined by the Band to
Band (B-B) transitions and in the domain of large wavelengths the low transmission
is determined by the high reflection due to free carriers [32]. Analysing the
transmission spectra in the domain of fundamental absorption one can get infor-
mation concerning the optical band gap and the study of reflection and transmission
Fig. 2.12 Semiconductor optical window
spectra in the IR range may conduct to an important series of information such as:
the superior limits of the optical window, the value of plasma frequency, etc.
The transparency domain of a semiconductor (“the optical window”) is com-
prised between the edge of fundamental absorption corresponding to the kg
(gap) wavelength and kp the wavelength of conduction electron plasma oscillations
(Fig. 2.12).
• Intrinsic Absorption (fundamental). Optical Transition between Bands.
In an intrinsic semiconductor, photons with energies below the gap cannot excite an
electron-hole pair and their energy is lost (Fig. 2.13a). If the energy of photon is
equal or higher that the bandgap energy Eg, the photon absorption determines a
transition of the electron from valence band to conduction band (intrinsic transi-
tion). In the case in which the photons energy exceeds the gap, the excess of energy
is lost in a rapid thermalization process.
Fig. 2.13 Energy-band diagrams showing the light-absorption mechanism in a bulk

semiconductor
The transitions from conduction band to valence band can be direct or indirect
ones. In a direct intrinsic transition the wave vector k of charge carriers remains
unchanged after the transition between bands. The indirect transitions occur when
the minimum of conduction band and the maximum of valence band are not aligned
and the transitions of charge carriers occur with the change of k vector value. Both
direct and indirect transitions could be allowed or forbidden. The calculus of
transition probabilities is strictly of quantum nature.
The minimal energy (hc/kg) of absorbed photons which conducts to intrinsic
transitions is called fundamental absorption edge (optical band gap). From the
spectral dependence of absorption coefficient near the edge of fundamental
absorption one can obtain information concerning the nature of transitions involved
in the absorption process.
• Factors Determining the Shift of Fundamental Absorption Edge.
In a n-type degenerate semiconductor (high doped semiconductor), the electrons
occupying the inferior positions into the conduction band block the transitions B-B
(Band to Band) and lead to a shift of the fundamental absorption edge to higher
energies. The phenomenon is known as Burstein—Moss effect [33, 34].
Eg ¼ Ego þ DEBM
g ð2:64Þ
The variation of the band gap due to the Burstein—Moss effect is given by:
h2 2 2=3
DEgBM ¼ 3p n ð2:65Þ
2meh
where n is the concentration of free electrons and meh is the reduced effective mass
of electrons and holes:
1 1 1
¼ þ ð2:66Þ
meh mh me
mh being the holes effective mass and me the electrons effective mass.
On the other hand in addition to this, the decrease of band gap could occur due to
the formation of a delocalized states band (Mott) at the bottom of conduction band
[29, 35].
Furthermore, the randomised distribution of the impurities into the crystal lattice,
has as a consequence the presence of a band tail (Urbach); the different interactions
which influenced the mean occupation time of electronic states upon the Fermi level
conduct also to the extension of the fundamental absorption edge.
Excepting the Burstein-Moss shift, which is quite easy to estimate for a parabolic
conduction band, the influence of the others effects is difficult to be estimated, and
the calculus could become very complex.
• Extrinsic Absorption.
The extrinsic absorption occurs in doped semiconductors (extrinsic semiconduc-
tors) when the absorption of photons with energies lower than the band gap con-
ducts to the displacement of an electron from the valence band to a local impurity
level, or from a local impurity level to the conduction band.
• Free Carriers Absorption.
When the energy of incident photons is not sufficiently high to determine
Band-Band transitions or Band-Local Level transitions, we talk about free carriers
absorption. The optical phenomena corresponding to this wavelength domain could
be understood onto Drude theory basis, for free electrons into metals [36].
Low frequency electromagnetic radiations incidents onto semiconductor surface
interact with the free electrons. A part of the radiation could be reflected, other part
absorbed and the rest is transmitted. In Drude theory it is demonstrated that the
radiations having frequencies lower than the frequency corresponding to the elec-
tron plasma (k > kp) are strongly reflected and the transmission is reduced to zero.
The frequency of plasma oscillations is given by [36]:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2pc ne2
xp ¼ 2p fp ¼ ¼ ð2:67Þ
kp e0 e1 me
e0, e∞ are the dielectrics constants for vacuum and for the material at high fre-
quencies respectively, e—the electron charge, n—electrons concentration.
This frequency defines the limit at which the electrons become unable to stop the
electric field of the incident electromagnetic radiations and the materials become
transparent for the radiations having frequencies higher than xp.
The “transparency domain” in Drude theory corresponds to the condition xs
xps 1, where s is the relaxation time, the condition xps > > xs 1 corre-
sponds to the “reflection domain” and 1 > xs > 0 corresponds to absorption
domain (transparency zero).
Hence one can remark that the edges of semiconductors optical window, kg and
kp, are depending on the concentration of free carriers.
The increase of optical window width in the sense of kp moving to larger values
is done by the decreasing of free carrier concentration. For a fixed small carrier
concentration, the condition of transparency xps 1, (as xp is fixed due to n
fixed) suppose an increase of the mobility ðl ¼ e s me Þ:
• Absorption of light in a semiconductor material with a metallic interface.
In an intrinsic semiconductor, photons with energies lower than the gap energy
can’t be absorbed (Fig. 2.14a). However recent studies showed that if the semi-
conductor interfaced with a metal, the excitation of surface plasmons in the metal
generates short-lived highly energetic carriers that can be injected into the con-
duction band of a semiconductor [37].
Fig. 2.14 Energy—band diagrams comparing the light absorption mechanism in a bulk
semiconductor and a semiconductor interfaced with a metal. Adapted from Chalabi and
Brongersma [37], © 2013 Macmillan Publishers Limited
Hence when the metal’s Fermi level EF is above the valence band of the
semiconductor, some sub-bandgap photons can photogenerate hot electrons that are
sufficiently energetic to be injected into the semiconductor’s conduction band hence
even photons with energies lower than the band gap energy can be harvested
(Fig. 2.14b).
• Absorption of light in organic semiconductors.
In organic semiconductors the nature of bonding is fundamentally different from
inorganic semiconductors. Organic molecular crystals are Van des Waals-bonded
implying a considerably weaker intermolecular bonding compared to the covalent
bonds of inorganic semiconductors. Consequently the delocalization of electronic
wave functions among neighbouring molecules is much weaker. The situation in
polymers is somewhat different, since the morphology of polymer chain can lead to
improved mechanical properties. However the electron interaction between adjacent
chains is usually also quite weak in this class of materials [38].
Owing to weak electronic delocalization, the optical absorption spectra of
organic molecular solids are very similar to the spectra in the gas phase or in
solution. Nevertheless, solid state spectra can differ in detail with respect to
selection rules, oscillator strength and energetic position; moreover, due to the
crystal structure or packing polymer chains a pronounced anisotropy can be found.
Additionally disordered organic solids usually show a considerable broadening. In
Fig. 2.15 are schematically shown the optical spectra of molecules in different
surroundings [38].
As a consequence of this weak electronic delocalization, organic semiconductors
have two important peculiarities, as compared to the inorganic counterparts: one is
the existence of well-defined spin states (singlet and triplet) like in isolated mole-
cules, which has an important consequence for the photophysics of these materials;
the second one originates from the fact that optical excitations (“excitons”) are
usually localized on one molecule and therefore have a considerable binding
Fig. 2.15 Schematic representation of optical spectra of organic molecules in different

surroundings. D1 and D2 denote the respective solvent shift in solution and solid state, respectively
energy, typically 0.5–1 eV. Thus, in a photovoltaic cell this binding energy has to
be overcome before a pair of independent positive and negative charge carriers is
generated [38].
2.7 Superlattices. Photonic Crystals and Metamaterials
In a conventional material, the response to electric and magnetic fields, and hence to
light, is determined by the atoms and molecules arranged in a periodic crystal
structure (Fig. 2.16).
Fig. 2.16 Periodic potential in a crystal (a). Periodic potential in a superlattice (b)
Fig. 2.17 Photonic crystals or metamaterials with a 1D (a), 2D (b) and 3D (c, d) periodic
structure constituted from different materials or any artificial units (d) Reprinted with permission
from D. Ö. Güney, Th. Koschny, and C. M. Soukoulis, “Intra-connected 3D isotropic bulk
negative index photonic metamaterial,” Opt. Exp. 18, 12352 (2010) © 2010 Optical Society of
America
By engineering many tiny identical structural units (artificial atoms) in a periodic

arrangements, a huge combination of new materials can be tailored. These new
class of materials with a periodic structure in 1D, 2D or 3D have completely new
properties compared to constitutive materials (Fig. 2.17).
From geometrical point of view superlattices, photonic crystal and metamaterials
are similar. Generally the term of superlattices is employed in electronics to define a
periodic structure of two or more materials layers (see Chap. 2, Sect. 2.4). If the
superlattice is made of two semiconductor materials with different band gaps, the
electrons are confined in a periodic multi quantum well potential (similar to the
periodic potential in a single crystal) that modify the conditions for charges to flow
through the structure. In function of the thickness of the constitutive layers, different
type of carrier conduction mechanisms can occur.
A photonic crystal is a periodic optical nanostructure that affects the motion of
photons in much the same way that ionic lattices affect electrons in solids. Photonic
crystal are also called semiconductors of light [39]. In a semiconductor there is a
band gap for electrons between the valence and conduction band and the electrons
cannot have energies on levels which correspond to the gap. In a photonic crystal, a
periodic structure is created by regions of different dielectric constant, which can be
approximated by a periodic potential. Although “photonic” refers to light, the
principle of the band gap applies equally well to electromagnetic waves of all
wavelengths [39].
The band gap in a semiconductor arises from the diffractional interaction of the
electron wave function with the periodic atomic lattice resulting in a destructive
interference for particular wavelengths. To observe the diffraction of light, a peri-
odic lattice of artificial atoms is necessary with the lattice constant comparable with
the light wavelength for which the bandgap is needed. That is why for visible
wavelengths the lattice constant and artificial atoms should be in the range of
hundred nanometers [40]. Photonic crystals occur naturally in opals or in butterfly
wings (Fig. 2.18).
2.7 Superlattices. Photonic Crystals and Metamaterials 43
Fig. 2.18 Natural photonic crystals a Opals. b Photonic crystal structure in the butterfly wings
Reprinted with permission from Yablonovitch [39]
The difference between photonic crystals and metamaterials is that in photonic

crystals the lattice constant have to be comparable in size with the wavelength
(a ffi k), because the effect of the band gap arises from diffraction. In the case of
metamaterials the subunits (artificial atoms) and lattice constant have to be much
smaller than the wavelength (a k) because diffraction should not appear [40].
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Chapter 3
New Trends in Solar Cells Research
3.1 Functioning Principles and Current Status
Solar cells converts the solar photons energy into electrical energy. The first solar
cell was realized in 1954 at Bell Laboratories. The functioning principles of this
first generation solar cells are based on a p-n homojunction realized in a bulk
semiconductor (Silicon or GaAs). Figure 3.1 depicts the charge carriers’ distribu-
tion and band diagram levels before and after junction formation.
When a p-n junction is formed, the large carrier concentration gradients cause
the diffusion of carriers, so that the holes diffuse from p-type semiconductor to
n-type semiconductor and the electrons from n-type semiconductor to p-type
semiconductor. Hence, after the equilibrium is reached at the interface of the
p-doped region and n-doped region, a narrow layer without mobile charge carriers
is formed. This space charge set up an electric field (Fig. 3.1), which oppose the
diffusion of majority carriers (holes in p-side and electrons in n-side) across the
junction. At this point the Fermi levels (EF) of n-type semiconductor and p-type
semiconductor are equal. The internal electric field favours the motion of minority
carriers (holes in n-zone and electrons in p-zone). When the p-n junction is illu-
minated the photons having energies greater than the band gap will generate
electron-holes pairs in the two regions. The electrons photo-generated in the p-zone
will be accelerated by the internal electric field conducting, if the external circuit is
closed, to a current flow.
The conversion of the radiative energy into electrical energy in a p-n junction
solar cell is based hence on the absorption of a photon, followed by the formation of
an electron-hole pair, then by the charge separation and charge transport towards
the electrodes and finally by an orderly movement of electrons in a circuit.
The various processes of generation of carriers, diffusion, recombination and
drift are fundamental to operation of solar cells and the electrical transport prop-
erties in the constitutive materials play a significant role in determining the effi-
ciencies of solar cells. The basic theory of electrical transport in homogenous single

46 3 New Trends in Solar Cells Research
Fig. 3.1 Schematic structure of p-n junction and energy band diagram before (a) and after thermal
equilibrium (b)
crystal materials and thin films polycrystalline materials have been discussed pre-
viously in Chap. 2.
The functioning principles and the understanding of this first generation pho-
tovoltaic cells conducted to the development of the subsequent and then to the new
generation solar cells.
Thin films technology allowed to reduce the devices weight and cost by the
reduction of materials quantities. Hence in the second generation solar cells the p-n
junctions in bulk materials were replaced by homo- and hetero- p-n junctions in thin
films using the previous semiconductors silicon (amorphous) but also new semi-
conductor materials such as CdTe, CdS, CIGS.
The electrical characteristics of these polycrystalline films are strongly influ-
enced by the bounding surfaces of individual crystallites and grain boundary
phenomena can strongly influence solar cells efficiencies. The potential energy
barriers associated with the grain boundaries dominate the carrier mobility in the
active layers and thus control the resistivity. Hence in function of grains orientation,
the resistivity in parallel or perpendicular direction to the substrate could be dif-
ferent [1]. In a solar cell, increased resistivity primarily results in a decrease of the
fill factor FF with little effect on Jsc or Voc (see Eq. 3.2 and Fig. 3.2). The defects
and impurity causes recombination of excess carrier ultimately reducing the
effective minority carrier lifetime in an inhomogeneous manner, this results in a
moderate loss in Jsc and Voc. For some kinds of thin films solar cells, the reduction
of series resistances loss due to poly-crystallinity, can be almost entirely over-
come by using transparent conducting electrodes such as ITO or FTO [1].
Moreover, in the past two decades there have been few emerging solutions to
bring the photovoltaic production cost affordable for immediate and new applica-
tions. Solar cells made up of organic materials or by mixing organic and inorganic
materials (third generation solar cells), are one such promising answer to make
renewable energy cost effective in all different means with added advantages of
extremely light weight, flexibility over design and processing techniques.
In organic solar cells, the charge carriers’ separation is not governed by the
electric field at the space charge region but by the light-induced charge separation,
which is determined by the band position of the materials and electrodes work
3.1 Functioning Principles and Current Status 47
Fig. 3.2 a Energy band profile of solar cells based on light induced charge separation, b Typical
J-V response of solar cell in dark and under illumination. Relevant parameters such as Voc, Jsc and
maximum power available from this solar cell are highlighted
function [2] (Fig. 3.2a). The light induced electrons and holes separated at the
interfaces should reach each counter electrodes to be collected as a photocurrent and
for a high energy conversion it is necessary to reduce a number of losses occurring
during the transport of carriers through electrodes [3].
In the case of organic solar cells where the donor and acceptor materials are
blended together, the charge carriers are separated at the interface by the exciton
dissociation and percolated toward each electrode through a continuous path of
polymer network. The open circuit is governed by the difference of the Fermi levels
of two materials [3]. The electron conducting material and the hole conducting
material should be chosen so that the energy level line-up encourages the electrons
and holes to flow smoothly without energy losses.
In the absence of a clear established theory of charge transport in organic
materials, the understanding and control of mechanisms governing the organic and
hybrid solar cells functioning is quite difficult.
The typical response of a solar cell in dark and under illumination is given in
Fig. 3.2b.
For the characterization and comparison of different solar cells performances two
magnitudes are important: the power conversion efficiency (PCE) and the external
quantum efficiency EQE.
For the determination of PCE, devices should be illuminated by a standard light
source simulated to solar AM 1.5 spectrum.
The power conversion efficiency is basically the ratio of electrical power gen-
erated to the incident optical power and under standard characterization PCE is
given by:
Voc Jsc
gð%Þ ¼ FF ð3:1Þ
Io
where Voc is termed as open circuit voltage, Jsc is short-circuit current density and Io
is the incident intensity of the light source (100 mW/cm2 for standard irradiation
conditions). FF is called fill factor and is defined by:

Vm Im
FF ¼ ð3:2Þ
Voc J sc
where Vm corresponds to the maximum voltage point and Jm the maximum current
density point measured from the experimental J-V curves and are pointed in
Fig. 3.2.
Another important characterization of a solar cell is given by measuring the
external quantum efficiency of photoactive composition used in devices geometry.
EQE measured in % is basically the ratio of photo-generated electrons to the per
incident monochromatic photon which is given by the relation:
Table 3.1 Solar cells efficiencies certified in the research laboratories

Generation Type Year η (%) first η (%) in Industrialized
report 2016
Bulk material
I Monocrystalline silicon 1954 6 25.3 Yes
GaAs—bulk 1978 22–23 27.5 Yes
Multi-crystalline 1984 15 21.3 Yes
silicon
Multi-junction (staked) 1984 19.5 – Yes
Thin films—inorganic materials
II Silicon—amorphous 1976 1.1 14 Yes
CdTe 1976 9 22.1 Yes
CIS (Cu, In, Se), CIGS 1977 6–7 22.6 Yes
GaAs—thin film 2005 25 28.8 Yes
Multi-junction 1988 27.6 38.8 Yes
(monolithically)
Thin films—organic materials
III Dye sensitized oxide 1991 7–8 11.9 Yes
(liquid/solid)
Organic solar cells 2001 3 11.5 Yes
Multi-junction 2008 5–6 10.6 No
(tandem)
Bulk and thin films—organic and inorganic materials
IV Quantum dot solar 2008 1.8 11.3 No
cells
Perovskite solar cells 2012 9.7 22.1 No/yes
The table gives for each kind of technology the year and the efficiency of the first solar cell report
and the efficiencies achieved today. These data correspond to single solar cells without
concentrators or other mirrors optical systems [4]. The table also indicate if the solar cells are
fabricated at industrial scale at the moment when the book was written
3.1 Functioning Principles and Current Status 49

1240Jsc
EQEð%Þ ¼ 100 ð3:3Þ
kIo
where Io is the incident intensity of the light source (mWcm−2), Jsc is short-circuit
current density (mA/cm2) and k is the radiation wavelength.
Table 3.1. indicate the values of the first reported conversion efficiency and the
reached efficiencies actually in the research laboratories for the main types of solar
cells in function of their active material and technology.
3.2 Plastic and Paper Substrates
• OPV—solar cells on plastic substrates

The development of the new generation solar cells starts with the deposition of
thin films solar cells on new substrates such as plastic and paper and large area
deposition methods such as roll to roll and ink jet. We can distinguish in principal
two classes of the 3rd generation solar cells: the organic solar cells in which the
active materials are constituted by organic materials (small molecules and poly-
mers) and the hybrid solar cells, in which the active materials are constituted by
organic and inorganic materials such as: dyes, titanium or zinc oxide nanoparticles
or porous and mesoporous thin films, polymers, quantum dots, perovskites etc.
For these solar cells the light-induced charge separation takes places not only at
the semiconductor/semiconductor interface but also at the semiconductor/adsorbed
molecules interface, organic material/organic material interface,
semiconductor/quantum dot interface etc. [3].
When the conductivity of the material is not high, there is an energy loss in the
transport of electrons in the high-resistive materials to the electrode. The back
reaction of the separated charges carriers towards the fundamental state, also
reduces the external quantum efficiency. The recombination on localized energy
levels created by defects or impurities causes’ important current leakage.
However, after two decades of research, organic photovoltaics (OPV) has now
reached record efficiencies above 10%, competitive processing costs and shorter
energy payback times and different companies stared to produce OPV and plastic
electronics devices at large scale such as: Konarka, Flexcell, Belectric OPV,
Heliatek, Aromor Group, Plextronics, InfinityPV etc.
Frederick C. Krebs and collaborators from Technical University of Denmark
presented in 2009 the first public demonstration of large area organic solar cells
deposited on plastic substrate (Fig. 3.3). In 2014 they founded the start-up Danish
company InfinityPV (Fig. 3.4) [6].
Beside the roll to roll technology for thin films solar cells deposition on plastic
and paper substrates, ink-jet is another suitable solution process technology.
Fig. 3.3 First public demonstration of large area organic solar cells deposited on plastic
substrates. Reprinted with permission from Frederik Krebs et al. [5] © 2009 Elsevier
http://www.nanotechwire.com
Fig. 3.4 a Organic solar cell foil produced by InfinityPV Company, a Danish start-up company
founded in 2014. Image Courtesy from http://infinitypv.com/. b Organic solar cells deposited on
plastic substrates by the roll to roll method
• DSSC—solar cells on plastic substrates

In 2015, Disasolar French SME in collaboration with CNRS, CEA and the
National Institute for Solar Energy (INES) presented a world premiere by creating
the first polychrome plastic solar panel. The solar panel in Fig. 3.5 consists of
organic solar cells of different shapes and colours, printed by inkjet technology on a
flexible substrate of 15 15 cm2.
This realization makes it possible to expect new applications on a large number
of supports. In the case of polychrome modules, the various colours (three for this
demonstrator) are obtained by using different active layers, themselves composed of
the mixture of a commercial polymer and a fullerene. Due to the different treatments
of each of these active layers, the groups of cells are successively printed colour by
colour in a very specific order.
Obviously, the polychrome modules have more losses than monochrome mod-
ules. For a polychrome module of 100 cm2, with the design presented for this
3.2 Plastic and Paper Substrates 51
Fig. 3.5 a DISASOLAR—CNRS innovation [7] (2015). Polychromic organic solar cells
deposited on plastic substrates by inkjet technology, b Inkjet printer
demonstrator, the yield drops to 2.2% compared to 4.5% or more for a monochrome
module [7].
• DSSC—solar cells on paper substrates
In recent years, new tests are done by using paper substrates. B. Wang and L.
L. Kerr realized the first dye sensitized solar cells (2011) by using paper as support
for one of the electrodes (Ni) (Fig. 3.6). The other one consisted in a FTO film
deposited on glass substrate. The investigated solar cells were: paper/Ni/TiO2 //
electrolyte // Pt/FTO/glass and paper/Ni/ZnO // electrolyte //Pt/FTO/glass [8].
TiO2 commercial pastes mixed with acetylacetone, or ZnO pastes (ZnO
nanopowder dispersed into a solution with acetic acid, ethanol and water) were
spread on Ni coated paper substrates by doctor blade method. Films were subse-
quently annealed in a paper drier at 90–200 °C for 30 min. The dye used in this
study was N719 dye. The electrolyte was made with 0.1 M LiI, 0.05 M I2, 0.6 M
tetrabutylammonium iodide and 0.5 M tert-butyl-pyridine in dry acetonitrile. The
counter electrode was made of Pt coated FTO glasses. The characteristics of this
inverted solar cell were Voc = 0.56 V, Jsc = 6.70 mA/cm2, FF = 0.33 and
η = 1.21%.
• OPV—solar cells on paper substrates
N.S. Sariciftci group report in 2014 a 4% efficient organic solar cells fabricated
on paper substrates with a Zinc, Polyethylenimine (PEIE) coated layer, acting as the
back contact and evaporated oxide/metal/oxide (MoO3/Ag/MoO3) as
semi-transparent top electrodes [9] (Fig. 3.7). The active materials consisted in
polymers-fullerene blends: P3HT:PC70BM and PTB7:PC70BM. The performances
obtained for the paper/Zn/PEIE/P3HT:PC70BM/MoO3/Ag/MoO3 solar cells were:
Jsc = 5.5 mA/cm2, Voc = 590 mV, FF = 0.54, η = 1.8% and for paper/Zn/PEIE/
PTB7:PC70BM/MoO3/Ag/MoO3, Jsc = 10.6 mA/cm2, Voc = 710 mV, FF = 0.55,
η = 4.1%.
Fig. 3.6 a The picture represent the first side: paper/Ni/ZnO of a two sides assembled DSSC solar
cell having the following architecture: paper/Ni/ZnO+Dye // electrolyte // Pt/FTO/glass. The
characteristics of this inverted solar cell are Voc = 0.56V, Jsc = 6.70 mA/cm2, FF = 0.33 and
η = 1.21%. Adapted with permission from Wang and Kerr [8] © 2011 Elsevier. b DSSC solar
cells architecture
Fig. 3.7 OPV solar cells on paper substrates. Reprinted with permission from Leonat et al. [9] ©
2014 ACS Publications
• Amorphous silicon—solar cells on paper substrates

Elvira Fortunato and Rodrigo Martins groups published in 2015 the results
obtained for a thin film (p-i-n) amorphous hydrogenated silicon solar cell on paper
substrate [10]. The PV structure device consisted of: paper/Al/Ag/a-Si:H(n)/a-Si:H
(i)/a-Si:H(p)/IZO. A layer of Al/Ag was used for the back contact, with thicknesses
3.2 Plastic and Paper Substrates 53
of 80 and 40 nm, respectively, deposited in vacuum by thermal resistive evapo-

ration. The n–i–p hydrogenated amorphous silicon (a-Si:H) layers were deposited
by PECVD, and the front transparent electrode IZO (200 nm) was deposited by RF
magnetron sputtering from an IZO target at room temperature. The characteristics
of the best amorphous silicon solar cell deposited on paper substrates were:
Voc = 0.82 V, Jsc = 10.19 mA/cm2, FF = 0.4, η = 3.40%.
3.3 New Transparent Electrodes (IMI and Graphene)
The total extinction of Indium’s natural resources is estimated to be by 2025.

Beside, almost all existing electronic devices (mobile phones, tablets, screens,
computers) and almost new generation thin film solar cells used ITO (Indium Tin
Oxide—Sn doped In2O3) as a transparent electrode. Therefore, indium knows an
increasing demand, driven by the market for flat screens and should undergo very
soon strong price increases. The thickness of thin layers of ITO for electronic and
optoelectronic devices is of 150 up to 700 nm. The reduction of the thickness of the
ITO films below 150 nm is not possible due to the increase in the electrical
resistivity with the decrease in thickness, due to the well know size effect in
semiconductors. Many studies were done the last 10–15 years in order to find
alternative semiconductors for the replacement of ITO. The number of materials
with equivalent properties are not so numerous. For inorganic semiconductors the
increase of the electrical conductivity by doping, conducts to a decrease of the
optical transparency and is difficult to find the optimal doping balance in order to
have at the same time a high transparency and a high electrical conductivity. The
principal single layer transparent conducting thin films are listed in Table 3.2.
The quality of transparent conducting electrodes is evaluated in function of their
figure of merit, which is related to their electrical resistivity and transmission
coefficient in the visible range. The figures of merit of Fraser and Cook and Haacke
are the most employed ones.
Table 3.2 Thin films transparent conducting materials

Inorganic materials/matrix In2O3 SnO2 ZnO
Doping elements Sn (ITO), F, Te Sb, F (FTO), P Al (AZO), In (IZO), Ga
Optical band gap (eV) 3.5–3.7 4.0–4.5 3.2–3.6
Work function (eV) 4.1–5.5 4.2–4.4 4.3–4.4
Organic materials PEDOT:PSS PANI Graphene
Work function (eV) 5.1 4.5–4.7 4.5–5
In bold are indicated the most used doping materials and the called transparent conducting
materials. For example F doped SnO2—Fluor Doped Tin Oxide (FTO), Al doped Zinc Oxide
(AZO) etc.
Fraser and Cook figure of merit is defined as [11]:
T
FTC ¼ ð3:4Þ
Rsh
where Rsh is the sheet resistance and T is the transmission coefficient. The sheet
resistance is defined as:
Rsh ¼ 1=rd ð3:5Þ
where d is the film thickness and r is the electrical conductivity.

The figure of merit defined by Haacke weights less in favour of sheet resistance
and is one of the most employed to evaluate the qualities of transparent conducting
films. Haacke figure of merit is given by [12]:
T10
UTC ¼ ¼ rd expð10adÞ ð3:6Þ
Rsh
where a is the absorption coefficient.

Beside the electrical conductivity and optical properties another very important
parameter for solar cells and optoelectronic applications is the work function. The
highest value of the work function is still that one of ITO, about 5.1 eV. The poly
(3,4-ethylenedioxythiophene) polystyrenesulfonic acid (PEDOT:PSS) polymer thin
films have also high values of the work function but their electrical conductivity is
much lower that ITO electrical conductivity, about 0.2 X−1 cm−1 [13] compared to
about 4103 X−1 cm−1 for ITO [14].
In our previous studies on transparent conducting electrodes, we showed that a
promising alternative to ITO single layers films (150 nm) for plastic applications,
but not only, is their replacement with a multilayer electrode: ITO(20 nm)/Metal
(7 nm)/ITO(20 nm). These oxide/metal/oxide films provide many advantages [14]
Fig. 3.8a. The figure of merit that characterizes this type of electrodes is as high as
that one of ITO single films, but the amount of ITO is reduced by 4. In addition, the
stability of the mechanical and electrical properties is remarkable and makes this
type of structure very attractive not only for conventional applications, but also for
any type of electronic and photovoltaic application on flexible substrate, unlike the
ITO who is fragile and deteriorating after repeated mechanical bendings. In 2014,
the group of Brabec [15] in Germany realised the first Organic Photovoltaic Cell
(OPV) using ITO/metal/ITO electrodes on plastic substrates (Fig. 3.8b) and con-
firms the mechanical, optical and electrical properties of these films and their
suitability for OPV applications. Later, in 2015, the German company
BELECTRIC OPV, present, at the world exhibition of Milan, the first large scale
OPV modules on plastic substrates using the IMI type electrodes [16] (Fig. 3.8c).
Another very promising element of choice is graphene, which transparency
attains 98% and which electrical conductivity is as high as 0.96 106 X−1 cm−1.
S. Bae et al. from Korea presented in [17] the fabrication technology for large area
deposition by roll to roll of graphene on plastic substrates (Fig. 3.9).
3.3 New Transparent Electrodes (IMI and Graphene) 55
Fig. 3.8 a IMI sputtered electrodes on plastic substrate Reprinted with permission from Girtan
[14] © 2012 Elsevier. b First flexible module using IMI sputtered stack as a transparent electrode
Reprinted with permission from Kubis et al. [15] © 2014 Elsevier, c BELECTRIC OPV modules
at the Universal Exhibition Milan 2015 Reprinted with permission from Berny et al. [16] © Open
Access Creative Commons (CC) Licence 2016
Fig. 3.9 a Schematic diagram of the roll-based production of graphene films grown on a copper
foil. The processes are divided into three steps: (1) the adhesion of polymer supports, (2) copper
etching and (3) transfer to the target substrate. b Photographs of the roll-based production of
graphene films on copper foil produced by the process shown in panel (a). Reprinted with
permission from Bae et al. [17] © 2010 Macmillan Publishers Limited
Graphene can fulfil multiple functions in photovoltaic devices: as the transparent

conductor window, photoactive material, channel for charge transport, and catalyst
[18].
Some examples of organic solar cells involving graphene layers are given in
[18, 19] with configurations such as: plastic/metal/ZnO/P3HT:PCBM/PEDOT:PSS
(Au)/Graphene/PMMA and glass/ITO/PEDOT:PSS/P3OT:Graphene/LiF/Al for
which the obtained performance were of: Voc = 0.38 V, Jsc = 10.48 mA/cm2,
FF = 0.34, η = 1.39% for the first cell and Voc = 0.92 V, Jsc = 4.2 mA/cm2,
FF = 0.37, η = 1.4% for the second one. For DSSC solar cells, one of the studied
configuration was Quartz/Graphene/TiO2/dye/Spiro-MeO-TAD/Au for which
Voc = 0.7 V, Jsc = 1.01 mA/cm2, FF = 0.36, η = 0.26%. Other possible applica-
tion was proposed for p-i-n amorphous silicon solar cells graphene
electrode/p-i-n/back electrode [19].
3.3.1 Electrodes Work Function
The electrodes work function can be measured by using a surface Kelvin probe
system (Fig. 3.10).
The principle of method is based on Lord Kelvin experiment. When two con-
ducting materials with different work functions are brought together, (via an
external wire contact, for example), electrons flow from the material with the lower
work function to the one with the higher work function (Fig. 3.11a). If the two
Fig. 3.10 Kelvin Probe

System. Image courtesy Prof.
Iain Baikie, Director KP
Technology Ltd
materials are connected through a dielectric in the configuration of parallel plate

capacitor, equal and opposite surface charges will form (Fig. 3.11b). By applying
an external potential to the capacitor, the surface charges disappear completely at
the moment at which the external potential equals the contact potential (Fig. 3.11c).
The contact potential difference is given by:
/2 /1
VCP ¼ ð3:7Þ
e
By measuring the contact difference potential and knowing the work function of
one of the electrodes (for example of a gold tip /1 ¼ 5:0 eV) the work function of
the other electrode car be determined.
An interesting observation which allow a fast estimation of different electrode
materials work function is given by an experiment described by Girtan [20] using a
polymer:fullerene solar cell configuration. The electrodes work function measure-
ments were performed using Al as a reference electrode (E1) and Al, Cu, Ag, Au,
ITO, ITO/Ag/ITO, ZnO/Au/ZnO etc. as samples probe electrodes (E2). A polymer:
fullerene blend of P3HT-poly(3-hexylthiophene-2,5-diyl) and PCBM—
Methanofullerene Phenyl-C61-Butyric-Acid-Methyl-Ester was used as semicon-
ducting material in a planar solar cell configuration (Fig. 3.12).
The active polymer:fullerene layer was exposed to a standard solar simulator
illumination at 100 mW/cm2, AM 1.5. The origin of Voc in organic solar cells is
still not clear and various models have been presented to explain the dependence on
the nature of electrodes, donor (/) acceptor materials, illumination intensity or
temperature but, yet, none of them is suitable enough to explain correctly all the
experimental data. In most of cases it is considered that the Voc is determined by the
difference of the electrodes work functions, which is coherent with Kelvin exper-
iment, without mentioning the dependence on the nature of active materials, or the
illumination. As a general observation in a transversal geometry and for standard
Fig. 3.11 Energy and charge diagram illustrating Kelvin probe technique principle. Adapted with
permission from I.D. Baikie and P.J. Estrup, Rev. Sci. Instrum 69, 11 (1998) 3903
E (eV)
Al
E1 E2 0.25
P3HT: PCBM Cu 0.33
Glass Ag
0.43
Au 0.58
ITO
Fig. 3.12 a Configuration used for measuring the open circuit voltage Voc. b Relative position of
work function levels established on the basis of experimental Voc measurements. Reprinted with
permission from Girtan [20] © 2013 Elsevier
illumination (1000 W/m2) for the Al-ITO pairs of electrodes with or without dif-
ferent buffers layers, the open circuit voltage of solar cells based on P3HT:PCBM is
about 450–660 mV, for the PCDTBT:PCBM solar cells is about 850–890 mV and
for MDMO–PPV:PCBM solar cells is about 770–870 mV [21]. In connection with
the experimental data given in Table 3.3, Fig. 3.12 presents the relative positions of
the electrodes in function of the work function values estimated in the assumption
that the open circuit voltage is given by the formula [22]:
eVoc ffi WextE2 WextE1 ð3:8Þ
By imposing to the work function of Aluminium the value of 4.3 eV (given in

literature) the calculated values for the work functions of the others materials Cu,
Ag, Au, ITO are coherent and in very good agreement with the literature data (see
Tables 3.3 and 3.4). The only metal which shows a slight deviation from literature
data is Au. This discrepancy for gold was already evidenced by other authors and,
in the case of the metal-insulating-metal (MIM) model and was attributed to the
formation of interface dipoles [22].
Table 3.3 Measured open E1 E2 Voc (mV)

circuit voltage from I–V
characteristic curves at Al Al 0
1000 W/m2 irradiation under Al Cu 250
solar simulated light AM 1.5, Al Ag 330
using different combinations Al Au 430
of electrodes, in a planar
Al ITO 580
diode configuration
Al ITO/Ag/ITO 550
Al ZnO/Au/ZnO 500
Table 3.4 Comparison Electrode Work function (eV)

between the calculated work
Calculated Literature
function values of different
electrodes based on formula Al 4.30 (imposed) 4.1–4.3
(3.8) and the literature data Cu 4.55 4.5–5.1
Ag 4.63 4.5–4.7
Au 4.73 4.8–5.1
ITO 4.88 4.7–5.5
ITO/Ag/ITO 4.85 –
ZnO/Au/ZnO 4.80 –
The three layers electrode ITO/Ag/ITO and ZnO/Au/ZnO were prepared as

described in [14] and we remarked that the work function of these
oxide/metal/oxide electrodes is as high as for ITO single layers. The oxide thin
films thickness is about 20 nm and the metal layer thickness is about 7–8 nm.
The reliability of this method is sustained by the very good correlations between
the measured values obtained for Cu, Ag, Au and ITO and the values given in
literature (see Table 3.4).
The principle of work function measurements allows to easier understand the
functioning principle of organic solar cells like ITO/PEDOT:PSS/P3HT:
PCBM/LiF/Al, which is one of the most studied polymer: fullerene bulk hetero-
junction solar cell (Fig. 3.13).
From the point of view of a work function measurement, this system can be seen
as a two different work function electrodes separated by a semiconducting material.
The two electrode materials are ITO and Al. Due to the difference of their work
function a current will flow when an external wire connect the two electrodes
separated by a semiconducting (organic) materials (PEDOT:PSS and P3HT:
PCBM). PEDOT: PSS and P3HT are conductive polymers sensitive to light, hence
when the materials are exposed to light, electrons-holes pairs (excitons) are
generated.
Al
LiF
P3HT:PCBM
PEDOT:PSS
ITO
Glass / Plastic
Fig. 3.13 a Classical architecture of an organic photovoltaic solar cell ITO/PEDOT:PSS/P3HT:

PCBM/Al. b Band energy diagram
Different from classical p-n junction, solar cells with spatially separated p- and
n-type regions, bulk heterojunction solar cells consist of an intimate mixture of an
organic “p-type” with an organic “n-type” semiconductor, generating nanoscaled
p-n junctions. In this configuration PCBM acts as an acceptor and P3HT is the
donor material. LiF and PEDOT:PSS are buffer layers [23].
To achieve substantial energy-conversion efficiencies, these excited electron–
hole pairs need to be dissociated. The dissociation can occur at interfaces of
materials with different electron affinities or by electric fields, or the dissociation
can be trap or impurity assisted. Blending conjugated polymers with
high-electron-affinity molecules like C60 has proven to be an efficient way for rapid
exciton dissociation [24]. The generated electrons after absorption into the polymer
are transferred to fullerenes molecules.
Other intensively studied polymers for organic solar cells were: MEH:PPV,
MDMO:PPV, PCDTBT etc. in similar configurations such as: ITO/PEDOT:PSS/
MEH:PPV-PCBM/LiF/Al; ITO/PEDOT:PSS/MDMO:PPV-PCBM/LiF/Al etc. [23].
3.4 Strategies for Increasing the Absorption
(i) Light trapping. Plasmonics solar cells

(ii) Quantum dots and intermediate band gap
(iii) Absorbing material—Perovskites (DSSC, OSC, c-Si, a-Si, CIS, CIGS)
(iv) Optical materials—optical convertors. Optical systems.
The efficiency of single-junction solar cells is limited by a series of optical and
electrical losses. The dominant loss processes (more than 60%) is due to the mis-
match between the broad solar spectrum and the mono-energetic absorption char-
acteristics of the single gap semiconductor material. Due to the discrete band
structure of semiconductors, only photons with energies close to bandgap energy
(Eg) are efficiently absorbed and contribute to the electrical output of the solar cell.
In order to reduce these spectral losses and increase the energy conversion efficacy,
many strategies can be considered (i) light trapping, (ii) semiconductors band gap
engineering, (iii) new active materials with high absorption coefficients (iv) optical
convertors, (v) multi-junctions solar cells, (vi) optical convertors optical systems.
3.4.1 Light Trapping. Plasmonics Solar Cells
Surface plasmon (see definition on Chap. 2) can be used to control the colour of
materials by controlling the shape and size of metallic nanoparticles introduced in a
matrix. The oldest applications of these nanoparticle properties are church window
glasses or ancient glass vases, in which the colour is given by small gold
nanoparticles.
3.4 Strategies for Increasing the Absorption 61
Fig. 3.14 a Light trapping by scattering from metal nanoparticles at the surface of the solar cell.
b Light trapping by the metal nanoparticles embedded in the semiconductor. c Light trapping at the
metal/semiconductor interface. Reprinted with permission from Atwater and Polman [25] © 2010
Nature Materials, d Surface plasmon polariton propagation
By using the plasmonic effect the absorption can be increased by light trapping.
H.A. Atwater and A. Polman describe in [25] different light trapping configurations
by using metallic nanoparticles (Fig. 3.14).
The first configuration (Fig. 3.14a) corresponds to the light trapping by scat-
tering from metal nanoparticles at the surface of the solar cell. In this case light is
preferentially scattered and trapped into the semiconductor thin film by multiple and
high-angle scattering, causing an increase in the effective optical path length in the
cell. The second one corresponds to the light trapping by the excitation of localized
surface plasmons in metal nanoparticles embedded in the semiconductor
(Fig. 3.14b). The excited particles’ near-field causes the creation of electron–hole
pairs in the semiconductor. The third configuration corresponds to the light trapping
by the excitation of surface plasmon polaritons at the metal/semiconductor interface
(Fig. 3.14c). A crenelated metal back surface couples light to surface plasmon
polariton or photonic modes that propagate in the plane of the semiconductor layer
(Fig. 3.14d) [25].
3.4.2 Quantum Dots and Intermediate Band Gap
The optical band of semiconductors and the solar cells conversion efficiencies are in
a strong correlation. In Chap. 2 of this book we saw that a photon can be absorbed
by a semiconducting material only if it energy is superior to the band gap.
Figure 3.15a gives the solar irradiance spectrum in function of photons energy
and Fig. 3.15b gives on the left axis the absorption coefficient (lines) for different
semiconductors materials (CdS, GaAs, amorphous Silicon, Ge, CdTe, monocrys-
talline silicon) in function of wavelength and, on the right axis, the corresponding
conversion efficiencies (circles) of solar cells based on single homo-junctions of
these materials in function of semiconductors band gap (top axis in eV).
As one can see the maximum solar irradiance is comprised between 400 nm and
1000 nm. Besides, the band gap of GaAs is about 1.44 eV (861 nm), of CdS is of
2.30 eV (539 nm), of Si is about 1.12 eV (1107 nm), of CdTe is about 1.44 eV
Fig. 3.15 The spectral

irradiance from the sun (top)
and the absorption coefficient
in a variety of semiconductor
materials for solar cells as a
function of the light
wavelength (bottom)
(861 nm), of amorphous silicon of 1.30 eV (954 nm) and we remark that these are
the semiconductors for which the highest conversion efficiency are obtained.
Of course the efficiency does not depend only on the semiconductors band gap
but also on other parameters in connection with the charge mobility, recombination
mechanisms and charge harvesting.
The engineering of the optical band gap of semiconductors, or solar cells using
combinations with two or more semiconductors are interesting solutions which
were and are exploited to increase the light absorption.
The engineering of semiconductors optical band gap can be done by using
quantum dots (QD). Quantum dots are tiny particles with diameters in the range of
2–10 nm (10–50 atoms). Their properties are intermediate between bulk semi-
conductors and discrete molecules. Due to their small size, the electrons are con-
fined in a small space (quantum dots). Generally, as the size of the crystal decreases,
the difference in energy between the highest valence band and the lowest con-
duction band increases. Hence, more energy is then needed to excite the dot, and
consequently, more energy is released when the crystal returns to its ground state,
resulting in a colour shift from red to blue in the emitted light (Fig. 3.16).
As a result of this phenomenon, quantum dots, from the same material, can emit
any colour of light simply by changing the dot size. Additionally, due to the highly
tunable properties by the precise control of the size of the produced nanocrystals,
Fig. 3.16 a Semiconductor band gap decreases with increase in size of the nanocrystals quantum
dots. Adapted from [26]. b Photoluminescence of quantum dots tuned by QDs size or
concentration (image courtesy Prof. Dmitri V. Talapin, University of Chicago)
QDs are of wide interest. The relationship between the optical band gap and
quantum dots size is given by [27]:

h2 1 1 1:8e2
Egnano ¼ Egbulk þ þ ð3:9Þ
8m0 r 2 me mh 4pee0 r
where r is the radius of the nanoparticle. The second term is the particle-in-a-box
confinement energy for an electron-hole pair in a spherical quantum dot and the
third term is the Coulomb attraction between an electron and hole modified by the
screening of charges by the crystal.
Low-temperature solution-processed solar cells incorporating organic semicon-
ductors and colloidal quantum dots (QDs) are a potential alternative to conventional
solar cells fabricated via vacuum or high-temperature sintering processes for
large-area, high-throughput, and low-cost manufacturing. PbS and PbSe QDs can
already be tuned across the near-infrared spectrum from k = 2200 nm to
k = 600 nm wavelength, encompassing the range of ideal band gaps for optimum
efficiency in both single and multijunction solar cells [28]. As an example, L.Y.
Chang et al. explore an alternative heterojunction solar cell based on PbS QDs and a
low-temperature solution processed. Figure 3.17 shows the device architecture and
the band diagram of PbS QD/CdS bilayer heterojunction solar cells.
PbS QDs of a wide band gap ( 1.5 eV, as determined from the first absorption
excitonic peak at k = 850 nm) are used to ensure energetically favourable electron
transfer from PbS QDs to CdS and to reduce the interfacial recombination current.
Light is incident on the heterojunction from the side of the PbS where excited states
are mainly generated in the smaller-energy-band gap PbS QDs, and the larger gap
CdS can act as an optical spacer. Energy levels are given in Fig. 3.17b [28].
Another possibility to increase the solar cells efficiency by semiconductors band
gap engineering was proposed by Luque and Martí [29] who suggested the intro-
duction of an intermediate band into the active semiconductor band gap (Fig. 3.18).
Fig. 3.17 a Schematic of the PbS QD/CdS heterojunction device. b Energy band diagram
showing band edges of isolated 1.5 eV PbS QDs and CdS along with electrode work functions.
Reprinted with permission from Chang et al. [28] © 2013, American Chemical Society
Hence low energy photons from IR solar spectrum region can be efficiently
absorbed by two steps transitions. Starting from this theoretical concept, rising
experimental efforts have been made in the last decade to realise intermediate band
solar cell (IBSC). Different technological approaches have been investigated for the
implementation of a high-efficiency IBSC. These can be divided into three large
groups: (i) nanostructures, such as quantum dots, (ii) highly mismatched alloys,
semiconductor alloys where band anticrossing effects take place and (iii) semicon-
ductor bulk materials containing a high density of deep-level impurities [30]. The
realization of the intermediate band and the investigation of it presence are difficult
to achieve and require the development of specific experimental procedures.
Recently the existence of the intermediate bandgap was clearly put in evidence
in GaSb/GaAs quantum dot intermediate band solar cells, by measuring for the first
time, absolute quantum efficiency (QE) which clearly reveals the three characteristic
bandgaps of an IBSC. GaAs-based QD-IBSC prototypes containing ten layers of
Fig. 3.18 Band diagram of an intermediate band solar cell (IBSC), showing the bandgap (Eg), the
sub-bandgaps (EH, EL) and the CB, IB and VB. “(1)”, “(2)” and “(3)” represent photon
absorptions. Reprinted with the permission from Yang et al. [31] © 2013 Macmillan Publishers
Limited, part of Springer Nature
n-doped GaSb QDs were fabricated by molecular beam epitaxy on heavily n-doped
GaAs (100) substrates [32].
3.4.3 Absorbing Material—Perovskites (DSSC, OSC, CIS,

CIGS, a-Si, C-Si)
Organic-inorganic halide perovskites have several features such as: long charge
carrier lifetime, long diffusion length and ambipolar charge transport capability
which made them very attractive materials for solar cells. Since the first report, in
2009, [33] the efficiencies of organic–inorganic hybrid solar cells based on
methylammonium lead halide (MAPbX3) perovskites rapidly increased from 4 to
21% in 2016 [34]. The fast rise of the perovskite solar cell field was possible by the
ease with which a wide range of high-quality materials can be fabricated via simple
solution processing methods and it is believed, currently, that perovskite solar cells
are the most promising next-generation photovoltaics solar cells. The typical solar
cells architecture is: FTO/TiO2/Perovskite/Spiro-MeO-TAD/Au. In particular, their
facile synthesis directly on the substrate at low temperature made them very suitable
for applications on plastics substrates. The perovskites structural arrangement is
given in Fig. 3.19a. The high efficiencies of solar cells based on the perovskite
materials CH3NH3PbI3 and CH3NH3PbI3-xClx can be explained by the high
absorption coefficient of these materials (see Fig. 3.19b).
Historically, perovskite solar cells derived from dye-sensitized solar cells
(DSSC) solar cells (Fig. 3.20). This technology start with the liquid
electrolyte-based mesoscopic DSSC (1991), then the liquid electrolyte was replaced
Fig. 3.19 a Crystal structure of cubic perovskites ABX3 methyl ammonium lead halide (iodine)
perovskites: CH3NH3PbI3 (MAPbI3). Reprinted with permission from P. Gao, M. Graetzel, M.K.
Nazeeruddi, Energy Environ Sci, (2014), 7, 2448. b Absorption coefficient of CH3NH3PbI3 and
CH3NH3PbI3–xClx. Reprinted with permission from M.A. Green [35] © 2014 Nature Publishing
Group
Fig. 3.20 Historic evolution of dye-sensitized solar cells (DSSC) technology: DSSC (1991),
ssDSSC (1997), ETA cell (2005), MSSC perovskite (2012). Reprinted with permission from
Snaith [36] © 2013 American Chemical Society
by a solid state organic p-type hole conductor—ssDSSC (1997), followed by the

replacement of the dye by an extremely thin absorber layer—ETA cell (2005) and
finally by the replacement of ETA with a perovskite absorber deposited on a porous
insulating scaffold, meso-superstructured solar cell—MSSC (2012) [36].
As quantum dots compounds, inorganic–organic hybrid materials, based on
CH3NH3 (=MA)Pb(I1−xBrx)3 perovskites, can be colourful tuned. The band gap
engineering brought about by the chemical management of MAPb(I1−xBrx)3 per-
ovskites can be controllably tuned to cover almost the entire visible spectrum,
enabling the realization of colourful solar cells (Fig. 3.21). Band-gap tuning of
MAPbX3 can be achieved via substitution of I with Br ions, which arises from a
strong dependence of electronic energies on the effective exciton mass [37].
Jun Hong Noh et al. fabricated inorganic–organic heterojunction solar cells by
using an entire range of MAPb(I1−xBrx)3 as light harvesters on mesoporous
(mp) TiO2 and polytriarylamine (PTAA), which act as hole-transporting materials
(HTMs).
The architecture of fabricated solar cells was: FTO/denseTiO2/
mpTiO2+perovskite/PTAA/Au. The cells with MAPb(I1−xBrx)3 performed stably at
x = 0.2 compared with other compositions, and the substitution of I with Br also led
to improved efficiency with a maximum power conversion efficiency of 12.3%
under air-mass 1.5 global (AM 1.5G) illumination of 100 mW/cm2 intensity.
The exponentially increase interest on perovskite materials conducts to their
extremely fast application on all categories of previously studied solar cells, starting
from the third generation organic solar cells (OSC) and continuing with the second
generation (CIS and CIGS solar cells) and finally but not last with the first gen-
eration solar cells (a-Si amorphous silicon, and c-Si monocrystalline silicon).
On the basis of a classical polymer: fullerene solar cell, Fig. 3.22, presents the
architecture and the conversions efficiencies obtained for a solar cells in which the
polymer was replaced by a perovskite thin films.
Fig. 3.21 Photographs and UV–vis absorption spectra of MAPb- (I1−xBrx)3. a UV–vis absorption
spectra of FTO/dense-TiO2/mp-TiO2/MAPb-(I1−xBrx)3/Au cells measured using an integral
sphere. b Photographs of TiO2/MAPb(I1−xBrx)3 bilayer nanocomposites on FTO glass substrates.
c A quadratic relationship of the band-gaps of MAPb(I1−xBrx)3 as a function of Br composition
(x), d Power conversion efficiencies of the heterojunction solar cells as a function of Br
composition (x). Reprinted with permission from Noh et al. [37] © 2013 American Chemical
Society
Fig. 3.22 Structure of perovskite solar cells. a Device architecture, b energy-band diagram of the
devices with PEDOT:PSS and CPE-K as the HTL (Hole Transporting Layer), c solar cell
performance: current density—voltage (J–V) curves. Reprinted with permission from Choi et al.
[38] © 2017 Macmillan Publishers Limited, part of Springer Nature
The device preparation was done as following: a poly

(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), was spin-cast at
5000 rpm on ultraviolet ozone-treated ITO substrates and dried at 140 °C for
10 min. A poly[2,6-(4,4-bis-potassiumbutanylsulfonate-4H-cyclopenta-[2,1-b;3,
4-b’]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (CPE-K)CPE-K film was
deposited from solution by spin-cast on the top of the PEDOT:PSS film. After
transferring samples into nitrogen-filled glovebox, precursor solutions of
MAPbI3-XClX perovskite were spin-cast at 7000 rpm on top of PEDOT:PSS and
CPE-K layer, and baked at 90 °C for 60 min. A PCBM solution with a concentration
of 1.3 wt% in chloroform was spin-cast at 3000 rpm on top of the perovskite layer.
Subsequently, an Al electrode with thickness of 100 nm was deposited on top of the
PCBM under vacuum (<10−6 Torr) by thermal evaporation. The area of the Al
electrode defines the active area of the device as 3.30 mm2 [38].
Others architectures involving perovskite materials were proposed for tandem
solar cells including a-Si, c-Si, CIS and CIGS solar cells.
Tandem or multi-junction solar cells were studied and manufactured, since long
time, for all categories of solar cells: bulk or thin films, organic or inorganic, and
consist into a stack of two (tandem) or more p-n junctions made of different
semiconductor materials connected in series. Each semiconductor material will
absorb the part of solar spectrum corresponding to its optical band gap and the total
multi-junction solar cell were absorbing more light than each individual unijunction
solar cells. Hence the open circuit voltage and the generated photocurrent are
increased. The work principle of multijunction solar cells is described in Fig. 3.23a.
Following this idea, the new proposed tandem solar cells based on perovskite
materials are depicted in Fig. 3.23b, c [36].
A 2-terminal perovskite/Si multijunction solar cell was developed by J.P. Maiola
et al. [39] by depositing a perovskite sub-cell on top of the tunnel junction (Fig. 3.24).
The back of the Si sub-cell was first metallized, then a 30nm-thick TiO2 layer
was deposited on the planar n++ c-Si front surface by atomic layer deposition. This
TiO2 layer is the n-type heterojunction for the perovskite sub-cell. TiO2 is a good
electron-selective contact for c-Si because of its conduction-band alignment, which
also facilitates the electron transport from the TiO2 layer into the n++ Si tunnel
junction layer. The perovskite was deposited onto a mesoporous TiO2 layer in a
two-step conversion method. An organic p-type heterojunction contact,
spiro-OMeTAD, was deposited by spin-coating on top of the perovskite. The top
silver nanowire (AgNW) electrode was deposited by mechanical transfer from a
Fig. 3.23 a Schematic illustration of multijunction solar cell work principle, b c-Si—perovskite
HIT (heterojunction with intrinsic thin layer) cell tandem where i intrinsic, a amorphous,
c crystalline, and TCO transparent conducting oxide. Shows a perovskite—thin film tandem,
c CIGS, CIS—perovskite tandem devices. Sunlight is incident from the top. Reprinted with
permission from Snaith [36] © 2013, American Chemical Society
Fig. 3.24 a The device structure of a 2-terminal monolithically grown perovskite/Si

multi-junction solar cell with an n-type Si base, b The polished SEM image is taken at 45° tilt
to show the Ag nanowire mesh (500 nm scale bar), c Total device reflection and EQE of the
perovskite and Si sub-cells of a typical perovskite/Si multi-junction cell. The perovskite sub-cell
EQE is corrected to match the measured JSC and the silicon sub-cell EQE is reported as measured,
d J-V curve of the 2-terminal perovskite/silicon multi-junction solar cell under AM1.5G
illumination. Forward and reverse-bias scan directions are shown with 5 s measurement delay per
data point. Steady-state values for JSC, VOC, and MPP are measured by averaging over 30 s after
reaching steady state. Reprinted with permission from Mailoa et al. [39] © 2015 AIP Publishing
LLC
sprayed film on a plastic substrate. The silver nanowire electrode (before transfer)
had a sheet resistance of 9 X/□ with a peak transmission of 89.5%. A lithium
fluoride (LiF) anti-reflection layer was then deposited by thermal evaporation.
The efficiency of this one of the first 2-terminal multijunction prototype is low
compared to the record efficiency for perovskite or Si cells, due to limitation in
current of the perovskite sub-cell. However further improvements of individual
cells and their connecting interface can yield a 29.0% efficient tandem, with the
ultimate efficiency potential of these monolithic tandems surpassing 35% [39].
The advances in solar cells research and the new achievements on these new
type of tandem solar cells shows that all technology: inorganic, organic or hybrid
can converge and conduct to new promising devices.
To break through as a reliable technology for large scale area applications, all
these new materials and technologies need to be accompanied by a satisfactory
durability. Enhancing the stability of materials and devices, which are continuously
exposed to external factors such as light, heat, in-diffusing oxygen and humidity, is
the next critical issue. Therefore, the development of cost-effective new solar cells
with high efficiency along with a good stability is an important task to address.
Many aspects related to these materials still need to be understood including the
materials’ photo-stability and device working principles.
3.4.4 Optical Materials—Optical Convertors. Optical

Systems
For an optimal industrial development of all classes of photovoltaic solar panels,

several aspects should be taken into account such as: the solar cell efficiency, the
materials and technology costs, the lifetime of materials and devices stability and
the quality of encapsulation materials. The advantage of frequency converter glasses
is that they can be used in replacement of usual silica glasses without any modi-
fication in the solar panels fabrication technology.
The mechanisms of up-conversion, down-conversion or down shifting can be
exploited in order to convert the infrared or ultraviolet light into visible light, which
can thus be efficiently absorbed by most semiconductor materials used for solar
cells. The increase of the number of absorbed photons leads to an increase of the
generated electron-hole pairs number and thus to an increase of the generated
photocurrent (Fig. 3.25).
Two configurations are possible: (1) front converter (the converter is placed on
the top of the solar cell) and (2) rear converter (the converter is placed behind the
solar cell). The configuration (1) is used in the case of down-conversion and
Fig. 3.25 a Energy diagrams showing photon energy conversion by down-shifting,

down-conversion and up-conversion, b Potential gain by down- and up-conversion solar photons
energy for a silicon solar cell
down-shifting whereas the configuration (2) is used in both cases: up-conversion

and down conversion. Up and down converters are based on rare earth doped
materials which may modify the photons energies in order to adjust them to the
corresponding value of the band gap of the active material. By tuning the properties
of the optical convertors in function of the optical band gap of the solar cell
semiconductor, this concept can be used to improve the efficiency of all types of
solar cells (Si, GaAS, CIS, CIGS, DSSC or OSC). The first theoretical studies on
the improvement of solar cells efficiency by the use of energy convertors, were done
by Trupke et al. [40, 41]. The theoretical calculations show that the device effi-
ciency can be increased in the following configurations: front down-converter, rear
up-converter and rear down-convertor (Fig. 3.26). The front up-converter config-
uration does not increase the device efficiency.
The properties of rare-earth (RE) doped glasses have attracted a great attention
due to potential applications in many fields such as solid state lasers, fiber and
waveguide amplifiers and spectral converters for solar cells, due to numerous
energy levels and long-lived excited states of RE ions. Fluoride glasses exhibit a
wide transparency from ultraviolet (UV) to infrared (IR), a low phonon energy and
they allow achieving high RE doping rates.
The phenomenon of “up and down conversion” has been demonstrated exper-
imentally for many rare earth (RE) doped materials (glass or crystal) under
monochromatic laser radiation excitation and claimed as potentially suitable for
solar energy conversion, but only few experimental studies have been performed
under solar simulator conditions.
Fig. 3.26 Theoretical calculations (a) Upper limits for the solar energy conversion efficiency of
the up-converting system as a function of the band gap for the minimum emission case (open
squares). The Shockley-Queisser limits for conventional single-junction solar cells are plotted for
the same concentration factors for comparison (solid lines). Reprinted with the permission from
Trupke et al. [40] ©. b Efficiency of the system: Shockley–Queisser limit for a conventional solar
cell (solid line), efficiency of the system with the converter located on the front surface (open
squares), efficiency of the system with a converter with one impurity located on the rear surface
(solid circles). Non-concentrated radiation from a 6000 K sun is assumed for all curves. Reprinted
with the permission from Trupke et al. [41] © 2002 J. App. Phys, AIP Publishing
M. Girtan and collaborators studied the Pr3+–Yb3+ co-doped ZBLA glasses [42]
and Tm3+ doped fluoride ZLAG glasses [43] as down convertor encapsulation
glasses for silicon solar cells under solar simulator illumination conditions in order
to check the real capacity of these down convertor glasses to increase solar cells
efficacy.
The schematic energy levels diagrams and the possible energy transfer
(ET) processes involved in the down-conversion mechanism are described in
Figs. 3.27 and 3.28.
In the case of Pr3+–Yb3+ co-doped ZBLA glasses, photons having energies
higher than 2.57 eV (482 nm) can be absorbed by Pr3+ ions and excite the levels
3
P0, 3P1, and 3P2. By successive des-excitation of these levels, two photons can be
emitted. In the presence of Yb3+, after the excitation of the levels 3P0, 3P1, or 3P2 of
Pr3+, a depopulation of the excited state can occur through two sequential resonant
ET steps between Pr3+ and Yb3+ with 1G4 acting as the intermediate level by two
routes [42].
The luminescence spectrum of Tm3+-doped ZLAG glass under 467 nm shows
two emission bands at 650 and 794 nm. In the conversion processes reported here,
one blue phonon is converted into one red photon at 650 nm or one NIR photon at
974 nm. The down shifting luminescence at 794 nm corresponds to the spectral
region where Si solar cells exhibit high response and thus could be used to enhance
solar cells efficiency [43].
In order to evaluate the photon conversion efficacy on the electrical response of
solar cells, the electrical J-V characteristics were plotted [42, 43] for a silicon solar
cell, under solar simulator irradiation. The increase of the solar cells efficiency is
not significant for the studied rare doped glasses in the configuration presented
above.
Fig. 3.27 a J-V characteristics measurements configuration b Schematic energy level diagram of
Pr3+ and Yb3+ ions explaining the energy transfer process between the dopants route 1 and route
2. Reprinted with permission from Merigeon et al. [42] © 2015 Elsevier
(b)
1D 1D
2 2
25 4
3
1G 1G
4 4
(a) 20
467 nm
CR
794 nm
Energy (× 10 3 cm-1)
650 nm
2
15 3F 3F
2,3 2,3
1
3H 3H
4 4
10
3H 3H
5 5
3F 3F
5 4 4
0 3H 3H
6 6
Tm3+ Tm3+
Fig. 3.28 a Schematic view of J-V characteristics measurement configuration with the down
convertor in the front of the silicon solar cell. b Energy levels diagram of Tm3+ with
cross-relaxation (CR) mechanisms between two Tm3+ ions. Reprinted with permission from
Maalej et al. [43] © 2016 Elsevier
The improvement of energy transfer mechanism, the increase of the absorbance

and also a better collection of converted photons are necessary in order to make this
kind of glasses of future interest for large scale applications. The deposition in thin
films is also a possible solution to be exploited in the future in order to reduce the
fabrication cost and reduce the optical losses.
Moreover in order to be able to apply this concept in the most efficiently way,
cheap materials absorbing in UV and IR domain and emitting in visible domain are
needing to be founded.
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Chapter 4
Trends in Photonics
The name “Photonics” derived from the Greek word “photos” meaning “light” and
photonics is closely related to “optics” as the “science of light” in the classical way as a
wave (classical optics) and in the quantum way as a particle (quantum optics). With the
development of lasers and data transmission, the term of “Photonics” was introduced
from the necessity to describe a research field, whose aim was to use light to perform
functions that usually fell within the domain of electronics such as information pro-
cessing. Hence, Photonics can be defined as the science referring to generation,
transmission, amplification, detection, modulation and manipulation of photons.
Moreover taking into account all the interactions of the light with the matter,
photonics is therefore related to many other scientific area defined such as: “op-
tomechanics”, “optoelectronics”, “electro-optics”, “quantum electronics”, “mag-
netoptics”, “plasmonics”, “polaritronics” etc.
4.1 New Materials (Metamaterials and Graphene)
Metamaterials are artificial crystals that could manipulate beams of light in the same
way that silicon and other semiconductors control electric currents. Eli
Yablonovitch mentioned in an article published in Scientific American, Inc. [1]
“that patterning photonic crystal thin films into optical circuits would represent the
ultimate limit of optoelectronic miniaturization by producing integrated circuits that
combine conventional electronics and photonics and extending the domain of
bandwidth to optical signals”.
Hence, if we remember the theory of band formation in natural crystals pre-
sented in Chap. 2 and the electronic transport in materials, we can imagine the huge
area of research and applications that metamaterials will open both for electronic
and photonic transport.
While current electronics and photonics are based on sand (silicon and silicon
dioxide), carbon (in both bulk and graphene form) might be also the future element
78 4 Trends in Photonics
(a) (b)
Fig. 4.1 a Metamaterial b Graphene sheet
of choice. Due to the absence of an optical band gap, graphene absorbs all photons
at any wavelength. If incident light intensity becomes strong enough, due to the
Pauli blocking principle, the generated carriers fill the valence bands, preventing
further excitation of electrons at valence band. Hence, this property could poten-
tially be exploited to realize short and very intense light pulses lasers with a wide
optical response ranging through ultra-violet, visible, infrared to terahertz.
Moreover, graphene structure specificity and charge transport properties open up
new research possibilities through graphene plasmonics (Fig. 4.1).
Also, as in the case of transparent electronics, graphene may open the Era of
photonics devices on flexible substrates.
4.2 New Carrier Information Vectors (Plasmons

and Surface Plasmons Polaritons)
Plasmon (see the definition of plasmon and surface plasmons in Sect. 2.6) offers at
least two, unique, highly important benefits: (1) the possibility to transmit infor-
mation with higher frequency (about *100 THz) and (2) the ability to confine light
in very small dimension objects.
The interaction of light with the surface plasmons of a metal surface give rise to
a particle called surface plasmon polariton (SPP).
SPP are (infrared or visible) electromagnetic waves, which travel along a
metal/dielectric interface in the same way that light can be guided in an optical
fiber. An SPP will propagate along the interface until its energy is lost, either by
absorption in the metal or by scattering into other directions. The term “surface
plasmon polariton” explains that the wave involves both charge motion in the metal
(“surface plasmon”) and electromagnetic waves in the air or dielectric (“polariton”).
SPPs can be excited both by electrons or photons. Excitation by electrons is created
by firing electrons into the bulk of a metal.
The generation of SPP by photons excitations waves is not possible unless special
techniques are employed to achieve phase matching. Among these techniques we
4.2 New Carrier Information Vectors (Plasmons and Surface … 79
can mention the prism coupling and grating coupling. Prism coupling is possible in
two configurations: Otto configuration and Kretschmann configuration.
In the Otto configuration, the light illuminating the wall of a prism is totally
internally reflected. A thin metal film is positioned close enough to the prism wall
so that photon tunnelling occurs through the air gap between the prism and the
surface. An evanescent wave can interact with the plasma waves on the metallic
surface and hence excite the plasmons.
In the Kretschmann configuration, the metal film is evaporated on top of a glass
prism. The film is illuminated through the dielectric prism. At a certain angle of
incidence where the in-plane component of the photon wave vector (k) in the prism
coincides with the SPP wave vector on an air-metal surface, resonant light tun-
nelling through the metal film occurs and a sharp minimum is observed in the
reflectivity from the prism interface indicating that light is coupled to surface
plasmons with almost 100% efficiency.
The mismatch of wave vector between the in-plane momentum kx ¼ k sin h of
incident photons wave vector k ¼ 2p=kph and the surface plasmon wave vector
b ¼ 2p=ksp (b is the real part of a complex parameter called the propagation
constant of the traveling waves) can also be overcome by using diffraction effects at
a grating pattern on the metal surface [2].
For a one-dimensional grating of grooves with lattice constant a, as depicted in
Fig. 4.2c. phase-matching takes place whenever the condition: b ¼ k sin h nG is
fulfilled, where G = 2p/a is the reciprocal vector of the grating and n = 1, 2, 3.
As with prism coupling, excitation of SPPs is detected as a minimum in the
reflected light.
The surface plasma frequency is given by [2]:
xP
xSP ¼ pffiffiffiffiffiffiffiffiffiffiffiffi ð4:1Þ
1 þ ed
here ed is the relative dielectric permittivity and xP the bulk plasma frequency given
in Eq. (2.67).
For example if the plasma frequency is about 10 eV, depending on the electrons
concentration in the thin film and on their effective mass, and if the dielectric is the
air (ed = 1) the surface plasma frequency at the interface gold/air will be about
7.0 eV (*170 nm).
Fig. 4.2 a Prism coupling in Otto configuration b Prism coupling in Kretschmann configuration
c Grating coupling of a light with wave vector k impinging on a metal grating surface of period a
Hence, the wavelength of surface plasmon polaritons can be much shorter than
the wavelength of incident photons and the application of SPPs can enable sub-
wavelength optics in microscopy and lithography beyond the diffraction limit.
4.3 Optical and Plasmonic Waveguides
The optical fibers and in general the optical wave guides, act as the transport
“cables” for the electromagnetic waves and can be considered in photonics as the
equivalent of the electrical cables in electronics. The waveguides can transport light
electromagnetic waves or surface plasmon polariton waves.
4.3.1 Optical Waveguides
To fabricate an electromagnetic waveguide a thin film (or a fiber), made of high

refractive index material (n2) is embedded between lower index materials (n1).
Hence if the electromagnetic wave arrives to the boundary at an angle which is
greater than the critical angle of total reflection, the electromagnetic wave is con-
fined inside the film (or inside the fiber).
The main parameters characterizing the waveguides are the refractive index and
the film thickness (or fiber diameter).
In an optical fiber, the refractive index difference in the core and cladding
determines the transverse modal structure of the fiber. The single mode fiber
(Fig. 4.3), is preferred for long distance data transmission, because the transmitted
optical signal pulse does not suffer distortions.
Optical waveguides can be realised also using organic materials like polymers
(PMMA or MEH-PVV). Figure 4.4a. depicts a ITO/SiO2/MEH-PPV/SiO2/Al sys-
tem that was published in [3] in 2010. The high refractive material MEH-PPV
Fig. 4.3 Light pulse propagation in an optical fiber a multimode fiber b single mode fiber
4.3 Optical and Plasmonic Waveguides 81
Fig. 4.4 a The structure of a conjugated polymer thin film waveguide sample adapted from Zhang
et al. [3] b Organic solar cell adapted from Ameri et al. [4]
(n = 2.40) is embedded into a lower refractive material, SiO2 (n = 1.48). The

architecture of this optical organic waveguide remind the architecture of organic
solar cells ITO/PEDOT:PSS/MEH-PPV:PCBM/LiF/Al Fig. 4.4b [4] (Table 4.1).
4.3.2 Plasmonic Waveguides
Figure 4.5 describes the architectures of metal-insulator-metal (MIM) and

insulator-metal-insulator (IMI) plasmonic waveguides. The relative electric per-
mittivity of the metal and dielectric are denoted by em and ed, respectively. The ratio
between the absolute value of em and ed is given by:
j em j
q¼ ð4:2Þ
ed
Park et al. [2] demonstrate that light trapping occurs without losses in the MIM
waveguide if q < 1.28 and for the IMI waveguide if q < 1.
In analogy with the electric current flow, the plasmonic “flow” can be divided
into two branches of a circuit. Figure 4.6 depicts the experimental scheme devel-
oped by Zia and Brongersma [18] to study the surface plasmon polariton
propagation.
The SPPs are first launched along the surface of a patterned Au film (on the left)
by an attenuated total reflection technique. These SPPs then excite the guided
polariton modes supported by two adjacent metal stripe waveguides. These stripes
perform an analogous role to the slits in the traditional Young’s double-slit
experiment. An apertured cantilever probe is used to locally tap into the guided SPP
Table 4.1 Lasers wavelengths and refractive index for different materials
Metals
Name n (450 nm) n (550 nm) References
Ag 0.40 0.26 [5]
Au 1.54 0.43 [6]
Al 0.70 1.04 [5]
Oxides
Al2O3 1.76 1.75 [5]
In2O3 1.86 1.78 [7]
ITO 1.99 1.86 [8]
ZnO 1.99 1.95 [9]
TiO2 2.63 2.51 [5]
SiO2 1.48 1.47 [5]
Glass 1.53 1.52 [5]
Polymers or small molecules
PEDOT:PSS 1.56 1.55 [10]
PPV 1.85 1.85 [11]
PMMA 1.49 1.49 [12]
MEH-PPV 2.40 2.10 [13]
Pentacene 1.50 1.52 [14]
Polystyrene 1.59 1.59 [12]
Polycarbonate 1.5–1.7 1.5–1.7 [12]
CH3NH3PbI3 2.82 2.88 [15]
Laser wavelengths
Name k (nm) References
InGaN blue laser 405–440 [16]
AlGaInP red laser 635 [17]
AlGaAs fiber optic com. 1064
InGaAsN fiber optic com. 1310
InGaAsP fiber optic com. 1625
Fig. 4.5 Trapping of light in plasmonic waveguides a (MIM) metal-insulator-metal and b (IMI)
insulator-metal-insulator waveguides. Reprinted with the permission from Park et al. [2] © 2010
OSA
4.3 Optical and Plasmonic Waveguides 83
Fig. 4.6 a Schematic of an experimental configuration used to visualize Young’s double-slit

experiment for SPPs. b Schematic of the equivalent dielectric structure used to model SPP
propagation and diffraction. Reprinted with the permission from Zia and Brongersma [18] © 2007
Macmillan Publishers Limited, part of Springer Nature
waves and scatter light towards a photodetector in the far field. The detected signal
provides a measure of the local field intensity just under the tip [18].
A graphene plasmonic waveguide was realised by Jin Tae Kim and Sung-Yool
Choi by embedding chemical vapour deposited graphene strips in a perfluorinated
acrylate polymer. With a low refractive index and material loss, this
two-dimensional metal-like plasmonic waveguide acts as a light signal guiding
medium for high-speed optical data transmission. 2.5 Gb/s optical signals were
successfully transmitted via 6 mm-long graphene plasmonic waveguides [19].
4.4 New Generators (Spasers)
Today, much of the long and medium distance data transmission in the world takes
place over optical fibers along which propagate light pulses from semiconductor
lasers.
As with solar cells, photodiodes or light emitting diodes (LED) the work prin-
ciple of a semiconductor laser is based on the theory of a p-n junction.
The difference from a LED is that in the case of the semiconductor lasers the p-n
junction is so heavily doped that the p and n doped semiconductors become
degenerate. This means that the Fermi level is situated in the valence band and in
the conduction band, respectively (Fig. 4.7a). At equilibrium, due to the high
potential barrier (eV0) electrons can’t move from a side to another. If the degen-
erately doped p-n junction is forward biased (Fig. 4.8b) by a voltage greater than
the band gap: eV > Eg, the applied voltage diminished the built-in potential barrier,
eV0 to almost zero. In these conditions electrons and holes can now flow from one
side to the other and recombine by emitting photons. By heavily doping and
pumping, the number of electrons in the conduction band near Ec will be greater
than the number of electrons in the valence band near Ev and hence is realised the
inversion of population in a laser diode. The population inversion takes place in a
layer along the junction, also call inversion (i) layer or active region, and for this
Fig. 4.7 a Graphene two-dimensional metal-like plasmonic waveguide b Illustration of surface

plasmon waves into graphene. Reprinted with permission from Fei et al. [20]. Copyright © 2013,
Rights Managed by Nature Publishing Group
Fig. 4.8 a Highly doped p-n junction at equilibrium b Inversion of population and semiconductor
laser function principle for the direct polarisation of the p-n junction
reason semiconductor lasers are also called p-i-n junction lasers. The emitted
photon with the energy Eg cannot excite electrons from EV (since there are no
electrons there) but can stimulate the electrons to fall from the conduction band to
the valence band, the active region is then said to have “optical gain”. The pumping
mechanism is realized by the forward diode current.
Even if the work principle of light emitting diodes and laser is based on the same
phenomena: the emission of photons by electron-hole recombination, the emitted
light characteristics are very different. The electromagnetic waves emitted by lasers
are monochromatic and coherent. LED’s generate multiple wavelengths which are
not coherent. For LED the peak output power is measured in milliwatt. For regular
laser output power is measured in watt.
4.4 New Generators (Spasers) 85
Fig. 4.9 a Regular laser vs b Random laser. Reprinted with permission from Wiersma [21]. ©
Macmillan Publishers Limited, part of Springer Nature. c ZnO ultraviolet random laser diode on
copper substrate. Reprinted with permission from [22, 67] © 2014 OSA
In a regular laser the light bounces back and forth between two mirrors that form
a cavity. After several passes through the amplifying material in the cavity, the gain
amplification can be large enough to produce laser light (Fig. 4.9a). Last decade a
new class of lasers, called random lasers (LR) have been also developed (Fig. 4.9b,
c). In a random laser light is confined into a highly disordered gain medium, not by
conventional mirrors, but by random multiple scattering between particles in the
disordered material. The gain medium keeps the light trapped long enough for the
amplification to become efficient, and for laser light to emerge in random directions
[21, 22]. The laser, pumped with incoherent light emits coherent light in random
directions.
Random lasers give the opportunity to fabricate easy less expensive lasers in
thins films on plastic or paper substrates. C. Tolentino et al. demonstrated in 2012
the first directional random laser emission from a dye-doped polymer film in the
presence of a scattering medium consisting of TiO2 nano-membranes [23]. I. Viola
et al. demonstrate in 2013 the first random laser on a piece of paper [24] (Fig. 4.10).
Random lasers produce speckle-free images and the generated images exhibit
superior quality than images generated with spatially coherent illumination [25].
The broad emission solid angle of a random laser is ideal for displays and appli-
cations such as sensing chips, coding documents or banknotes, intelligent packages,
by realizing integrated RL devices that would manifest itself with a unique emission
spectrum, only when excited using a suitable light [24].
A laser, is hence, a device that emits light through a process of optical ampli-
fication based on the stimulated emission of electromagnetic radiation. The term
“laser” originated as an acronym for “light amplification by stimulated emission of
radiation”. In the same way, if in place of photons we have plasmons we can create
a spaser: “surface plasmon amplification by stimulated emission of radiation”, or, if
photons are replaced by phonons a saser: “sound amplification by stimulated
emission of radiation” etc.
The first experimental demonstration of a spaser was done in 2009 [26]. The
phenomenon, involve resonant energy transfer from excited molecules to surface
plasmon oscillations and stimulated emission of surface plasmons in a luminous
mode. As for spintronic, physicists and engineers expect a faster and more compact
Fig. 4.10 Preparation of a paper-based photonic device. a Fabrication process: the left side
reports the oblique view and the right side the cross section along the dash-dotted line. b Confocal
microscopy of the structure of native paper. c–f Photographs of one of the microfluidic circuits
realized on paper after adding a fluorescent dye to the sample reservoirs. The images show a
reference empty device (c) and different images of devices partially filled with a lasing dye
demonstrating the high flexibility of integration of the lasing paper that can be bent (d), rolled
(e) and vertically aligned (f). Scale bars: 100 mm (b); 5 mm (c); 1 cm (d–f). Reprinted with the
permission from Viola et al. [24] © 2013 Royal Society of Chemistry
electronics. The ability of the spaser to actively generate coherent surface plasmons
could lead to new opportunities for the fabrication of photonic devices and have an
impact on technological developments seeking to exploit optical and plasmonic
effects on the nanometre scale.
By extending the laser-diode technology, Flynn et al. [27] demonstrated an
optically pumped spaser capable of generating > 25 mW of external peak power
from SPP-radiation conversion (Fig. 4.11). The optical gain was enhanced by
distributing eight quantum wells (QWs) on each side of the Au film throughout the
long-range SPP mode profile. The SPP mode at 1.46 lm was designed using the
transfer-matrix method with suitable semiconductor indices of refraction and Au
dielectric constant derived from ellipsometric measurements of evaporated Au
films. Important advantages of this design include room temperature operation near
a communication wavelength and an architecture suitable for extension to
all-electrical operation [27].
In a similar way as the gold thin film, when subjected to radiation, a graphene
sheet could become the place of the appearance of a plasmon amplification by
stimulated emission of radiation.
Spaser based devices can be used as an alternative to those based on electrical
currents such as transistors, microprocessors, memories and screens while over-
coming current limits to their miniaturization. The use of graphene and carbon
nanotubes appears to be particularly well suited because these materials are more
than a hundred times stronger than steel and can lead heat and electricity much
better than copper.
4.4 New Generators (Spasers) 87
Fig. 4.11 a Au-film plasmonic waveguide sandwiched between two dies containing the quantum
wells (QW) stacks. b The ridge architecture after dies are flip-chip bonded. c Rendering of the
bonded dies pumped from above and emitting diagnostic radiation to the right. d End-on
micrograph of the output facet, showing above-threshold diagnostic radiation at 1.46 lm emitted
from the end of the SPP waveguide over the width of 100-lm-wide confining ridge. Reprinted
with the permission from Flynn et al. [26, 27] © 2011 OSA
Lasers and spasers are the equivalent in photonics of the electrical generators.
The radiation emitted by a laser can be continuous but also pulsed. By using the
ultrafast saturable absorption in graphene the continuous radiation can be trans-
formed in pulsed radiation (Fig. 4.12) [27, 28].
4.5 Modulators (Electro-Optic, Electro-Plasmonic

or Opto-Plasmonic)
The electro-optic modulator is the component that converts the information con-
tained in an electrical signal into an optical information by modifying the phase or
the amplitude of the optical signal. A simple scheme of the electrical-optical and
optical-electrical data signal conversion is depicted in Fig. 4.13.
There are many types of electro-optic modulators. The most simple that we can
imagine are the light emitting diodes as transmitter and the photodiodes as recei-
vers. If the optical data transmission will be replaced in the future with faster
circuits using plasmons as information carrier vectors new electro-plasmonic or
optic-plasmonic modulators [29] will take the place of the actual electro-optic
modulators. The high potential for nanoscale light manipulation and the develop-
ment of a fully CMOS compatible electro-optical plasmonic modulator, said to be a
Fig. 4.12 a Graphene saturable absorber functioning principle. Image courtesy Dr. Zhengping
Wang, reprinted with permission from OSA Publishing China. b Experimental setup for the
tunable mode-locked fiber laser (LD: laser diode, WDM: wavelength division multiplexer, EDF:
erbium-doped fiber, ISO: isolator, OC: optical coupler, PC: polarization controller) Reprinted with
permission from Lee [28] © 2015 OSA
Fig. 4.13 The principle of data transmission by the electrical-optical and optical-electrical signals
conversion
future key component in chip-scale photonic circuits [30]. Last decade, surface
plasmons based elements are studied as a means of overcoming the size limitations
of photonic circuits for use in high performance data processing nanodevices [31].
Jin-Soo Shin and Jin Tae Kim proposed a silicon optical modulator using a
graphene-integrated hybrid plasmonic waveguide. This optical device is based on
the surface plasmon polariton absorption of graphene embedded in a hybrid Si slot
waveguide [32].
By electrically tuning the graphene’s optical properties, the mode attenuation
coefficient of the plasmonic waveguide is switched and hence the intensity of the
guided mode at the output port is modulated. The waveguide structure is highly
compatible not only with CMOS fabrication processes but also with CMOS electronic
device structures. In fabrication, the input Si waveguide and the lower part Si structure
in the hybrid plasmonic waveguide can be formed using a conventional
silicon-oxide-insulator (SOI) platform. The upper Si component in the hybrid plas-
monic waveguide can be configured using poly-Si. The vertical structure of the
graphene integrated hybrid plasmonic waveguide is similar to that of a MOS structure.
4.5 Modulators (Electro-Optic, Electro-Plasmonic or Opto-Plasmonic) 89
Fig. 4.14 a Pentacene organic electronic transistor b an artist view of a single-molecule optical
transistor as the standard symbol for an electronic transistor. Credit Robert Lettow. Reprinted from
ETH Zurich. “Optical computer closer: Optical transistor made from single molecule.” © Science
Daily, 3 July 2009. (https://www.sciencedaily.com/releases/2009/07/090702080119.htm)
Light from the Si waveguide is coupled into the hybrid plasmonic waveguide
when the Si waveguide and the graphene-integrated hybrid plasmonics waveguide
are highly synchronized [32].
4.6 Electronic and Optical Transistors
Hwang and Sandoghdar et al. [33] demonstrate in 2009 that a single dye molecule
can operate as an optical transistor and coherently attenuate or amplify a tightly
focused laser beam, depending on the power of a second ‘gating’ beam that controls
the degree of population inversion.
In electronics, the use of organic molecules remind the electronic transistors
using small molecules like pentacene [34–36] Fig. 4.14.
The optical transistor is the last basic element needed in photonics or in “plas-
monics” which will permit to be able to realize the same functions as an integrated
electronic circuit not by using electrons, but photons or plasmons. Researchers called
such a future plasmonic device, with transistors like properties, “plasmoster” [37].
4.7 Electronic Integrated Circuits and Photonics

Integrated Circuits (PIC)
By comparing the four basic elements in electronics and in photonics: the electron
in electronics vs the photon and plasmon; electrical cables vs optical fibers and
plasmonic wave guides; electrical circuits vs optical circuits; electrical transistors vs
Fig. 4.15 a Electronic integrated circuits versus photonic integrated circuits b Schematic view of
basic functions that an optical circuit must be able to perform to manage the flow of light in a
photonic crystal structure. Reprinted with permission from [38] © SPIE 2013, Image courtesy Dr.
Imanol Andonegui, University of Basque Country
optical transistors and plasmosters; electrical generators vs. pulsed lasers and spa-
sers we remark that photonics has built up, step by step, all the tools already
available in electronics.
These similarities lead to the idea that, in the future, we may be able to replace
devices that use electrons flows (mobile phones, computers, displays, etc.) with
equivalent devices that use photonic or a plasmonic flows (Fig. 4.15).
The new photonic devices are similar to the electronics ones. For instance, in
transparent flexible electronics and in third generation solar cells, new promising
electrodes are composed of three layer oxide/metal/oxide. We find these same
structures in photonics for plasmonic wave guides. This is also the case for organic
solar cells and organic wave guides [39] (Fig. 4.16).
By combining these two sciences: electronics and photonics, “plasmonics”
emerge as a n0ew research field at nanoscale dimensions. The name of “plas-
monics” was introduced in 2001 by Harry Atwater, an early pioneer in nanopho-
tonics and plasmonics devices.
4.8 Optical Data Transmission (LIFI and VLC)
LIFI (Light Fidelity) is a wireless communication system similar to Wi-Fi, but

using visible light instead of radio waves [40]. The information data is transported
by electromagnetic waves as is the case in the radio transmissions but the fre-
quencies correspond now to the visible spectrum range (see Table 1.3, Chap. 1).
The technology uses light emitting diodes as signal transmitters by switching the
current to the LEDs off and on at a very high rate. In LIFI technology the switch
on/switch off rate is too high to be noticed by the human eye and one of the
advantage is that the available bandwidth of the visible light spectrum is much
larger than that of the RF spectrum. This information transport is interesting for data
4.8 Optical Data Transmission (LIFI and VLC) 91
Fig. 4.16 Graphene applications in electronics and photonics
transport at small distances. Due to numerous obstacles on the light propagation,

LIFI cannot be used for data transmission on long distances, but in small pieces like
aircraft cabins or hospitals rooms (Fig. 4.17). This technology can be interesting
because it avoids interference with other radio waves. On long distances the
information need to be transmitted by using optical fibers in order to avoid losses.
That means the optical data signalis transported at long distance by the optical
fibers, then is transformed in electrical signal at medium transport distances and
again in optical signals if the LIFI-LED technology is used for very short distance
Fig. 4.17 Data transmission by LIFI

data transmissions. At our best knowledge at this moment there are no systems
which can transform directly the (wired) optical signal transported by optical fibers
in wireless optical signals, without using the electrical signal conversion.
The idea of Visible Light Communication (VLC) remember us the photophone
of Alexander Graham Bell far back in 1880. The signal containing the information
(speech) was transmitted by modulating a light beam, which travelled through air to
the receiver (Fig. 1.10, Chap. 1).
At present, the rate in LIFI transmission is about 100 Mb/s, by comparison in
optical fiber is of 10Tb/s–1Pb/s and in WIFI of 1–300 Mb/s.
4.9 Optical Manipulation (Optical Antennas, Optical

Tweezers, Photonic Motors)
Optical antennas are devices that convert freely propagating optical radiation into
localized energy and vice versa. They enable the control and manipulation of
optical fields at nanometre scale [41, 42]. By linking the propagation radiation and
confined/ enhanced optical fields the optical antennas give the opportunity to find
applications in optical characterization, manipulation of nanostructures optical
information processing, slow light and low-loss metamaterials [43–45].
The study of optical forces have gained an impressive development due to their
noncontact nature and ability to influence the motion of objects.
The huge research work done the last ten, fifteen years proved that we can move
and spin small objects just by using light beams [46–56].
By using the forces exerted by a strongly focused beam of light is possible to
trap and move objects ranging in size from tens of nanometres to tens of
micrometres. These optical tools, called “optical tweezers” becomes, with the
technology improvement, important instruments for the research in the fields of
medical applications, biology and physical chemistry.
After optical tweezers [57–61], rotations of polystyrene ball by lasers beams
[49], recent work demonstrates the realisation of the world’s fastest man-made
spinning object by rotating an optically levitated microsphere at 600 million rpm
[62].
Another example of a spin movement by using light, is the Crookes
radiometer (Fig. 4.18), known also as a heat engine run by light energy or a light
mill. Here the rotating movement is due to the collisions, in low vacuum, of the air
molecules with the vanes having a reflecting face in one side and an absorbing
(dark) one in the other side. Even different, all this experiments proves the power of
light and maybe the possibility in the future to realise photonic motors.
The light–matter interaction can be used not only for advanced studies in the
energy conversion, information transport and optical manipulations but also in the
emergent area of levitated optomechanics [62].
4.10 Laser Propulsion 93
Fig. 4.18 a Crookes radiometer b Optical manipulation of 16 polystyrene micro-particles each of

3 µm in diameter. The trapping beams (output modes) and the white-light illumination are both
delivered by multimode optical fibres. Reprinted with permission from Čižmár and Dholakia [49]
© OSA Publishing 2011
4.10 Laser Propulsion
Photon propulsion has been considered to be one of the best available propulsion
concepts, as a next generation propulsion that can make interstellar flight possible.
However, compared with its theoretical progress, its actual demonstration either in
laboratory settings or space environment has progressed very slowly [63].
Lightcraft experiments were done in Germany and USA. Results on vertical
flight and pendulum experiments carried out with a simple paraboloid type light-
craft in the air-breathing mode have been reported in [64, 65]. Pulsed laser energy
of up to 400 J/pulse was delivered from a highly reproducible e-beam sustained
CO2-laser at repetition rates up to 45 Hz. The lightcraft mass was varied in the
range of between 22 and 55 g. An average thrust of 1.1 N has been derived from
the flight data and the highest impulse coupling coefficient found in the pendulum
experiments was 33.3 10–5 Ns/J [65]. A first demonstration of a photonic laser
thruster was reported in 2008 in [66].
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Chapter 5
Energy Conversion or Direct Use?
After discussing about data transmission, materials, transport phenomena in solid

state materials, solar energy conversion into electricity and photonic devices, this
last chapter is devoted to the Energy.
Energy, from ancient Greek word, “enérgeia” means “force in action”. Hence,
energy and forces are strongly linked. The more intense are the forces, the greater
the associated energy is. The energy stored in a quantity of water which falls is due
to the gravity forces, the origin of the energy stored in a litter of fuel is due to the
forces that link the atoms, the origin of nuclear energy is due to the high attraction
forces of nucleons inside the nucleus of atom. The existence of the “energy” is
proved by the effects that can be remarked when the energy is transformed from a
form to another one. The main known energy forms today are: the mechanical
energy, the thermal energy, the chemical energy, the electrical energy, the mag-
netical energy, the nuclear energy and the radiative energy. Generally the notion of
energy is also associated to the “dynamics of a mass”: bodies in movement, atoms
in movement, electrons in movement etc. Table 5.1 presents the different types of
energies and the mathematical associated formulas.
All bodies from macroscopic, to microscopic and nanoscopic scale can be seen
as energy containing boxes, the smallest “box” for transporting the energy being the
photon.
Withal, the thermodynamics physics principles indicate that energy is conserved.
That means that energy can’t be created and can’t be destroyed. Thus, at Universe
scale, the total energy is the same and at human scale and as an absolute value, we
have enough energy, or in any case, this energy is the “same” and we can’t
“produce” more. We can only transform it from one form to another. The only
problem, if we can say that, is that, in general, this energy is not in the desired form
and the efficiency to transform it from a form to another is rarely equal to one
(100%).
For today human activities, different renewable or non-renewable sources of
energies are used for transportations, for rotations or translations in different

98 5 Energy Conversion or Direct Use?
Table 5.1 Different types of energies and associated mathematical formulas

Energy type Mechanical Thermal Chemical Electrical Magnetic Nuclear Radiative
Movement Bodies Molecules Atoms Electrons Atoms Nucleons Photons
of or energy
stored in
Formula 2 mv
1 2
i KT
2
DH 1 qQ
4pe0 r
m B Dmc2 hm
mc 2 DG I Rt
2 2 LI
1 2
2 kx
1 2
K mMr
industry processes or domestic activities, for public and domestic buildings heating
or cooling, for lightening, for communications, informatics activities etc.
Moreover, while humanity has proved it can thrive on technologies derived from
sand by constructing cities, photovoltaics panels for producing electricity, elec-
tronics devices and a planetary communication network, it remains to be seen
whether the same can be said for carbon in its different allotropic forms: graphene,
fullerene, diamond, etc.? Will carbon be the future element of choice of all new
modern technologies? (Fig. 5.1).
At planetary scale, we can see the Earth as a source of energy in terms of its total
mass and of the energy contained in all links (links between atoms, nucleons etc.).
The nuclear reactions, fuel or other non-renewable natural resources’ burn, are
equivalent to an irreversible diminution of the planet mass. Besides, the Earth
receives continuously energy from the Sun and this energy is the source of our
planet life including our existence itself. At human time scale this process of
energy—reception is infinite.
If the need of “energy” is translated by the need of “dynamics” or “movement”
or “perpetual movement” that means a perfect equilibrium should be found in order
to be able to maintain this continuous “movement”. Perpetual movement or cyclic
processes exist in nature: the Earth turns around the Sun, the Moon turns around the
Earth and Erath turns around it’s own axis, electrons “turns” around the nucleus. It
can also be observed with the continuous cycle of water, the wind, the tides etc.
Fig. 5.1 Today and future materials for electronics and photonics
5 Energy Conversion or Direct Use? 99
Fig. 5.2 Simplified scheme of motors work principle
A “dynamics” or a motor functioning, supposes, in general, a difference between

masses, charges (electrical potential) or temperatures. The small-mass bodies turn
around big-mass bodies. The electrons flow when a difference of the electric
potential exists. A thermal motor turns when a difference of temperature exists
(Fig. 5.2).
Except the magnetical energy, all types of transformation of energy from a form
to another are well known and exploited today. Table 5.2 resumes these transfor-
mations and the called associated effects.
The conversion efficiency, η, of the energy from a form to another is defined as
the ratio between the final desired form of obtained energy and the initial consumed
energy. This ratio is a sub unitary number for the most of energy transformation
processes. That means that the more we multiply the transformations process more
the smallest the total conversion efficiency is.
The nonsense for multiplying energy transformations can be simply understand
by an easy mathematical calculus. If the processes to obtain the energy in a specific
form, pass by two transformation processes with the efficiencies η1, η2 (ex:
η1 = 0.9, η2 = 0.8) the effective conversion efficiency is:
geff ¼ g1 g2 ¼ 0:72 ðgeff \g1 ; geff \g2 Þ
For three transformations (ex: η1 = 0.9, η2 = 0.8, η3 = 0.7), the effective con-
version efficiency is:
geff ¼ g1 g2 g3 ¼ 0:507 ðgeff \g1 ; geff \g2 ; geff \g3 Þ
In other words, more we transform the energy more we “loose” it because just a
small part is transformed in the desired exploitable energy form and the rest of the
initial energy is transformed in general in thermal “wasted” energy which today is
difficult to be exploited or transformed further.
Today we transform most of energy resources into electricity in order to meet
most of our needs. However, with the recent progress in science the question that
100
Table 5.2 Energy transformations

Transformation Initial energy
Mechanical Thermal Chemical Electrical Magnetical Nuclear Radiative
Final Mechanical kinetic/potential Thermal Explosion Electrical motors Alpha Laser
energy motors muscle radiation propulsion
Thermal Frictions Heat Combustion Joule effect – Nuclear Direct heating
exchanger reaction
Electrical Electro-magnetic Seebeck effect Electro-chemical Transformer – Beta Photovoltaic
generators Fuel cell radiation
Magnetical Dynamo or – – – – – –
alternators
Chemical Matches Synthesis Chemical Electrolysis – Radioactive Photo-synthesis
reactions decay Photo-chemical
Nuclear Particle Supernova – Synchrotron – Nuclear Mössbauer
accelerator isomerism spectroscopy
Radiative Synchrotron Incandescence Chemical Light – Gamma Non-linear
luminescence emitting radiation optics
diode
5 Energy Conversion or Direct Use?
5 Energy Conversion or Direct Use? 101
Fig. 5.3 Solar energy exploit for photonics and electronics devices
could rise is: “it will be possible in the future to exploit directly solar energy for all
our modern life essentials without transform it in electricity?” (Fig. 5.3).
For heating, we can and already use often solar energy directly, without trans-
forming it. If light storage is possible through plasmons, laser cavities, or light
trapping as in the black body model, it will be possible to directly use solar energy
for lighting too. Optical manipulation and optical engine concepts have already
been experimentally demonstrated, and the progress in photonics with optical cir-
cuits, optical transistors, etc. has shown that photonic or plasmonic informatics
might be possible too. If laser propulsion will be achieved, and optical engines will
work, we may also have in the future motors working with light.
Theses promising steps towards the direct use of light for different applications
may let us think that in the future the simple direct use of solar energy will be
plentiful to turn on all the machines of our upcoming modern life.
Conclusions
Arriving at the end of this book the lecturer will found that we are at the beginning
of new and huge research areas. Artificial materials with periodic structures open
the Era of a completely unknown field in materials physics. The replacement of
silicon with carbon and carbon based materials, and the replacement of electrons
with photons in electronics will completely revolutionize the existing device fab-
rication for information transport.
Beside “Plasmonics”, the emerging research field at the interface between
electronics and photonics, “Spintronics” (spin transport electronics) and
“Magnonics” are other new emerging fields, associated to spin and magnetic
interactions, which will contribute in the future to the manufacturing of new data
transport systems. As photonic crystals, which are metamaterials with alternating
refractive index, a magnonic crystal is a magnetic metamaterial with alternating
magnetic properties.
Solid state physics fundamentals, applied first for the understanding of the
electron transport in periodic structures, can be hence extended to the study of other
particles-waves transport in periodic natural or artificial structures. As the tailoring
of optical band gaps for photons in photonic crystals, the nanotechnologies give the
opportunity to tailor magnonic bandgaps, analogues to the electronic band gaps that
are formed in all natural semiconductors. Hence all fundamentals of electronics
devices functioning can be extended to put in place the new work principles and
manufacturing procedures of new devices based on new particles: plasmons,
photons, spin waves etc.
The understanding of the magnetic part of the light will completely change the
understanding of photon-electron interactions and today understanding of electronic
and photonic devices. The unexplained yet and strange behaviour of perovskite
materials used in the new class solar cells will be maybe also explained through the
magnetic interactions between the light and perovskites material units cells.
The full understanding of light magnetism origin and the magnetic interactions
will complete the unfilled zones of energy transformation knowledge (Table 5.2). It
will also explain the Universe formation, the nuclear forces, the elements formation,

Sciences and Technology, https://doi.org/10.1007/978-3-319-67337-0
104 Conclusions
the stars and living matter cycles, the abundance and scarcity of elements on Earth
and Universe, will explain the continuous movement of electrons around the
nucleus and the reason of the quantification of electronic levels in atoms, the
rotation period of the little stars around the big ones, the terrestrial magnetism, etc.

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SPRINGER BRIEFS IN

APPLIED SCIENCES AND TECHNOLOGY

More information about this series at http://www.springer.com/series/8884

Future Solar Energy Devices

ISSN 2191-530X ISSN 2191-5318 (electronic)

© The Author(s) 2018

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Angers, France Mihaela Girtan

1 A Parallel Between Electronics and Photonics . . . . . . . . . . . . . . . . . . 1

4.4 New Generators (Spasers) . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 83

1.2 Carrier Vectors and Transport Cables

Electronics is based on the transport phenomena of electrons and photonics on the

1.3 Pulse Generators

The development of electronics and of photonics have led to a lot of applications

1.4 Data Transmission by Analog and Digital Signals

The necessity to communicate is an ancestral need. The necessity to express an

Fig. 1.6 Communication evolution

Fig. 1.7 Analog versus

Table 1.2 Alphabet and Arabic numerals in Morse code

Satellite Radio 10–50 Mb/s Many km

1. C. Roychoudhuri, Fundamentals of Photonics (SPIE Press Book, 2008)

2.1 Bands Energies Formation in Solids Crystalline

© The Author(s) 2018 15

The understanding of charge transport in low dimensional systems (thin ﬁlms,

2.2 Charge Carriers Transport in Bulk Semiconductors

The calculus of transport coefﬁcients in bulk materials (electrical conductivity,

If an external perturbation is applied to the solid, such as: an electric ﬁeld, a

is the velocity of electron in the crystal and E—the energy.

Hence, in the approximation of ﬁrst order:

The equilibrium distribution function of electrons for degenerate semiconductors is

and for non-degenerate semiconductors, by Boltzmann distribution function:

We consider the case of non-degenerate semiconductors and we replace f0 with

mn being the effective mass of the electron, in the crystal,

It is easy to show that r~k f0 ¼ 0 and the relation (2.15) becomes:

Considering the expression (2.7) for f1 we deduce:

Now introducing (2.13), (2.14) and (2.17) into (2.12) we obtain:

and after simpliﬁcation:

So rel. (2.19) becomes:

and we obtain the vector equation:

The equation is of type: ~ a þ~

This means that we can ﬁnd the ﬁnal solution ~

The electron current density is given by:

where dsk = dkxdkydkz is the elementary volume in the space k.

By changing the variable k to E (the energy) we have:

By calculus and taking into account that:

we can expresses jnx as:

Here n is the charge carriers concentration (electrons), ln—electrons mobil-

where, s0 is a parameter depending on material nature and sometimes on temper-

Hence, the electrons mobility for non-degenerate semiconductors can be expressed

According to (2.29), the electrical conductivity for n-type non-degenerate

Hall Coefﬁcient in the Relaxation Time Approximation

For a p type non-degenerate semiconductor, the Hall coefﬁcient of holes is:

and for mixed conduction:

In the hypothesis s ¼ s0 E p using the formulae of average value we deduce:

Seebeck Coefﬁcient in the Relaxation Time Approximation

and in the assumption s ¼ s0 Ep

2.3 Transport Coefﬁcients in Thin Films. Semi-classical

In addition to the carriers scattering mechanisms presented in the bulk single

The electrical conductivity is obtained in a similar way as in the case of bulk

For Non-degenerated Semiconductors [12]

with C1(1/c) and C1(2/c) given by:

The presented formulas correspond to the Fuchs-Sondheimer and Schrieffer theo-

rg expðEa =KT) ð2:57Þ