Advances in Material Research and Technology

Shadia Jamil Ikhmayies Editor

Advances in Energy
Materials
Advances in Material Research and Technology

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Shadia Jamil Ikhmayies, Physics Department, Isra University, Amman, Jordan
This Series covers the advances and developments in a wide range of materials such
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Shadia Jamil Ikhmayies
Editor

Advances in Energy
Materials

123
Editor
Shadia Jamil Ikhmayies
Jabal El-Hussain
Amman, Jordan

ISSN 2662-4761 ISSN 2662-477X (electronic)

Advances in Material Research and Technology
ISBN 978-3-030-50107-5 ISBN 978-3-030-50108-2 (eBook)
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Preface

Energy materials are those materials that can be used in any technology to produce,
enhance, generate, convert, transmit, utilize, or store energy. They include materials
used in photovoltaics, fuel cells, batteries, supercapacitors, thermoelectrics, hydro-
gen technologies, and phase change materials. Energy materials are key roadblocks
to improve performance in a number of important energy technologies including
energy storage in batteries and supercapacitors, and energy conversion through solar
cells, fuel cells, and thermoelectric devices. Since energy is a key issue of the
modern society, and the world-wide demand for energy is growing, this great
challenge can be meet by using sustainable, efficient, and renewable energy sources.
Hence, the development of energy materials is necessary for the development of
energy production, conversion, transmission, and storage technologies. That is,
without continuous advancement of energy materials and developments of new
ones, it is not possible to increase the performance of energy technologies. So,
continuous research is necessary to accelerate the advances in energy materials, to
have energy technologies of higher performance and lower cost, and to increase the
efficiency and improve the sustainability of energy systems.
This book presents recent research on energy materials from various aspects,
synthesis of energy materials to energy storage devices, focusing on materials that
can potentially be used in the production of solar cells. It discusses in detail the
latest synthetic methods, processes, characterization methods, and applications of
materials like perovskite materials, metal sulfides, metal oxides, nanomaterials, and
phase change materials. The book contains nine chapters which include funda-
mental and recent applied research on the design of different energy materials used
in different forms of renewable energy conversion, harvesting, storage, and uti-
lization. Materials scientists, chemists, physicists, materials and renewable energy
engineers, people in industry, in addition to graduate and undergraduate students in
physics, chemistry, and different branches of engineering will benefit from this
book. This book supplies the reader with the basic knowledge of applied research
and innovation and provides with the relevant information on the materials used in
energy technologies, including background information on the technology itself.

v
vi Preface

The first three chapters of the book share a relationship with the materials that are
used in the manufacture of solar cells. The first chapter entitled “Studies on Synthesis
and Various Characteristics of Green Materials for Energy Conversion Applications”
by Ranjana Jha et al. focuses on the green materials, where various green materials
and their synthesis techniques have been discussed in details. The primary focus of
this chapter is to use green materials for energy devices. The second chapter entitled
“Advancement in CdIn2Se4/CdTe Based Photoelectrochemical Solar Cells” by
Subhash Chander deals with the preparation of cadmium indium chalcogenide thin
films from aqueous medium by the simple and cost-effective spray pyrolysis method,
and the consequent use of the produced films in heterojunction solar cell applica-
tions. The third chapter entitled “Cadmium Sulfide Thin Films by Chemical Bath
Deposition Technique” by M. S. Aida and S. Hariech describes the usefulness of
chemical bath deposition (CBD) technique—which is a low cost method—to pro-
duce high quality thin films of cadmium sulfide for large-scale applications. The
fundamentals of CBD were described with emphasis on growth mechanisms and the
influence of key parameters on the films.
The fourth chapter entitled “Development of the Concept of a Spheroidal Shape
Anode for a Solid Oxide Fuel Cell” by Bogdan Vasyliv and Viktoriya Podhurska
presents a calculation of stress and strain distributions in the YSZ–NiO spheroidal
shape anode-substrate for a solid oxide fuel cell (SOFC) under the pressure of an
operating environment using the finite element analysis. The authors compared the
features of the spheroidal shape anode with those of the cylindrical shape anode.
They also suggested the radii ranges for the cylindrical and spheroidal parts of the
anode ensuring its improved deformation resistance and more uniform stress
distribution.
The next two chapters share a relationship with nanomaterials based photo-
voltaics. The fifth chapter entitled “Advances in Nano-Materials Used in
Photovoltaic/Thermal Systems” by Ali H. A. Al-Waeli and Hussein A. Kazem
presents classifications of PV/T systems, principles, and performance. The chapter
provides a case study of three different PV/T systems which are; nanofluid and
nano-phase change material (nano-PCM) based PV/T, a water-based PV/T with a
PCM tank, and water-based PV/T with water tank. The findings show overall
improvement in thermophysical properties as nanoparticles are added to the base
fluid (water) and phase change material (PCM). Moreover, highest performance is
attributed to the nanofluid and nano-PCM based PV/T system. The sixth chapter
entitled “Si Quantum Dots for Next-Generation Solar Energy Harvester” by Mrinal
Dutta focuses on the progress and growth of Si quantum dots (QDs) based pho-
tovoltaic devices with the synthesis techniques as well as the broad range emission
properties of these Si QDs. The author discussed the issues related to p-type and
n-type doping of these QDs, reported the performances of several photovoltaic
devices, and discussed several routes for optimizing the performance of these Si QD
cells.
The seventh and eighth chapters are related to perovskite materials and their use
in energy harvesting and energy storage. The seventh chapter entitled “Progress in
Growth and Development of Perovskite Single Crystals and Their Potential Use in
Preface vii

the Future Devices” by Mrinal Dutta and Aishik Basu Mallick provides recent
research and elaborated discussion on the growth of perovskite single crystals by
different growth techniques, and the fascinating properties of these perovskites
single crystals. In addition, the authors focus on the applications of these single
crystals in energy harvesting and high energy radiation detection. The eighth
chapter entitled “Perovskite Oxides as Advanced Energy Materials for Solid Oxide
Fuel Cell and Supercapacitor Applications” by P. Muhammed Shafi presents a
detailed explanation of the crystallographic structures and physiochemical proper-
ties of the ABO3-type perovskite oxides (where A and B are cations of different
atomic and mass numbers). It focuses on the applications toward anionic as well as
cationic storage mechanism for the supercapacitor electrodes and towards all the
three components (cathode, anode, and electrolyte) of solid oxide fuel cells
(SOFCs).
Finally, the ninth chapter entitled “Phase Change Materials” by Rabab Jarrar
discusses the main types of Phase change materials (PCMs) with their advantages
and disadvantages. It presents some of the efforts made to overcome the disad-
vantages during the last three decades and those made to improve their performance
and to demonstrate their most common thermal applications.

Amman, Jordan Shadia Jamil Ikhmayies

Contents

Studies on Synthesis and Various Characteristics of Green Materials

for Energy Conversion Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Ranjana Jha, Medha Bhushan, and Rekha Bhardwaj
Advancement in CdIn2Se4/CdTe Based Photoelectrochemical
Solar Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Subhash Chander
Cadmium Sulfide Thin Films by Chemical Bath Deposition
Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
M. S. Aida and S. Hariech
Development of the Concept of a Spheroidal Shape Anode
for a Solid Oxide Fuel Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Bogdan Vasyliv and Viktoriya Podhurska
Advances in Nano-Materials Used in Photovoltaic/Thermal
Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Ali H. A. Al-Waeli and Hussein A. Kazem
Si Quantum Dots for Next-Generation Solar Energy
Harvester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Mrinal Dutta
Progress in Growth and Development of Perovskite Single Crystals
and Their Potential Use in the Future Devices . . . . . . . . . . . . . . . . . . . . 159
Mrinal Dutta and Aishik Basu Mallick
Perovskite Oxides as Advanced Energy Materials for Solid Oxide Fuel
Cell and Supercapacitor Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 181
P. Muhammed Shafi
Phase Change Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
Rabab Jarrar

ix
Studies on Synthesis and Various
Characteristics of Green Materials
for Energy Conversion Applications

Ranjana Jha, Medha Bhushan, and Rekha Bhardwaj

Abstract Energy has become one of the major concerns of the twenty-first century
because of the social progress and development in human standard of living.
The requirement for energy is increasing constantly, even though conventional
combustion-based energy will keep on playing a leading role in gathering our
demands in near future. The impending scarcity, rising price and increasing envi-
ronmental pollution of fossil fuels are approaching humans to build up sustainable,
low-cost and clean energy. Sustainable development is integrity of multidiscipline
thought combining social, environmental and economical aspects to build a live-
able human system. The sustainable development can be done by synthesizing green
materials. Green materials hold exceptional physical and chemical properties and
are found in nature in plenty, non-toxic and cost-effective. This chapter focuses on
green materials originating from the principles to reduce or eliminate the hazardous
substances in synthesis of chemical products. At fundamental level, researches in
green materials create alternatives to conventional materials or process that present
an ecological benefit. So, it deals with the description of cost-effective and low-
temperature-based synthesis which involves handling of non-toxic elements. Green
materials can be useful for a variety of fields such as in science and technology for
energy, construction of buildings, pollution management, engineering applications
and materials science. Green materials can be synthesized with the aim of energy
production.

Keywords Sustainable development · Green materials · Synthesis ·

Characteristics · Clean energy

R. Jha (B)
Research Lab for Energy Systems, Department of Physics, Netaji Subhas University of
Technology, New Delhi 110078, India
e-mail: [email protected]
M. Bhushan · R. Bhardwaj
Research Lab for Energy Systems, Department of Physics, Netaji Subhas Institute of Technology,
University of Delhi, New Delhi 110078, India

© Springer Nature Switzerland AG 2020 1

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_1
2 R. Jha et al.

List of Abbreviations

ZnO Zinc oxide

TiO2 Titanium dioxide
MoO3 Molybdenum trioxide
NiS Nickel sulphide
ZnS Zinc sulphide
g-C3 N4 Graphitic carbon nitrides
I sc Short-circuit current
V oc Open-circuit voltage
I Current
V Voltage
Pmax Maximum power
MPP Maximum power point
I mp Maximum current
V mp Maximum voltage
LED Light-emitting diode
OCV Open-circuit voltage
Pej Power
j Current density
Pef,max Maximum power
jmp Current density at maximum point
V mp Voltage at maximum point
ηPCE Efficiency
PCE Photovoltaic conversion efficiency
I LED Particular value of current for which its efficiency is maximum
V LED Particular value of voltage for which its efficiency is maximum
ϕT Total power radiated by the LED
PLED Electrical power (I LED · VLED ) supplied to it
FF Fill factor
jph Short-circuit photocurrent
V oc Open-circuit voltage
P Power
SQ limit William Shockley and Hans Queisser limit
HER Hydrogen evolution reaction
OER Oxygen evolution reaction
PEC Photoelectrochemical cell
Studies on Synthesis and Various Characteristics … 3

1 Introduction

There are limited resources on earth such as wood, ore and minerals that are vanishing
rapidly. The processes of converting them into useable products deplete the essen-
tial elements and pollute the environment which affects the ecosystems of many
animals and plant species. It is an urgent problem of reversing this issue. According
to report released by World Energy Council, global energy demand will increase
from year to year. In fact, the demand for energy will double by the year 2060.
However, primary energy demand will be in its peak until the year 2030. This primary
energy source includes energy derived from coal, oil and gas. Coupled with envi-
ronmental concern like global warming, the adoption of emerging energy sources is
beginning to encroach into the dominance of the primary energy source. Generally,
these emerging energy sources are referred as alternative energy resources which
are not derived from fuel and coal. Such alternative energy resources include, but
not limited to, solar energy, hydroelectric energy and wind energy. Therefore, it is
the goal of each inventor and researcher to design efficient energy devices where
maximum useful energy can be extracted. Sustainable development is a widespread
concept of modern culture. The idea has seemed to be vital strength in growth by
conserving natural resources. The development of novel and superior quality mate-
rials is one of the largely used efforts in setting up this concept. On the whole,
sustainable development is globally recognized dictate and it consists of non-toxic
and eco-friendly mechanized resources and equipments. Green synthesis, manufac-
ture and method optimization, play significant role in sustainable development but
also testing, performance evaluation and reliability are very important [1]. Future
growth in these resources will significantly depend on assurance with sustainable
training in research and equipments. “Sustainability” is a great deal than a current
catchphrase, though the exercise of the word has definitely enlarged in rate of recur-
rence, the perception itself is barely new, and it is one of the motivations or thoughts
that drives us to write this chapter.

1.1 Why Sustainable Environment?

Sustainability is related to all features of the entity such as constructing eco-friendly

homes and providing organic food, and use of renewable energy that look after its own
resources. The idea of sustainable progress was crucial and made familiar first in 1987
report “Our Common Future” prepared for the World Commission on Environment
and Development. Sustainable ecology, standard of living or a society is one that
supports itself and its environment.
Sustainability composed of three major factors, environmental protection, social
development and economic development, each of them depends on each other.
4 R. Jha et al.

1. Environmental Protection
Supporting and creating a sustainable ecology take part in important role on ecolog-
ical safety and security. Relations with surroundings are called as “sustainable” only
if it does not devastate the surroundings and resources given by it. Environmental
protection involves the assessment of use of resources that affects the environment.
The negative effects for environment should be minimized.
2. Social Development
Human and social welfare is an integral part of sustainability. The one who has
knowledge about sustainability and if its significance can be effectively transferred
to them, those are attracted more towards sustainability. It should be ensured that
creature should have access to basic resources, so that their health is being protected.
Human being can enjoy a good quality of life within a sustainable environment.
3. Economic Development
Sustainability devoid of economic growth cannot be succeeded. In order to encourage
persons, community and society to put in resources in sustainable development, there
must be a number of incentives for lasting return. Financial accomplishment is quite
a prejudiced concept.
The basic confront of sustainability consequently is to dissociate the value of living
and human being aspirations from energy and material intensities to accomplish them.

1.2 Various Strategies to Create Sustainable Environment

Sustainable surroundings do not represent living with no luxuries but somewhat being
conscious of resource expenditure in a way that continues their supply for the future
and lowering needless wastage. Environmental skill is the study regarding finding
ways to guide a sustainable life. There is a variety of strategies to create sustainable
environment:
• Using green material for energy conversion devices.
• Installing and developing energy-efficient devices.
• If we are conserving the energy, it itself means generating source of energy.
• Reducing domestic energy uses.
• Turning off the lights and electronic appliances or devices if not using.

1.3 What Are Green Nanomaterials?

Green nanomaterials are the new material synthesized using the principles and prac-
tices of green chemistry. Green chemistry is a set a chemical philosophy that encour-
ages to reduce or eliminate the use and generation of hazardous substances and to use
Studies on Synthesis and Various Characteristics … 5

natural sources, un-hazardous solvents and energy-efficient processes in the synthesis

of nanomaterials. In today’s developing and challenging environment, green nanoma-
terials fulfil growing demand for energy, devices and extensive range of applications
in various sectors with improved quality. Green materials are synthesized in required
shape and size with better properties such as physical, chemical and optical proper-
ties that gives better performance according to the demands [2, 3]. There are various
green materials such as metal oxides (ZnO, TiO2 , MoO3 ), metal sulphides (ZnS and
NiS) and graphitic carbon nitride.

1.3.1 Green Materials for Energy Generation

Metal Oxides

Zinc Oxide
Zinc oxide (ZnO) is a multidimensional material due to their unique chemical, struc-
tural and physical properties. On the basis of morphology, ZnO can be classified
into new materials with potential applications. ZnO can arise into 1-D, 2-D and 3-D
structures. 1-D structures include nanorods, nanotubes, nano-needles etc. 2-D struc-
tures are nano-sheet, nano-plates and 3-D structures are nano flower, snowflakes, etc.
[4]. Due to their unique morphology, ZnO nanoparticles are used in various applica-
tions such as solar cell, LED, supercapacitor and batteries. ZnO is a wide band gap
semiconductor. It has two most stable states, hexagonal and cubic phases [5]. ZnO
is classified into two groups II and IV in the periodic table. ZnO has high excitonic
binding energy 60 meV [6]. It has low charge transfer resistance, large surface area,
high electron mobility, at room temperature. ZnO shows strong luminescence; thus,
it can be used as photo-anode in solar cell, such as electrode in LED and batteries
[7]. ZnO is also used in converter, sensors and energy generator, because ZnO has
high piezoelectric constant, hardness and rigidity. ZnO has wide band gap 3.37 eV,
and its prospective effects were observed on the electrical conductivity and optical
absorption properties of the materials [8]. It is an excellent emitter of UV light and
absorber and shows high electrical conductivity. Due to these properties, ZnO is used
as photo-anode in PEC and DSSC [9].
Titanium Dioxide
Titanium dioxide (TiO2 ) is a non-volatile, less soluble, stable compound. It has less
thermal conductivity and shows perverse characteristics. TiO2 has three stable states,
anatase, brookite and rutile, and their crystal structure is tetragonal, orthorhombic
tetragonal, respectively. Anatase and rutile phases occur naturally and are easily
synthesized in the laboratory [10]. Brookite phase is unstable and very difficult to
synthesize, at low scientific interest. TiO2 is amphoteric material, even through less
basic than acidic. Each phase has its own importance. Rutile phase is more compact
and has high refractive index and higher density than the anatase phase. Titanium
dioxide is non-toxic and eco-friendly material. Due to their excellent morphology
6 R. Jha et al.

and low energy band gap, highly crystalline materials are used in various industrial
applications. Titanium dioxide is used as photo-anode in various types of solar cell.
Titanium dioxide has high dielectric constant and high electrical resistance and shows
excellent electro-catalytic properties; due to these properties, TiO2 is used in gas
sensor, corrosion protective layer, etc.
Molybdenum Oxide
Molybdenum oxide is the one important class of transition metal oxide. Molyb-
denum oxide has several phases. Different phases of molybdenum dioxide depend
upon the concentration of precursors used during synthesis process, reaction time,
temperature, etc [11]. Molybdenum dioxide is reduced to (MoO3−x , 2 < x < 3)
and fully stoichiometric molybdenum trioxide (MoO3 ), accompanied by Mo4+ ions
oxidized to Mo5+ and Mo6+ , and its colour varies from dark blue to light yellow and
green/blue [12]. Molybdenum dioxide has excellent melting point, chemical stability
and high conductivity, because MoO2 has multiple valences which are induced by
sufficient amount of oxygen vacancies. Thus, these properties make it good candidate
of electrode in energy conversion devices [13].

Metal Sulphides

Nickel Sulphide
Nickel sulphide is the important constitute of metal sulphides and has many phases
such as NiS, Ni3+X S2 , Ni3 S2 , Ni7 S6 , Ni7 S2 , Ni3 S4 and NiS2 [14]. Out of these phases,
nickel sulphide has two prominent phases, β-NiS rhombohedral phase and α-NiS
hexagonal high temperature phase. Nickel sulphide has unique optical and electrical
properties, and it has low charge transfer resistance, high conductivity, long cycle
life, high theoretical capacity. Due to these properties, nickel sulphide has many
applications in energy conversion devices. Each phase of nickel sulphide has its own
applications such as NiS2 used as counter electrode in various types of solar cell and
Ni3 S2 used as electrode in supercapacitor, lithium-ion batteries and so on [15].
Zinc Sulphide
Zinc sulphides have two most stable states: one is hexagonal phase named as wurtzite,
and second state is cubic phase known as zinc blende. It has a large exciton energy
(40 meV) [16]. ZnS is a multifaceted wide-gap semiconductor that shows superior
chemical stability against hydrolysis and oxidation [17]. It is non-toxic unlike other
chalcogenide compounds including cadmium sulphides, selenides, etc [18]. Zinc
sulphide has wide energy band gap which is the highest value of the II-IV group
semiconductor [19]. In ambient atmosphere, ZnS has two polymorphs: cubic zinc
blende (ZB) and hexagonal wurtzite (WZ) [20]. Both the phases of zinc sulphide
can be used in energy conversion devices such as solar cell, batteries and LED [21].
As one of the most important semiconductors, ZnS with its wide and direct band
gap energy of 3.7 eV has been known for a long time as a multifaceted and superior
Studies on Synthesis and Various Characteristics … 7

phosphor host material [22]. ZnS has high theoretical and specific capacitance, high
cyclic stability, areal capacitance; due to these properties, ZnS is used as anode mate-
rials for electrochemical devices such as supercapacitor and lithium-ion batteries.
But it is also advantageous due to natural presence in abundance of S and Zn and
low cost [23].

Graphitic Carbon Nitride

Graphitic carbon nitride belongs to carbon nitride family. It can be synthesized by the
polymerization of melamine, dicyandiamide or cyanamide, and shows semiconductor
properties such as high mobility of charge carrier, large surface area, highly stable
and high theoretical capacity. Due to these properties, it can be used as electrode in
supercapacitor, batteries, solar cell [24, 25].

2 Synthesis of Green Energy Materials

2.1 Various Methods for Synthesis of Nanomaterials

2.1.1 Two Approaches for the Synthesis of Nanomaterials

(i) Bottom-Up Approach

The main aim of this approach is to synthesize uniform shape, size and distribution
of all the particles. It starts from atomic level to nanoscale level. It can be done in
solutions such as chemical vapour deposition and sol-gel. This method is generally
used for the synthesis of metallic nanoparticles. Bottom-up approach is more advan-
tageous than top-down approach in nanofabrication, because it produces less defects,
better short- or long-range order and homogeneous nanostructures. A disadvantage
of this approach is that the production of large scale is very difficult and also chem-
ical purification of nanoparticles is essential. The schematic illustration is shown in
Fig. 1.

(ii) Top-Down Approach

This approach is based on the bulk materials to make smaller, miniaturizing or

breaking down of solid materials into smaller particles by applying external forces.
In this method, many thermal, chemical and physical processes are used for the
formation of nanoparticles. This technique is a cost-effective technique, and we can
easily control the shape and size of nanoparticles. The main disadvantage of this
technique is impossible to get perfect surface, edges due to cavities and roughness
in nanoparticles. The schematic illustration is shown in Fig. 1.
8 R. Jha et al.

Fig. 1 Schematic illustration of the bottom-up and top-down technique

2.1.2 Hydrothermal and Solvothermal Methods

Hydrothermal and solvothermal methods are common methods which are used for
synthesis of inorganic nanoparticles. Hydrothermal/solvothermal synthesis carried
out in a pressurized vessel is known as autoclave. If water is used as a solvent, this
method is knows as hydrothermal method. If variety of solvent is used except water,
then the method is known as solvothermal method. Advantages of these methods are
that we can easily control the size, shape and crystalline phase of the nanoparticles
by changing the reaction conditions such as temperature, pressure, reaction time,
solvents ratio and pH. The schematic illustration is shown in Fig. 2.

2.1.3 Co-precipitation Method

Co-precipitation method is a very simple method for the synthesis of nanoparticles.

This method is generally used for the synthesis of fluoride, oxide or nanophosphors.
In co-precipitation method, two types of solutions are required: one is cation and other
is anion. For cation and anion solutions, we use nitrate, chloride, acetate, etc., used as
precursors, and distilled water, ethanol, cyclohexane, N,N-dimethyl formaldehyde,
etc., used as solvents. The cation and anion solutions are prepared separately, and
after that, precipitating agent is added drop-wise into another solution with constant
stirring which results in the formation of the desired compound. The main advantage
of this method is that large amount of nanoparticles can be easily synthesized in a
short time. Also, kinetic factor only helps to control the growth rate which limits the
particle size distribution. The schematic illustration is shown in Fig. 3.
Studies on Synthesis and Various Characteristics … 9

Fig. 2 Schematic
illustration of the
conventional hydrothermal
method

Fig. 3 Schematic
illustration of the
co-precipitation method
10 R. Jha et al.

Fig. 4 Schematic
illustration of the thermal
decomposition method

2.1.4 Thermal Decomposition Method

Thermal decomposition or thermolysis is a decomposition of precursors (metal

oxides, sulphides, etc.) in the presence of hot suitable surfactant. The decompo-
sition may be driven by light or heat. In this method, yield is more than the other
methods. This process is endothermic process, but there are some limitations such
as controlling nanoparticle size and poor uniformity of the particles. The schematic
illustration is shown in Fig. 4.

2.1.5 Sol-Gel Method

This is the most reliable method for the production of uniform particle size distribu-
tion. It is a wet-chemical technique which is generally used for synthesis of ceramics
nanoparticles. Metal alkoxides, nitrates and metal chlorides are used as precursors.
These precursors along with chelating agent and surfactant dissolve in de-ionized
water or other suitable solvent. Prepared solution is heated continuously with constant
stirring until solvent is transformed into sol, which will later get converted into gel.
This technique is simple and cost-effective, and it produces highly pure and uniform
nano-structured particles at low temperature. The schematic illustration is shown in
Fig. 5.

2.1.6 Microwave Synthesis

The basic principle of the microwave synthesis is the heating of materials by

microwave dielectric heating. This method depends on the capability of the materials
(reagent or solvent) to absorb microwave and convert it. Microwave radiations are
directly applied to the reactions not to the vessel, which increase the rate of reactions
and control the reaction parameters. In this synthesis technique, lower amount of
energy and lesser time is required. Less byproducts are formed in this process. Limi-
tation of this technique is choice of reactants. The schematic illustration is shown in
Fig. 6.
Studies on Synthesis and Various Characteristics … 11

Fig. 5 Schematic illustration of the sol-gel method

Fig. 6 Schematic
illustration of the
microwave-assisted synthesis

2.1.7 Micro-emulsion Technique

Micro-emulsion method is defined as macroscopically uniform, optically translucent

and thermally stable and isotropic dispersions constituting components, i.e. non-
polar phase (generally hydrocarbon, liquid or oil), polar phase (generally water)
12 R. Jha et al.

Fig. 7 Schematic illustration of the micro-emulsion technique

and surfactant. Surfactant molecules create interfacial layer separating organic and
aqueous phase. Micro-emulsion consists of mono-dispersed spherical droplets (5–
100 nm), water-in-oil and oil-in-water depending upon the surfactant. The nano-
droplet size can be varied by reaction parameters, e.g. types of stabilizer, surfactant,
temperature and pressure. The schematic illustration is shown in Fig. 7.

2.2 Different Green Precursors Required for Synthesis

of Green Materials

Nickel nitrate, nickel chloride, zinc acetate, thiourea, sulphur, L-cysteine, thioac-
etamide, titanium butoxide, titanium tetrachloride, molybdenum hex hydrate, urea,
de-ionized water, aqueous ammonia, CTAB, PVP, trisodium citrate, ethylene glycol,
etc., are required for the synthesis of green nanomaterials. Different green precursors
for synthesis of green materials are given in Table 1.

2.3 Different Reaction Conditions

There are several reaction conditions such as temperature, pressure and concentra-
tion of the precursors, reaction time and solvents, which affects structural, optical,
electrical and magnetic properties of the nanomaterials as discussed in Tables 2, 3
and 4.

3 Basic Characteristics of Green Materials

3.1 Structure and Morphology

Morphology of the green nanoparticles affects the efficiency of energy conversion

devices. Various nanostructures or morphology such as 1-D nanorods, nanotubes
and nanowires exhibits excellent charge transport properties which increase the
Studies on Synthesis and Various Characteristics … 13

Table 1 Different green precursors required for synthesis of green materials

Green material Precursors Method References
Nickel sulphide Nickel nitrate, nickel Hydrothermal, microwave, [26]
chloride used as nickel co-precipitation methods [27]
source [28]
Thiourea, thioacetamide
used as sulphur source
Zinc sulphide Zinc nitrate, zinc acetate Hydrothermal, microwave, [29]
used as zinc precursors micro-emulsion [30]
Thiourea, thioacetamide
used as sulphur source
Zinc oxide Zinc nitrate, zinc acetate Co-precipitation method [31, 32]
used as zinc precursors Sol-Gel [14]
Lithium hydroxide used
as oxidizing agent
Titanium dioxide Titanium butoxide, Hydrothermal method [33]
titanium tetrachloride Co-precipitation method [34]
Molybdenum dioxide Molybdenum hex Sol-gel and hydrothermal [35]
hydrate methods [36]
Graphitic carbon nitride Urea Thermal decomposition [37]
Hydrothermal method [38]

Table 2 Effect of temperature

Green material Effect of temperature References
Nickel sulphide Formation of different phases of nickel sulphide [39]
like NiS2 and Ni3 S2
Zinc sulphide Phase change from cubic to hexagonal wurtzite [40]
phase
Zinc oxide Different morphologies of zinc oxide observed [41]
(triangular, rose-like petal structure)
Titanium dioxide Flower-like, nanosheet-like structure observed in [42]
ZnO
Molybdenum oxide Band gap reduced from 3.67 to 3.36 eV [43]
Graphitic carbon nitride Band gap reduced from 2.85 to 2.47 eV [44]

Table 3 Effect of molarity

Green material Effect of molarity References
Zinc sulphide Band gap reduces from 3.69 to 3.36 eV [45]
Nickel sulphide Different morphologies like spheres, cubes and rods found [46]
Zinc oxide Increases non-uniformity of ZnO nanoparticles [47]
Titanium dioxide Conductivity of the TiO2 nanoparticles varies [48]
Molybdenum oxide Crystallite size of MoO2 decreases [49]
14 R. Jha et al.

Table 4 Effect of different precursors

Green materials Effect of different precursors References
Molybdenum dioxide Growth rate of nanoparticles increases [50]
Zinc oxide Different morphologies like nanorods and nanoprism [51]
found
Zinc sulphide Increases grain size [52]
Nickel sulphide Formation of different phases [53]
Titanium dioxide Increases the porosity of the nanostructure [54]
Graphitic carbon nitride Enhancement of electrochemical properties [55]

Table 5 Different morphologies of green materials and its applications

Green material Morphology Application References
Nickel sulphide Nano-flower Supercapacitor [57]
Nickel sulphide Microspheres Sodium-ion batteries [58]
Nickel sulphide Cubes Dye-sensitized solar cell [59]
Zinc sulphide Polyhedral Li–Na-ion batteries [60]
Zinc sulphide Microsphere Photocatalytic [61]
Zinc oxide Tripods Solar cell [62]
Zinc oxide Nano-tower Optical/electrical applications [63]
Titanium dioxide Nanorods Solar cell [64]
Titanium dioxide Beads Quantum dot co-sensitized solar [65]
cell
Molybdenum oxide Grains Solar cells [66]
Molybdenum trioxide Hexagonal rod Catalytic ozonation [67]
Graphitic carbon nitride Nanosheets Photocatalysis [68]
Graphitic carbon nitride Nanorods Solar cell [24]

charge/discharge rate [56]. Three-dimensional mesoporous nano-/macro-spheres

which have large surface area provide more catalytic active sites and increase elec-
tron transfer rate, which improve the efficiency of solar cell and supercapacitor as
given in Table 5.

3.2 Optical Properties

Optical properties of a material are defined as the interaction of materials with

different incident radiations such as photons, electric field and high energy electrons.
Optical properties of the nanomaterials depends upon the dimensions of the mate-
rials. If the size of the particle increases, energy band gap of materials decrease, for
Studies on Synthesis and Various Characteristics … 15

Table 6 Parameters affecting the optical properties of green materials

Green material Parameters affecting optical properties References
Zinc oxide Particle size decreases from 11 to 3.4 nm, and energy [69]
band gap of the materials changes from 3.53 to 3.65 eV
Nickel sulphide Particle size varies from 30.51 to 42.09 (reaction [70]
temperature increases), and energy band gap varies from
4.8 to 2.8 eV
Graphitic carbon nitride Increase in doping varies the band gap from 2.6 to [71]
2.52 eV
Zinc sulphide Concentration of precursor changes, and band gap varies [72]
from 3.73 to 3.64 eV
Titanium dioxide By varying the temperature, band gap varies from 0.33 [73]
to 0.18 eV
Molybdenum dioxide By varying the temperature, band gap varies from 3.67 [43]
to 3.36 eV

example optical absorption and emission shift to the higher energies for quantum dots.
Optical property of the nanomaterials depends upon the various parameters, shape,
size, surface characteristics and other variables including doping using surfactant,
etc., as given in Table 6.

3.3 Electrical Properties

The properties of the materials like conductivity and resistivity come under the cate-
gory of electrical property. Electrical property of the materials depends upon the
morphology, size and surface of the nanomaterials; e.g. if the diameter of nanowire
is decreased, electrical conductivity of the material is increased as given in Table 7.

Table 7 Parameters affecting the electrical properties of green materials

Green material Parameters affecting electrical properties References
Nickel sulphide Temperature increases; conductivity decreases [74]
Zinc sulphide Increase in crystallinity of the ZnS increases conductivity [75]
Zinc oxide Increases in temperature decrease the resistivity [76]
Titanium dioxide Increase in temperature decreases the conductivity [77]
Molybdenum dioxide Increase in effective mass increases the resistivity [78]
16 R. Jha et al.

Table 8 Parameters affecting the magnetic properties of green materials

Green material Parameters affecting magnetic property References
Zinc oxide When temperature increases, magnetic property changes from [79]
paramagnetic to ferromagnetic
Nickel sulphide At room temperature, nickel sulphide shows weak [80]
ferromagnetism
Zinc sulphide Crystallization atmosphere changes magnetic susceptibility [81]

3.4 Magnetic Properties

Magnetic nanoparticles are those particles which are affected by the magnetic field
applied. These particles contain elements like nickel, zinc, carbon, etc. Magnetic
property depends upon the size and morphology of the particles, for example ferro-
magnetism disappears and transforms into super-paramagnetic materials in some
cases when particles come in the range of nanoscale as given in Table 8.

4 Basic Operation for Energy Conversion Devices

The main characteristics of the operation of a solar cell, LED, battery with respect
to voltage, electrical current are described in this section.

4.1 Current–Voltage Characteristics

Solar Cell I–V Characteristic Curves

The operational properties of a solar cell under a substantial incident illumination
using the basic model are studied. The excitation by light generates more number of
electrons and holes in carrier bands that result in the division of the related Fermi
levels. By controlling the voltage V that exists between the two contacts of the solar
cell, the amount of recombination can be changed. I–V characteristic curves are
essentially a graphical illustration of the process of a solar cell or module summing
up the correlation between current and voltage in the present conditions of irradiance
and temperature. I–V curves as shown in Fig. 8 offer knowledge requisite to construct
a solar system that can work as close up to its most favourable peak power point (MPP)
as probable. Knowing I–V characteristics and maximum power of solar cell is vital
in deciding device’s performance and efficiency of solar cells.
Studies on Synthesis and Various Characteristics … 17

Fig. 8 I–V characteristics of

solar cells

I–V Characteristics of LED

In order to emit any wavelength of light, LEDs need a current to flow in the course
of it, since LEDs are current-dependant device. In LEDs, output light intensity is
dependent directly to the forward current flowing in the LED.
To protect LEDs from excess current flow, it should be made current limited by
means of a series resistor since LEDs are connected in a forward bias condition in
a power supply. LED should not be connected to a battery or power supply directly
since it can destroy instantaneously because high current will pass across it and burn
it out. The I–V curve is shown in Fig. 9.

Fig. 9 I–V characteristics of

LEDs
18 R. Jha et al.

Fig. 10 I–V characteristics

of batteries

I–V Characteristics of Battery

A battery is a collection of voltaic cells. It is a device that converts chemical energy to
electrical energy through electrochemical reactions. A battery characterizes a small
voltage. Alongside the quantity of cells associated in series, chemistry produces
the open-circuit voltage (OCV), which is approximately 5–7% higher on a wholly
charged battery. I–V characteristics of battery are shown in Fig. 10.

4.2 Power Conversion Efficiency

The main application of solar cell is to serve as a power supply unit that produces
electricity from sunlight or from ambient light in indoor applications. The central
feature to assess the solar cell performance is the electrical power that can be extracted
from the available radiation level. The electrical power at a given voltage operation
point of the solar cell, Pej , has the value shown in (Eq. 1):

Pej = j V (1)

The power is zero at both open- and short-circuit conditions. In between the
extreme cases of low power lies the maximum power point (MPP) at which voltage
(V mp ) the solar cell should be operated for electricity production. The maximum
power provided by the photovoltaic device is represented in (Eq. 2):

Pe f,max = jmp Vmp (2)

For the characterization of energy converter devices, the main figure of merit is
the maximum conversion efficiency of the solar cell, that is, the PCE that consists
of the electrical power supplied at MPP with respect to the incoming photon energy
Studies on Synthesis and Various Characteristics … 19

(Eq. 3):

jmp
ηPCE = Vmp (3)
ϕ

The PCE depends on the operation conditions that need to be defined. The PCE
of a solar cell is usually reported under simulated standard terrestrial spectrum AM
1.5G which bears an integrated power of φ = 1 kWm−2 = 100 mWcm−2 . This type
of illumination is usually denominated as “1Sun.”
The η (efficiency) of LED is the function of current passing across it. For every
LED, there is a value of I LED for that efficiency is found to be maximum. The
efficiency gets decreased when the operational temperature is increased.
This expression associates the current in photodiode I(m) kept back at a distance
m from the axis of cone to the total power radiated ϕ T emitted by the LED.
The efficiency η is given by (Eq. 4):

φT
η= (4)
PLED

where ϕ T represents the total power emitted by LED and PLED denotes the electrical
power (I LED · V LED ) applied to it [82].

4.3 Analysis of Fill Factor

The efficiency increases when the short-circuit photocurrent jph and open-circuit
voltage V oc increase, but ηPCE also depends critically on the MPP. The form of the
j–V curve decides that at what voltage value the electrons are extracted as electric
current. At lower voltage value, extraction of electrons is easy, and the current is
computed by quantum yield of the absorber. Though, a higher voltage produces a
current opposite to the photocurrent, and ultimately the power decreases. If the point
is close to V oc , then the operational voltage and current are much larger if V mpp occurs
at low voltage close to V oc /2. The parameter that tracks this property is the fill factor
(FF) defined as (Eq. 5):

jmp Vmp
FF = (5)
jph Voc

The fill factor depends on the form of the j–V curve (Fig. 11), determining the
MPP and exerting a large influence on PCE of the solar cell. If the FF is higher, the
fall in current at higher voltage can be delayed, and the electrons can be extracted at
high voltage while the current is closer to jph. For a good-quality diode attribute, the
power P should increase linearly at the lower voltage.
20 R. Jha et al.

Fig. 11 Analysis of fill

factor

4.4 Efficiency Limits

Efficiency limits were firstly computed by William Shockley and Hans Queisser in
1961. The conversion efficiency of solar cell is the fraction of conversion of power
from sunlight to the electrical energy under standard test conditions (STCs). The
modern SQ limit computation is a maximum efficiency of 33% for any kind of single
junction solar cells. The original estimation by Shockley and Queisser was 30% for
silicon solar cells. Recent solar cell’s conversion efficiencies differ by the energy
band gap of the semiconductor material used in the fabrication process [83].

5 Various Applications of Green Energy Materials

A solar cell or photovoltaic cell is a semiconductor device that converts the light
energy (certain wavelength) into electrical energy by photovoltaic effect. Solar cell
consists of absorption of photon, producing electron–hole pairs in a semiconductor
and charge-carrier separation. At present, three types of solar cells are available,
first-generation, second-generation and third-generation solar cells. First-generation
solar cells are made up of crystalline silicon wafers, and this technique is the oldest
technique and high power efficient technique. Second-generation solar cells are
thin-film technologies such as copper–indium–gallium–selenides (CIGS), gallium
arsenide (GaAs) and cadmium telluride (CdTe). Third-generation solar cells are less
commercial and consist of organic materials such as carbon nanotube and titanium
dioxide.
Studies on Synthesis and Various Characteristics … 21

5.1 Dye-Sensitized Solar Cells (DSSCs)

Dye-sensitized solar cell is a third-generation solar cell. Dye sensitized solar cells
consist of semiconductor photo anode (e.g. titanium dioxide, zinc sulphide etc.),
counter electrode (e.g. nickel sulphide, platinum, titanium disulphide etc.) and elec-
trolyte (e.g. iodine). Photoanodes are coated on substrates such as ITO/FTO, sensi-
tized with organic dyes for e.g. N3 that can absorb quantum dots (CdS, PbS etc.).
Electrolytes are injected between sensitizer and counter electrode which collects
electrons from the external circuit. Performance of the DSSCs depends upon the
properties (morphology, electrical, magnetic, etc.) of the semiconductor materials
such as large surface area required for absorption of dye which increases the charge
transport rate. This is an alternative of the silicon solar cell, because dye-sensitized
solar cell is cost-effective, less toxic and semi-transparent, and has high flexibility
and good performance [84].

5.2 Quantum Dot-Sensitized Solar Cells (QDSSCs)

QDSSC is a third-generation solar cell. QDSSC is a potential candidate for next-

generation solar cells due to unique optoelectronic features such as high light, mois-
ture stability and thermal stability. QDSSC is similar to DSSC, and dye is replaced
by new absorbing material, quantum dot. Titanium dioxide, zinc oxide, etc., are
used as photo-anode because they have large surface area, unique morphology, high
charge transport rate. Zinc sulphide is used as quantum dot because zinc sulphide
has a large band gap which is depending on the size of zinc sulphide particle [85].
Nickel sulphide and platinum are used as counter electrode because they have low
charge transfer resistance, high cyclic stability, unique morphology which helps in
the collection of electron from the external circuit.
The process of developing the DSSC versus QDSSC is deduced by the type of
sensitizer used, which is either an inorganic nanoparticle (QDs) or dye (DSSCs). The
superior optoelectronic properties of QDs, such as size dependent tunable energy
band gap and carrier multiplication (i.e. MEG multiple exciton generation effect),
enhance the performance of QDSSCs [86, 87]. CdS and CdSe have been studied as
semiconducting material for QDSSCs. But these are toxic in nature because of the
presence of Cd in it. So, there is a need of green material for QDSSCs.

5.3 Hydrogen Evolution Reaction

Water splitting consists of two reactions: one H2 (hydrogen evolution reaction) and
O2 (oxygen evolution reaction). Production of hydrogen evolution and oxygen evolu-
tion occur through water electrolysis process. Hydrogen evolution depends upon the
22 R. Jha et al.

desorbing of the molecules coming from cathode surface. These reactions generally
occur on noble metals such as Pt, Rh or Ru, because in HER and OER a large number
of electrons and protons are required. But these noble metals cannot be directly used
because of very high cost. So instead of using these noble metals we use nickel
sulphide, zinc sulphide, etc., because these materials have large surface area, higher
intrinsic activity and higher exchange current density.
Reason of Metal Sulphides in QDSSCs
Metal oxides can cause photocorrosion under band gap excitation, such as ZnO. So,
they are not active water splitting because of photocorrosion. Hydrogen production
can be improved by using metal sulphides with oxides. The reason is that metal
sulphides on the surface of metal oxides play a vital role in the separation of e− /h+
pairs and enhance the performance of hydrogen evolution [88].
In contrast, other metal oxides such as MoO3 [89] and TiO2 [90] possess supe-
rior photocatalytic activity for hydrogen generation. MoO3 on surface of polyimide
significantly enhances the photocatalytic activity for hydrogen evolution, which
ascribes to increase light absorption and the suppression of radiative recombination
of photogeneration of e− /h+ pairs.

5.4 Supercapacitor

Supercapacitor is a high-capacity capacitor which has high capacitance than the

normal capacitor. Supercapacitors consist of anode, electrolyte and cathode. The
anode (nickel sulphide, zinc sulphide, zinc oxide) and cathode materials have high
cyclic stability, low charge transfer resistance, large surface area, high theoretical
capacity. For increasing the cyclic stability of the electrode materials, we mix some
amount of carbonaceous materials. Generally, two types of supercapacitor are avail-
able depending upon the mechanism of supercapacitor: one is pseudosupercapac-
itor, and other is electric double-layer capacitors. Electric double-layer capacitor is
ascribed due to charge separation along with accumulation of electrolyte, and pseu-
dosupercapacitor originates from reversible faradic reaction. Nickel sulphide has
high theoretical capacity, low charge transfer resistance, high cyclic stability; due to
these properties, nickel sulphide is used as electrode in electrochemical devices such
as supercapacitor and lithium-ion batteries.

5.5 Batteries

Electrochemical energy sources which convert chemical energy into electrical energy
are called as battery, which consist of more than one cells. A cell consists of cathode
(nickel sulphide, zinc sulphide, zinc oxide), electrolyte, separator and anode. The
main function of the electrolyte is to allow ions to move between the electrodes
Studies on Synthesis and Various Characteristics … 23

and terminals. Usually, two types of batteries are available: one non-rechargeable
battery and rechargeable batteries like lithium-ion, sodium-ion batteries, etc. These
batteries are very useful because of high energy density, and low maintenance. The
main disadvantages of these batteries are poor cyclic stability, long charging times,
slow charging rate. Nickel sulphide, zinc sulphide and molybdenum dioxide are used
as electrode in charge storage devices.

5.6 Light-Emitting Diodes (LEDs)

LED is a semiconductor device that emits visible light when electric current passed
through it. If electric energy is applied, then inter-band transition takes place
resulting in luminescence which is called as electroluminescence. When a voltage is
applied in the metal nanoparticles, placed in ITO/FTO substrate through proper elec-
trode system. Then electronic transition takes places in metal nanoparticles which
help to emit light. The colour of the emitted light depends upon the energy difference
between valence band and conduction band of the materials.

6 Conclusions and Future Perspectives

In this chapter, the importance of sustainable environment, green materials, has been
discussed. Use of green or non-toxic materials and green technology is an effec-
tive tool for the alternative of green energy generation. Green nanomaterials would
provide an influential route for energy device fabrication. The primary focus of this
chapter is to use green materials for energy devices. Various green materials and
its synthesis techniques have been discussed in detail. Significant progress has been
reported for various green materials with properties and its potential applications.
The green materials can be applied as components in various energy conversion and
storage devices such as solar cells, hydrogen evolution reaction, supercapacitors and
batteries. Researchers have investigated the physical and chemical properties of green
materials. Potential applications of the green materials are recommended to provide
insight into the wide spectrum to which their properties such as optical, electrical and
magnetic can be utilized. Environmental issues we face every day cannot be solved
overnight, but with increasing discoveries in green nanotechnology, the goal can be
achieved significantly very soon.

Acknowledgements The authors are grateful to the vice chancellor of Netaji Subhas University
of Technology (formerly Netaji Subhas Institute of Technology) for financial support.
24 R. Jha et al.

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Advancement in CdIn2 Se4 /CdTe Based
Photoelectrochemical Solar Cells

Subhash Chander

Abstract Many binary and ternary chalcogenide semiconductor materials (viz CdS,
CdSe, CdTe, CdZnTe, CuInS2 , CuInSe2 , Bi2 CdS4 , CdIn2 Se4, etc.) have been used
to develop photoelectrochemical (PEC) solar cells for the sustained and efficient
capture of solar energy conversion. Because thin-film solar cell technologies are a
capable tactic for global and planetary-photovoltaics and offer a wide variability
of picks in terms of device designing and fabrication. Cadmium indium selenide
(CdIn2 Se4 ) has obtained very little consideration as a potential material for photo-
electrochemical cells. The manufacturing of thin-film-based heterojunction solar
cells done by using some chemical and physical techniques such as sputtering,
pulsed laser deposition, and evaporation. In spray pyrolysis technique (Fig. 1), a
desired equimolar aqueous solution of cadmium chloride, indium trichloride, and
selenourea in appropriate volumes can be taken onto preheated substrates (amor-
phous or conducting substrates viz. ITO, FTO, quartz, etc.). The preparative param-
eters (substrate temperature, solution concentration, quantity of solution) should be
optimized by a PEC method in order to get high-quality stoichiometric films. The
optimization of preparative parameters of the photoactive semiconducting electrode
by the photoelectrochemical method is a new, reliable, and unique technique in the
field of thin-film technology. So, this chapter deals with the preparation of cadmium
indium chalcogenide thin films from aqueous medium by cost-effective and simple
spray pyrolysis and consequently use of these films in heterojunction solar cell appli-
cations. It also extensively describes the physiochemical properties of CdIn2 Se4 thin
film as a potential window layer to the photoelectrochemical solar cells.

Keywords Energy materials · CdIn2 Se4 thin films · PEC solar cells · Recent
progress

S. Chander (B)
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER)
Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 29

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_2
30 S. Chander

1 Introduction

The solar energy is radiant energy produced by the sun, and every single day, the sun
radiates, or sends out, an enormous amount of energy. The sun radiates more energy
in one second than people have used since the beginning of time; this energy comes
from within the sun itself. The solar energy moves to the earth planet at a speed of 1.86
× 105 miles per second, the speed of light. Solar energy is also absorbed by plants, the
land, and the oceans. The public and world governments remained largely indifferent
to the possibilities of solar energy until the oil shortages [1]. Today, people use solar
energy to heat buildings and water and to generate electricity. Hence, considering
the industrial demand for reliable and a variety of new scientifically based future
technologies, thin-film studies have made tremendous advances in the last decade.
The advancements in the heterojunction solar cells have developed in several new
areas of research in the field of solid-state physics and chemistry [2].
There has been a growing interest during the past few decades in metal
chalcogenide thin films because of their promising applications such as solar
cell, light-emitting diode, thermoelectric coolers, optoelectronic devices, and
photoelectrochemical-based devices. To realize these applications, it is one of
primary importance to grow high-quality thin films and characterize their funda-
mental properties. The fabrication of thin-film-based heterojunction solar cells has
been done by using some chemical and physical techniques such as sputtering, pulsed
laser deposition, and evaporation. All these techniques have their own merits and
demerits, but spray pyrolysis technique has been attracting a great deal of attention
to deposit semiconducting thin films owing to its simplicity and low cost. So, this
chapter deals with the preparation of cadmium indium chalcogenide thin films from
aqueous medium by cost-effective and simple spray pyrolysis and, consequently use
of these films in heterojunction solar cell applications. The optimization of prepar-
ative parameters of the photoactive semiconducting electrode by the photoelectro-
chemical method is a new, reliable, and unique technique in the field of thin-film
technology [3]. The p-n junction-based single-crystalline silicon solar cells have been
favored due to their high efficiency (more than 25%), and the rigorous prerequisite
of very decorative configurations (for the realization of high efficiency) stalemates
a severe inadequacy that the industrial cost would be an extreme level. In recent
years, heterojunction-based photovoltaic devices have earned significant consid-
eration owing to their lower industrial cost, in spite of their comparatively small
power conversion efficiency. A number of methods/techniques can be employed to
fabricate heterojunction-based solar cell devices [4]. Thin-film solar cells (TFSC)
are an encouraging methodology for terrestrial and space photovoltaics and offer a
wide variety of choices in terms of device designing and fabrication [5]. A range
of substrates (flexible or rigid, metal, or insulator) can be used for deposition of
different layers (contact, buffer, absorber, reflector, etc.) exhausting diverse flexible
techniques which allowed tailoring and engineering of the layers for enhancement in
the performance of the solar cell device. Thin-film-based methods are not so energy-
concentrated as compared to silicon-based technologies and are flexible for bunch
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 31

processing, which results in a reduction in the total cost of the device. Recent studies
reveal that there is rapid advancement in the synthesis and design of bulk semicon-
ducting chalcogenide-based thin films for solar cell applications [6–9]. A thickness
of 2–4 μm of direct bandgap semiconductors (GaAs, CIGS, and CdTe) for the thin-
film-based photovoltaic cells is enough for light absorption while crystalline silicon
needs around 200–300 μm to absorb all the incident radiation. Owing to the narrower
layer generated, this commands to the more rapidly processing moves and yield-
lessening the principal cost. Solar cells made from these materials have demonstrated
module efficiencies of over 12% and are currently manufactured globally. Copper
indium gallium selenide and cadmium telluride based solar modules are having
power conversion efficiencies comparable to silicon-based solar modules designed
and developed, and their stability has also been well tested [10]. The maximum
obtained efficiency of these single crystalline silicon and thin-film-based solar cells
is limited to around 25%, which is less than the maximum hypothetical efficiency
limit of 33% as predicted by Shockley and Queisser for a single p-n junction solar
cell [11]. But efforts on n-CdIn2 Se4 /p-CdTe heterojunction solar cells fabricated by
low-cost and straightforward chemical spray pyrolysis technique have given less
coverage. This technique has some advantages over others like easy to vary the
precursor’s concentration and substrate temperature for controlling stoichiometry
and adherence of the deposited layers. So, this chapter will be a milestone in the
field of CdIn2 Se4 /CdTe thin-films based electrochemical solar cells by incorporating
research work done so far.

2 Significance of CdIn2 Se4 Material

The interest in the semiconductor–liquid junction has evolved parallel to develop

solid-state junctions. Even though there have been both academic advances and
market expansion in solar cell technologies in modern years, there persists a need
for enhanced efficiency, reduced-cost processing, and increased process yields. The
binary and ternary semiconducting materials can be grown on different types of
substrates employing the spray pyrolysis method [12–14]. The binary and ternary
chalcogenide materials (viz. CdS, CdSe, CdTe, CdZnTe, CuInS2 , CuInSe2 , Bi2 CdS4 ,
CdIn2 Se4, etc.) have been used to develop photoelectrochemical (PEC) solar cells
for the sustained and efficient capture of solar energy conversion [15–20]. Cadmium
indium selenide (CdIn2 Se4 ) is an n-type ternary semiconducting compound material
belongs to the II-III-VI group and has tetragonal and cubic structures with the lattice
constant of 5.823 Å [21, 22]. It was first produced by Hahn et al. [23], while CdIn2 Se4
crystals were prepared by Nitsche [24] employing the chemical transport method. It
is widely used in optoelectronic devices, nonlinear optics, semiconducting devices,
radiation detectors, laser materials, thermoelectric devices, solar energy converters,
etc. [25–27]. This material has been effectively utilized as a window layer owing to
its light-moving property with a thin direct bandgap and low electrical resistivity to
32 S. Chander

make different electronic and electro-optical devices. One of its proficient applica-
tions is in thin-film heterojunction solar cells or as a photoelectrode in the PEC cells.
The efficient operation of solar energy is the best encouraging approach to tackle the
concern related to the energy crunch. Consequently, effective solar energy conver-
sion into functional photovoltage by PEC cells has stimulated tremendous research
attempts.

3 Advancement in CdIn2 Se4 Thin Films

The compound CdIn2 Se4 material has given a little consideration as a potential
material for the PEC cells owing to its optical absorption property, narrow optical
bandgap (1.73 eV), and a low electrical resistance [28–31]. Great intense studies
on CdIn2 Se4 thin films have been made in recent years due to their exciting and
proposing tailored properties that extend the possibility of implementing innovative
applications in many modern applications such as solar energy conversion, nonlinear
optics, and optoelectronic devices [32, 33]. The fundamental needs of good thin-film
photoelectrode for PEC cells are low resistivity and large grain size, where later
one leads to lessening the grain boundary area of thin films with vital outcomes for
efficient energy conversion. The low resistivity of photoelectrode is required to mini-
mize the series resistance of PEC cells. CdIn2 Se4 thin films can be fabricated by a
number of physical and chemical processes viz slurry pasting technique [32], sol-gel
[34], thermal evaporation [35], pulsed electrodeposition [36], spray deposition [28,
37], potentiostatic cathodic electrodeposition [38], and laser ablation technique [39]
where every method has their own merits and demerits. The spray pyrolysis technique
is one of the most used processes since it is relatively inexpensive and convenient
for extensive area deposition and provided quality films having good photovoltaic
activity, high crystallinity, low electrical resistivity, and high thermoelectric power
[40]. In spray pyrolysis technique (Fig. 1), a desired equimolar aqueous solutions of
cadmium chloride, indium trichloride, and selenourea in appropriate volumes can be
taken onto preheated substrates (amorphous and conducting substrates viz. ITO, FTO,
quartz, etc.). The preparative parameters (substrate temperature, solution concen-
tration, quantity of solution) should be optimized by a PEC method in order to get
high-quality stoichiometric films.
After fabrication of high-quality CdIn2 Se4 thin films, one can be post-treated
by various treatment and then subjected to different characterization tools viz. X-ray
diffraction (XRD), scanning electron microscopy (SEM) coupled with energy disper-
sive analysis by X-rays (EDAX), atomic force microscopy (AFM), UV-Vis spec-
trophotometer, and source meter (i.e., electrometer) in order to investigate structural,
surface morphology (along with compositional), topography, optical, electrical, and
photovoltaic properties. The optical, photophysical, and photoluminescence proper-
ties of thin CdIn2 Se4 films are reported by different research groups across the world
[41–47].
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 33

Fig. 1 Schematic representation of the spray pyrolysis deposition method

The photoactive cadmium indium selenide (CdIn2 Se4 ) thin films are electrochem-
ically synthesized by Ahn et al. [12] at ambient temperature. The films found to be
nanocrystalline in nature and have 1:2:4 elemental chemical stoichiometric ratio for
Cd, In, and Se. Irregularly shaped islands having 400–500 nm in sizes and composed
of a large number of small spherical grains were verified from the atomic force
microscopy and the scanning electron microscopy images. The physical properties
of thin CdIn2 Se4 films are investigated by Dalchiele et al. [13], where the films were
grown by electrodeposition technique. The photoelectrochemical measurement in
the presence of 1 M poly-sulfide electrolyte revealed the device conversion effi-
ciency of 0.42% under the light illumination intensity of 80 mW/cm2 . Salem et al.
[14] prepared stoichiometric bulk ingot material of the quaternary CdGaInSe4 by
direct fusion of the constituent elements in vacuum-sealed silica tubes. All the films
exhibited n-type conduction and ohmic behavior with metallic films of Au, Cd, In,
Ag, and Sb. The optical constants of CdIn2 Se4 thin films within the spectral range
of 500–2000 nm are studied by El-Nahass [21], who also evaluated the refractive
index, absorption index, absorption coefficient, and forbidden energy gaps. Adpak-
pang et al. [29] synthesized CdIn2 Se4 powder via an aqueous chemical reduction
where they used Se metal, InCl3 , and CdCl2 ·2.5H2 O as precursors, NaBH4 as a
reducing agent, and water as a solvent. The CdIn2 Se4 phase was observed in some
preparative conditions with In(OH)3 contaminating phase. Though, In(OH)3 impu-
rity had disappeared when the reaction temperature was 130 °C with a reaction time
of 30 min while the particle size was found to be around 10 nm.
Neumann et al. [48] studied infrared reflectivity of CdIn2 Se4 single crystals at
room temperature in the wavenumber range from 180 to 4000 cm−1 for the polariza-
tion directions Ec and E. The spectra reveal two vibrational modes with nearly the
same frequencies for both polarization directions. It is concluded that these modes
are sphalerite-like in nature and their frequencies are primarily determined by the
34 S. Chander

properties of the In-Se bond. Guerrero et al. [49] prepared samples of CdIn2 Se4 by
the melt-and-anneal technique followed by annealing at 500 °C. The films found to
have p-structure and also calculated the deformation potentials of the valence and
conduction bands. The degree of crystallinity increases with increasing the annealing
temperature, while the elemental compositional analysis confirmed the nearly stoi-
chiometric nature of the films. The allowed direct and indirect optical transitions, and
both values of energy gaps were also decreased with increasing annealing tempera-
ture. Hady et al. [50] studied the structural, optical, thermoelectric power measure-
ment for several pre-annealed thin CdIn2 Se4 films having different thicknesses. Their
results showed that the pre-annealed films are n-type semiconductors, whereas free
charge carrier concentrations were used to calculate the free charge carrier mobility
from which the grain boundary potential barrier has also been evaluated. Trykozko
et al. [51] prepared CdIn2 Se4 crystals by means of chemical transport reactions
using iodine as a transport agent. They measured the reflectance of CdIn2 Se4 at
room temperature and at liquid nitrogen temperature within the range of 1.5–20 eV
using synchrotron radiation. The effects of temperature and pH on the formation of
thin CdIn2 Se4 films are investigated by Ruanthon et al. [34] where they fabricated
the films by sol-gel dip-coating method using cadmium, indium, selenium precur-
sors which were dissolved in the different solvents (ethanol, hydrochloric acid, and
acetic acid) to form metal alkoxides. The precursor solutions were mixed together in
the N2 atmospheric condition, and then, these metal alkoxides were hydrolyzed by
adding water and consequently poly-condensed by adding ethylene glycol to become
gels. These thin films were annealed at various temperatures in the N2 atmosphere
and characterized by SEM. Their results indicated that CdIn2 Se4 thin films fabri-
cated by the reaction at room temperature with pH4 and annealed at 450° in nitrogen
atmosphere are suitable for photovoltaic applications. Girija et al. [52] have fabri-
cated cadmium indium selenide thin films on glass substrate employing chemical
bath technique at different temperatures of 40 °C, 60 °C, and 80 °C. They tailored
the properties to the compound itself in order to find the potential applications for
optoelectronic devices. The films were found to have a cubic phase while presence of
elemental constituents was confirmed by EDAX. Their optical studies revealed that
the films have a direct transition with energy bandgap ranging from 1.55 to 2.28 eV.
Mahalingam et al. [38] reported the effect of deposition potential on the
microstructural parameters (crystallite size, strain, and dislocation density) where
they deposited thin CdIn2 Se4 films on ITO coated substrates at various deposition
potentials using potentiostatic electrodeposition technique. The prepared films found
to have polycrystalline nature with the preferential orientation of (200) diffraction
peak. They observed the stoichiometric behavior of well-defined composition at a
deposition potential of −950 mV and films exhibited direct bandgap value within the
range of 1.66–1.75 eV, which was varied with the deposition potential. Nikale and co-
workers [27] deposited well adherent and stoichiometric semiconducting n-CdIn2 Se4
thin films spray pyrolysis technique. The films found to have good photoactive and
photoactivity, while XRD patterns show the polycrystalline nature with a cubic crystal
structure. The crystallinity and texture coefficients were increased with the optimized
solution concentration, whereas surface morphology study reveals non-uniformity
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 35

of distributed grains that having different grain sizes. The lowest resistivity and acti-
vation energy achieved for films deposited at 12.5 mM concentration were about 3.9
× 101  cm and 6.8 meV, respectively, where grown films showed n-type conduc-
tivity. Salim and co-authors [35] have grown CdIn2 Se4 thin films employing thermal
evaporation technique using pre-synthesized ingot material. They observed that the
as-deposited films have amorphous nature, but the amorphous-to-crystalline phase
transition occurred at an annealing temperature of 200 °C as well as films showed
stoichiometric behavior as confirmed by EDAX analysis. The optical analysis of the
optical absorption coefficient revealed the existence of direct and indirect optical
transitions.
The microstructural and electrical properties of CdIn2 Se4 thin films have been
investigated by Sudha and co-workers [36], where they grow the films by pulsed
electrodeposition technique. Their AFM results showed that the as-deposited films
were well-adherent with uniformly grains distribution over the surface of the substrate
as well as films were highly transparent in the visible range having more than 80%
average transmittance. The direct optical bandgap was varied from 3.12 to 3.77 eV
and decreased with the duty cycle of the deposition process.
In 2017, Bhalerao and co-workers [31] had electro-synthesized the thin CdIn2 Se4
films and have (photo)electrochemically explored using current–voltage and capaci-
tance–voltage characteristics along with photoresponse, speed response, and electro-
chemical impedance studies. The improved photoconversion efficiency can be justi-
fied by hypothetical modeling of energy band illustration and equivalent circuited
model of impedance spectra of the PEC cells. Very recently, Degdas and Peksoz
[53] deposited cadmium indium selenide thin films on ITO coated substrates using
electrodeposition technique at a constant deposition voltage of −0.95 V. They used
CdCl2 , InCl3 , and H2 SeO3 precursors, while the Se concentration was enhanced
from 5 to 35 mM by a step of 5 mM as well as HCl was used to adjust the pH of the
electrolytes. They investigated the effect of concentration of Se source on film thick-
ness, surface morphology, film composition, crystallinity, donor density, mobility,
and optical band gap. They found that the film thickness was increased from 247
to 374 nm with the concentration of Se source, whereas Se concentration causes a
significant variation of surface morphology and elemental compositions of the films.
All the films have a tetragonal crystalline phase, while the energy bandgap is ranging
from 1.98 to 2.23 eV. The Hall-effect analysis confirmed the n-type semiconducting
nature and donor density which is found within the range of −1.3 × 1017 cm−3 and
−4.1 × 1018 cm−3 , whereas the mobility increased with the increasing of Se atomic
percentage which might be due to decrease in the donor concentration.

4 Photoelectrochemical (PEC) Solar Cells

The formation of a practical PEC cell is to convert the sunlight into electricity, and the
most vital element is the long-term stability of the solar device which shows sufficient
power conversion efficiency. This type of cell has consisted of a semiconductor
36 S. Chander

photoelectrode, an electrolyte, and a counter electrode, as demonstrated in Fig. 2.

The spacing from the photoelectrode to the counter electrode can be kept around
5 mm. The band bending of semiconductor photoelectrode may occur when both
electrodes are immersed in the electrolyte. The electron transfer can take place only
from the electrolyte into the conduction band, while hole transfer into the area of
the valance band because these types of transfers can only occur between two states
of the same energy, one empty and other filled. Under light illumination, electron-
hole pairs are generated in the depletion layer and separated by the electric field
present at the interface. The incident energy of the photon should be higher than the
energy bandgap of the semiconductor. The electron-hole pairs generated in the bulk
of the semiconductor are mostly lost through recombination. If a positive potential is
applied to the n-type semiconductor photoelectrode and illuminated, electron-hole
pairs are generated, and separated electrons rise to the top of the conduction band and
holes in the valence band. This process sets up a counter field under open-circuited
conditions. The counter field is at its maximum and is the open-circuited voltage
(V oc ) which is given by Eq. (1) [54].
   
nK T Iph
Voc = ln +1 (1)
e Io

Here, I o is the total output current, I ph is the photon-generated current, n is the

junction ideality factor, K is the Boltzmann constant, T is the temperature, and e
is the electronic charge. On the other hand, the counter electrode is being in the
same electrolyte, the photovoltage acts as a driving force for electrons to move
under short-circuit conditions from semiconductor electrode to the counter elec-
trode, and a regenerative cell is formed and is shown in Fig. 3. As discussed by

Fig. 2 Conventional schematic representation of the electrochemical photovoltaic cell

Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 37

Fig. 3 Direction of current flow and energy band level diagram for a PEC cell having n-type
semiconducting material

short-circuited current [55], the electrons pushed to the conduction band glide in the
direction of the interior, while the minority carriers (i.e., holes) come to the surface of
a semiconducting material where they encountered and reduce into the redox couple
form inside the solution. The part is dissolved by holes, transferred to the counter-
electrode, and consequently gets diminished. Such diminution is propelled by the
external connection from the semiconducting material.

4.1 Prerequisites to Make a PEC Cell

A photoelectrochemical (PEC) cell has consisted of a photoelectrode (made by a

semiconducting material), an electrolyte, and a countered electrode, as demonstrated
in the above Fig. 2. The following prerequisites are required to achieve excellent
performance of the device:

4.1.1 Semiconductor Photoelectrode

One of the most vital components to developing a PEC solar cell is the selection and
preparation of semiconducting material, which indicates the modifications in the
electrical characteristics of the solar cell device. The semiconducting photoelectrode
be supposed to fulfill the subsequent basic requirements as follow:
1. The energy bandgap of semiconducting material ought to be such that the utmost
portion of the solar radiation spectrum is utilized. Nearly, all the visible portion
38 S. Chander

of solar radiation arriving at the earth’s surface is focused within the range of
1.65–3.50 eV.
2. The power conversion cell efficiency should be high that varies with the
optical absorbance, bandgap energy, diffusion-length, electrical conductivity,
recombination of charge carriers, surface-states, etc.
3. The semiconducting photoelectrode has to be stable against erosion when it posi-
tioned inside the specific redox-electrolyte. So, the selection of semiconducting
materials is highly significant for a PEC cell.
4. The thickness of the semiconducting photoelectrode is supposed to be sufficiently
large to absorb the maximum photons of the incident solar radiation.
5. The series and shunt resistances must be small and large (as much as possible),
respectively, here ideal value of series and shunt resistances is zero and infinity,
respectively.
6. The manufacturing cost and power conversion cell efficiency would be an
acceptable range.

4.1.2 Electrolyte

The electrolyte is another critical factor of the PEC cells, and it consists by oxidized
and reduced species. These species are ionic species and are required in helping for
the transportation of photogenerated holes from the semiconducting photoelectrodes
to the countered electrodes. The energy band levels of electrolytes are analogous to
the solid-state theory of energy states, and Ef of the redox is equal to the Fermi energy
level of the semiconducting material. When the semiconducting photoelectrode is
engrossed into the electrolyte, the equipoise position is attained by the electron-
exchange at the electrolyte surface. The Fermi level of the semiconducting material
adjusts with the other counterparts, which generates a barrier height depending on
the solution species types and semiconducting material. The requirements for an
electrolyte are as follow:
1. Reduction–oxidation outcomes have to occur suitable to the band edges of the
semiconducting material.
2. Rate of charge transfers of oxidized/reduced species have to be elevated at the
semiconducting photo and countered electrodes.
3. The oxidized and reduced species along with supporting electrolyte concentration
in the solvent have to be suitable to achieve the expected current densities.
4. The optical absorbance/absorption of electrolyte has to be lowest. The electrolyte
ought to be non-corrosive to the photo and counter-electrodes.
5. The noxiousness, reactivity, and cost ought to be below as possible.

4.1.3 Countered Electrode

The countered electrode is required to fulfill recreating processes, and the species of
electrolytes are oxidized as the electrodes providing no netting chemical variation
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 39

in the composition of the electrolytes. The countered electrode is supposed to fulfill

the subsequent basic requirements as follow to enhance the performance of a solar
device:
1. The countered electrode must be chemically inactive.
2. Charge transfer between the countered electrodes and redox species inside the
electrolyte has to be quick.
3. As a countered electrode is engrossed into the electrolyte, the half-cell poten-
tial of the countered electrode has to match with the half-cell potential of
semiconducting photoelectrode.
4. Countered electrodes ought to be not expensive.

5 Advancement in CdIn2 Se4 /CdTe Based Thin Film Solar

Cells

5.1 Solar Cell Device Characterization

The solar cell characterization is the current–voltage measurements can be under-

taken under simulated sunlight, and the integration of spectral response with the solar
spectrum (having condition of AM1.5G and normalized intensity of 100 mWcm−2)
may provide information on different photovoltaic parameters viz short-circuit
current, open-circuited voltage, fill factor, cell efficiency, maximum power point,
and series/shunt resistances. The air mass (AM) number is given by the standard
relation (Eq. 2) [56].

1
Air Mass (AM) = (2)
cos θ
Here, θ is the angle of incidence. The radiant power as seen at the surface of the
earth is called AM1.5 and most widely used for evaluating solar cells (solar spectral
irradiance distribution incident at sea level from the sun at 45° above the horizon). The
current–voltage characteristics of a solar cell in the dark and illuminated junctions
are demonstrated in Fig. 4.
When the diode is illuminated, the dark current characteristic shifts down by
light generated current (I L ), and the characteristic curve describes three essential
parameters that give a complete description of a solar cell that is short-circuited
current (I sc ), open-circuited voltage (V oc ), and fill factor (FF). The short-circuited
current is obtained when the voltage drop across the junction is zero, which means
that under ideal conditions I sc is I L , but I sc is lower than I L due to the effect of
series and shunt resistances [57]. The maximum power point (MPP) is equal to the
area of maximum power rectangle as shown in Fig. 4 on the I–V curve which is
the point where maximum power is produced. It is a point on the current–voltage
40 S. Chander

Fig. 4 a Current–voltage characteristics of a solar cell in the dark and illuminated and b maximum
power rectangle

characteristics where the area of the resulting rectangle is largest. The fill factor (as
given by Eq. 3) is described as the ratio of the maximum available power to the
product of the open-circuited voltage and short-circuit current [58].

Vm × Im
FF = (3)
Voc × Isc

Here, V m and I m are maximum voltage and current (at maximum power point),
respectively. Typical commercial solar cells have a fill factor >0.70. Besides power
conversion efficiency, it is one of the most significant parameters for the energy yield
of a photovoltaic cell. It is well known that the PV cells with a high fill factor have
a low equivalent series resistance and a high equivalent shunt resistance, so less of
the current produced by light is dissipated in internal losses.
The power conversion efficiency (η) is a measure of the performance of a solar
cell which could be determined by the maximum output power of the device as the
ratio of power output (Pout ) to power input (Pin ), where input power is the sum over
all wavelengths which is commonly fixed at 100 mW/cm2 when solar simulators are
used [58].

Pout
η= (4)
Pin
FF × Vsc × Isc
η= (5)
Pin
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 41

5.2 CdIn2 Se4 /CdTe Heterojunction Based Solar Cells

A heterojunction is a junction between two dissimilar crystalline materials, and it

can be classified as abrupt and graded corresponding to distances during which the
electronic transitions from one material to others are completed near the interface.
For abrupt heterojunction, the region is within a few atomic distances, while for
graded heterojunction, it is of the order of several diffusion lengths. When photons
having energies between two bandgap energies pass through wide bandgap semi-
conductors, they generate electron-hole pairs in and near depletion regions on the
narrow bandgap side of the junction. The built-in-field at the junction separates the
holes before recombining in the depletion region and generation of photovoltage.
This is known as window effect and firstly reported first by Preston [59] and known
as heterojunction window effect, but interest in the heterojunction devices was stimu-
lated by the work of Kroemer and other researchers [60–63]. Though the p-n junction
solar cells of single crystalline silicon are preferred because of their high efficien-
cies of above 25%, the stringent requirement of very elaborate configurations for the
realization of high efficiency impasses a serious shortcoming that the manufacturing
cost would be very high [64] which leads to the search for low-cost solar cells. In
recent years, heterojunction-based solar cells have gained great attention because of
their lower manufacturing cost, in spite of their relatively low conversion efficiency
[11, 65, 66]. A variety of techniques could be used for the preparation of heterojunc-
tion solar cells [67, 68]. Thin-film solar cells (TFSC) are a promising approach for
terrestrial and space photovoltaics and offer a wide variety of choices in terms of
device designing and fabrication. A variety of substrates (flexible or rigid, metal, or
insulator) can be used for the deposition of different layers (contact, buffer, absorber,
reflector, etc.) using different flexible techniques those allowed tailoring and engi-
neering of the layers in order to improve device performance [69–79]. But efforts
on n-CdIn2 Se4 /p-CdTe heterojunction solar cells fabricated by simple and low-cost
chemical spray pyrolysis technique have given less coverage. This technique has
some advantages over others like easy to vary the concentration of precursors and the
substrate temperature for controlling stoichiometry and adherence of the deposited
layers. The next paragraph comprises the advancement in the field of CdIn2 Se4 /CdTe
based electrochemical solar cells.
During the last few years, the conversion efficiencies of PEC cells (also called
electrochemical photovoltaic cells) have risen steadily, and a number of systems and
reasons to excellent stability have been reported. The CdIn2 Se4 thin films having
n-type semiconducting nature are used to CdIn2 Se4 /CdTe based thin film solar cells
where CdTe thin films are having p-type semiconducting nature and then study
the current–voltage, capacitance–voltage, and spectral response characteristics, and
consequently, photovoltaic or performance parameters viz junction ideality factor,
fill factor, power conversion efficiency, flat-band potential (V fb ), and energy bandgap
(E g ) can be evaluated using these measurements.
The substrate cleaning plays an essential role in the device fabrication process,
and therefore prior to making a device, the required substrates should be successively
42 S. Chander

Fig. 5 Typical schematic device structure of CdIn2 Se4 /CdTe based electrochemical solar cells in
a substrate configuration

cleaned by ultra-sonication in detergent solution, deionized water, ethanol, acetone,

and 2-propanol and then should blow-dried with nitrogen and then treated in UV-
ozone for 20–30 min. The typical schematic device structure of CdIn2 Se4 /CdTe based
electrochemical solar cells in substrate configuration is demonstrated in Fig. 5.
The physical properties of thin CdIn2 Se4 films are investigated by Dalchiele et al.
[13], where the films were grown by electrodeposition technique. The photoelec-
trochemical measurement electrode in the presence of 1 M poly-sulfide electrolyte
revealed the device conversion efficiency of 0.42% under the light illumination inten-
sity of 80 mW/cm2 . The absorber p-CdTe type thick layer having optimized prepar-
ative parameters (viz. substrate temperature of 250 °C, solution concentration of
10 mM, solution quantity of 40 cc, spray rate of 2 cc/min, and pH (10)) was grown
onto FTO coated glass by Rajpure’s group [30] using spray pyrolysis technique. On
the absorber layer, a thin layer of n-CdIn2 S4 having optimized preparative parameters
(viz. substrate temperature of 360 °C, solution concentration of 50 mM, quantity of
solution of 56 cc, spray rate of 3 cc/min) was grown by same technique (as mentioned
above). FTO layer acts as a back contact while the front contact was made with the
help of silver paste. A thin layer of TiO2 was used as an antireflection coating.
This developed heterojunction solar cell under illumination was further tested for
their current–voltage (I–V ), capacitance–voltage (C–V ), power output character-
istics, and spectral response. They studied the photovoltaic parameters viz. power
conversion efficiency, fill factor, series and shunt resistances, junction quality factor in
the dark (nD ), and light (nL ) for the n-CdIn2 Se4 /p-CdTe heterojunction solar cells. The
device exhibited a maximum fill factor of 0.55 and a power conversion efficiency of
0.67%. Their I–V measurements suggested that the forward current in these junctions
involved tunneling while the forward current can be explained by a multi-tunneling
capture-emission model in which the hole emission process dominates the carrier
Advancement in CdIn2 Se4 /CdTe Based Photoelectrochemical … 43

transport mechanism. Bhalerao et al. [31] have fabricated (photo)electrochemical

CdIn2 Se4 thin-film solar cells using electro-synthesizing technique and analyzed
using current–voltage and capacitance–voltage characteristics along with photore-
sponse, speed response, and electrochemical impedance studies. The PEC perfor-
mance of the cell showed a good photoresponse, comparatively high short-circuit
current, and open-circuited voltage with better stability over the long duration with
the lower value of diffusion coefficient and high value of carrier lifetime to support
lower recombination rate. The improved photoconversion efficiency can be explained
with the help of theoretical modeling of the energy band diagram of the impedance
spectra of the PEC cells. The reduced interfacial charge transfer resistance of the
PEC cell after illumination is responsible for improving the photocurrent, which
has promise for low-cost photovoltaic device fabrication. There is intensive research
focused on the progress of CdIn2 Se4 thin film as a window potential layer to the PEC
solar cells.

6 Conclusions

The solar energy is radiant energy produced by the sun, and there has been an
increasing interest during the past few decades in metal chalcogenide thin films
because of their promising applications. The ternary chalcogenide CdIn2 Se4 semi-
conducting material has received very little attention as a prospective material for
photoelectrochemical (PEC) cells, but it may be used for the sustained and efficient
capture of solar energy conversion because it offers a wide variety of choices in
terms of the device designing and fabrication. The performance of solar cells can
be enhanced with the approaches adopted based on the materials layer processed
methods and the band alignment. The recent progress in CdIn2 Se4 thin-film material
has shown the practicability to develop high-efficiency PV devices as it is stable,
eco-friendly, and low cost. The fabrication of CdIn2 Se4 thin-film-based heterojunc-
tion solar cells was done by using some chemical and physical techniques. This
chapter deals with the preparation of CdIn2 Se4 thin films from aqueous medium
by cost-effective and simple spray pyrolysis and consequently use of these films
in heterojunction solar cell applications. It also extensively described the physio-
chemical properties of CdIn2 Se4 thin film as a potential window layer to the photo-
electrochemical solar cells. For CdIn2 Se4 /CdTe based solar cell technology to reach
the commercialization stage, this review also highlighted the significant research
progress and the patentability for further improvement in the power conversion effi-
ciency by the understanding of the window layer material and reducing non-radiative
recombination centers. The research efforts should be focused on the development
of new approaches for synthesizing CdIn2 Se4 thin film as well as the understanding
of device mechanisms and operation. The promising candidature of this material
remains a reality, and the technology may be enormously useful for the world and
society to cater to the current energy demand as a leading contender.
44 S. Chander

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Cadmium Sulfide Thin Films
by Chemical Bath Deposition Technique

M. S. Aida and S. Hariech

Abstract In this chapter, we describe the usefulness of chemical bath deposi-

tion (CBD) technique to produce high-quality thin films of cadmium sulfide for
large-scale applications. In terms of operation, CBD offers unique blend of cost-
effectiveness and rapid deposition rate of thin films with controlled morphology
and crystallite size. Compared to other expensive thin films deposition techniques,
this strategy involves the use of low-cost precursors, solvents and ambient condi-
tions or mild temperature (up to 70 °C). Here, we explain the fundamentals of CBD
with emphasis on growth mechanisms in CBD and influence of key parameters like
temperature, reaction time, substrates type, and solvent to grow high conformal thin
films for technological grade.

Keywords Thin films · Cadmium sulfide · Chemical bath deposition · Films

growth mechanism · Semiconductors

1 BII AVI Semiconductors and Metal Chalcogenides

BII AVI semiconductors are chemical compounds composed of two elements, where
B is an element of group II of the periodic table such as zinc, cadmium, and mercury
and A is an element of group VI: sulfur, oxygen, tellure, and selenium. Hence,
the formed binary compounds can be: oxides (ZnO, CdO), selenides (ZnSe, CdSe,
HgSe), sulfides (CdS, ZnS, HgS), and tellurides (ZnTe, CdTe, HgTe) [1]. This type
of semiconductors materials are also called metallic chalcogenides; their optical,

M. S. Aida (B)
Department of Physics, Faculty of Science, King Abdulaziz University, Djeddah, Kingdom of
Saudi Arabia
e-mail: [email protected]
Center of Nanotechnology, King Abdulaziz University, Djeddah, Kingdom of Saudi Arabia
S. Hariech
Department of Physics, Faculty of Science, University Frères Mentouri Constantine 1,
Constantine, Algeria

© Springer Nature Switzerland AG 2020 49

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_3
50 M. S. Aida and S. Hariech

electrical, and magnetic properties have been intensively studied [1]. Metal chalco-
genides semiconductors, with wide optical gap, are of considerable technological
interest because their emissions cover the blue and green spectral regions. They found
particularly several applications such as optoelectronic devices, lasers and detectors,
light emitting diodes (LEDs), nonlinear optical materials, optical fibers, thermal
imaging, radiation detectors, third-generation photovoltaic cells, magneto-optical
devices, and materials for magnetic storage of information [2–7].

1.1 Metal Sulfides and Cadmium Sulfide (CdS)

The existence of metal sulfides has long been known; since miners have always
observed sulfur as the mineralizer of metals. For a long time, chemists have directed
their researches in the field of mineralogy as well as that of chemistry. They attempt
to reproduce the different minerals in laboratories. Sulfur possesses the property
to combine directly with almost all metals. Quite often, the combination takes
place with mostly alkali metals, zinc, lead, copper, etc. because of the high affinity
between sulfur and these metals [8]. CdS is an interesting semiconductor; it found
a wide range of applications in photovoltaics, optoelectronics, catalysis, and biolog-
ical sensors [9]. CdS possesses excellent structural and optical properties allowing
it to be a good candidate as a buffer layer in CdS/CuInSe2 [10], CdS/CdTe [11],
CdS/CIGS [12], CdS/CuS [13] and recently in Cu2 ZnSnS4 /CdS thin film solar cells
[14], optical filters, gas sensors, [15] thin films transistors [16], semiconductor lasers
[17], and photoelectrochemical cells [18]. Various techniques have traditionally been
adopted to prepare high quality of metal chalcogenides thin films, each technique
has its own limits. For example, solid-state reactions occur only at high tempera-
tures to transition into molten states of solid reagents. However, techniques such as
spray pyrolysis, vapor deposition, and vacuum evaporation require high tempera-
tures to allow chalcogenides formation, and in contrast, the chemical methods such
as hydrothermal deposition, solvothermic, and chemical bath (CBD) can be used at
lower temperatures.

1.2 Chemical Bath Deposition Technique

Thin films chemical bath deposition (CBD) is a very old technique, also called solu-
tion growth technique. In 1835, Liebig presented the first report of deposition of
silver using this method [19, 20]. Earlier, CBD has been limited to the deposition of
lead compounds PbS and PbSe [21]; a wide range of substrates have been success-
fully used for these deposits; namely porcelain, ebonite, iron, steel … etc. [22]. The
range of metal chalcogenide films deposited by CBD has been gradually developed,
particularly in the 1980s. In 1982, there were approximately twenty metal chalco-
genide, which can be synthesized by this technique. Nowadays, it exceeds 50, mostly
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 51

are semiconductors [23]. The reason for this increasing interest is due to the benefits
of the attractive CBD technique. After the success of chemical bath CdS films depo-
sition on CdTe (and later on CuInSe2 films) to produce more efficient photovoltaic
(PV) cells by comparing to CdS films obtained by thermal evaporation [24–27], CdS
become the most studied material prepared by this technique [21].
The first CdS layer deposited by CBD and used in photovoltaic cells was achieved
by Birkmire et al. [28] reported that CdS film obtained by CBD leads to 10.6%
CuInSe2 based solar cells efficiency which is larger than that of (Cd, Zn) S prepared
by evaporation. The reached efficiency record of CuInSe2 cells using CdS prepared
by CBD is of 19.8% [29].
CBD technique enjoys several advantages:
• It is relatively simple and safe [30] due to the application over a wide range of
easy chalcogenide compounds preparation.
• The flexibility in the substrate choice.
• It is a useful and excellent technique for nanomaterial preparations such as
polycrystalline CdS films for optimal photovoltaic devices [24–26].
• It allows the deposition of homogeneous, adherent, and reproducible thin films
over a large surface [31].
• It is carried out at low temperatures as well as at relatively high temperatures.
• It is a slow process, in which the reaction time required is sometimes several hours
or even tens of hours [32]. This may favor the crystallites size and orientation
control [33].

1.3 Chemical Bath Deposition Mechanisms

Chemical deposition of films on solid substrate is achieved by means of reactions

occurring in an aqueous solution. It is based on the chemical transformation of
precursor through species exchange. If the exchanged species are electrons, the
deposition technique is called CBD redox or “electroless deposition.” While, if the
exchanged species are chemical elements, the technique is called CBD. During CBD
deposition, substrates are immersed in diluted solutions containing metal ions (Mn+ )
and a source of chalcogenide (Cm− ) such as sulfur S2− . The concept of the solubility
product (Ksp) is introduced for understanding the CBD deposition mechanisms. The
solubility product informs about the salt solubility. Consider a soluble salt (CdS for
example) in equilibrium with its saturated aqueous solution:

CdS(s) → Cd2+ + S2− (1)

where subscript s represents the solid phase. The CdS dissolves in water producing
a few amount of Cd and S ions. The solubility product (Ksp) is the concentrations
product of the dissolved ions as defined by the following equation:
  
Ksp = Cd2+ S2− (2)
52 M. S. Aida and S. Hariech

Table 1 Solubility products

Solid Ksp Solid Ksp
of different compound (at
25 °C) used in CBD Ag2S 3× 10−50 FeS 10−18
deposition AgCl 2× 10−10 HgS 6 × 10−35
AgI 10−6 PbS 10−28
Cd(OH)2 2× 10−14 PbSe 10−37
CdS 10−28 SnS 10−26
CdSe 4 × 10−35 SnS2 6 × 10−57
CdTe 10−42 SnSe 5 × 10−34
Cu2 S 10−48 Zn(OH)2 10−16
CuS 5 × 10−36 ZnS 3 × 10−25
Fe(OH)2 5× 10−17 ZnSe 10−27

more generally, for the dissolution:

MaXb → aMn+ + bXm− (3)

The solubility product of Ksp = [Mn+ ]a [Xm− ]b .

The more soluble is the salt, the greater is the solubility product Ksp.
A list of approximate values of Ksp for some semiconductors and related salts
encountered in CBD is given in Table 1.
When ions concentrations product exceeds the solubility product Ksp, two events
may happen:
• Formation of a precipitate (powder) in the solution. This process is called
homogeneous deposition
• Formation of a deposit on solid surface (substrate or the vessel walls). This process
is called heterogeneous process. Generally, both processes are concurrent and may
be present in the same time but with different rates.

1.3.1 Homogeneous Nucleation

The first stage of powder formation is the individual ions or molecules contact and
collision to aggregate and form embryos by coalescence. They are subsequently
enlarged by coalescence to form a stable nuclei as shown in Fig. 1.

1.3.2 Heterogeneous Nucleation

In heterogeneous nucleation, the nucleation step is achieved on the solid substrate

through embryon ions adsorption onto the substrate. Any substrate immersed in
the solution acts as a nucleation center. Generally in a alkaline aqueous solution
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 53

Fig. 1 Particles aggregation

and coalescence in solution

commonly used in CBD technique, the metallic ion forms a hydroxide precipita-
tion Cd(OH)2 rather than film formation. To prevent this homogeneous precipita-
tion, the Cd complexation is necessary. Ammonium hydroxide is a commonly used
complexant agent. Cd(NH3 )4 2+ complex is formed according to the reaction:

Cd2+ + 4NH3 → Cd(NH3 )4 2+ (4)

Films formation on the substrate is based on the chalcogenic ions slow release
in the solution, where free metal ions are complexed. The complexing agent should
not be too weak to prevent solution precipitation of the hydroxide and not too strong
to prevent the film from being deposited. Thereafter, the amount of ammonia to add
depends on Cd concentration, solution temperature, and pH [20].
The CBD mechanisms can be achieved through two different processes:
• The compound formation through ionic reactions involving free anions (ion-by-
ion mechanism)
• Decomposition of metal complexes (cluster-by-cluster mechanism).
These mechanisms are often unclear due to their complexity and their simulta-
neous occurring.

1.4 Ion-by-Ion Mechanism

This mechanism is the simplest one, when the ion product [Cd2+ ][S2− ] exceeds 10−28
the solubility product of CdS [19], consequently a solid phase of CdS will be formed.
The film growth occurs through sequential ionic reactions as follow:
 
Cd(NH3 )4 2+ → Cd2+ + 4NH3 dissociation of complex to free Cd2+ ions (5)

 
(NH2 )2 CS + 2OH− → S2− + CN2 H2 + 2H2 O formation of sulphide S2− ion
(6)
54 M. S. Aida and S. Hariech

Fig. 2 Schematic drawn of the deposition steps involved in ion-by-ion deposition process

Cd2− + S2− → CdS (CdS formation by ionic reaction) (7)

A complex is generally necessary to maintain constant metallic ions concentration

in the solution and to avoid the hydroxide precipitating. In this situation, the presence
of any solid surface (i.e., substrate, vessel walls) acts as nucleation center.
The adhesion and attraction of species on the substrate is achieved by the Van der
Waals force. Once the nucleation step starts on a substrate, the film growth becomes
easier, since deposition is easier on a covered surface than on a clean one. Films
growth by this process proceeds as follow (see Fig. 2):
A: Cd and S ions diffusion toward the substrate.
B: Nucleation of CdS facilitated by the substrate.
C: Formation of CdS nuclei by adsorption of Cd and S ions incoming from the
solution.
D: Subsequent growth of CdS.

1.5 Cluster-by-Cluster Mechanism

If the complexing agent concentration is low to prevent metal hydroxide formation,

small amount of Cd(OH)2 can be formed in a colloidal form. The metal hydroxide
Cd(OH)2 plays an important reaction intermediates during CBD process. CdS film
is then formed by reactions:
 
nCd2+ + 2nOH− → Cd(OH)2 n (formation of Cd(OH)2 cluster) (8)

 
Cd(OH)2 n + nS2− → nCdS + 2nOH− (exchange reaction) (9)

CdS is formed because its precipitation constant Ksp is 10−28 is too low by
comparison to that of Cd(OH)2 (2 × 10−14 ). Moreover, this is due to the free formation
energy of CdS that is more negative than that of Cd(OH)2 . Thereafter, CdS formation
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 55

occurs preferentially on the hydroxide surface rather than to nucleate separately in

the solution. Then CdS is homogeneously formed and precipitates in the solution.
The film deposition passes first by the hydroxide adhesion on the substrate. Then the
hydroxide conversion into CdS forming a primary CdS clusters deposition.
The films are formed via cluster-by-cluster process according the following steps
(as depicted in Fig. 3):
A: Hydroxide colloidal particles diffusion to the substrate, where they adhere.
B-C: Reaction with S ions. This reaction results in exchange of the hydroxide by
sulfide. This reaction occurs simultaneously on the surface-adsorbed colloids and
on the dispersed ones in the solution. The reaction will continue until the total
conversion of the hydroxide to sulfide.
D: The primary CdS particles aggregate to form a solid film.
Since in cluster-by-cluster process, films are formed through the colloids,
incoming from the solution, sticking on the substrate, the crystallite size cannot vary
too much with the film thicknesses. While in the case of ion-by-ion growth process,
since the crystal growth occurs through the nucleation on the substrate, the crystal
size may increase with increasing deposition time. It is possible that the mechanism
may change during the deposition, or both mechanisms occur in parallel.

Fig. 3 Schematic diagram of the different steps involved during the cluster-by-cluster deposition
mechanism
56 M. S. Aida and S. Hariech

2 CdS Thin Film Deposition

In this chapter, we focused on the growth mechanism of CdS thin films by chemical
bath deposition. Figure 4 depicted a schematic schema of the experimental setup
used for CdS thin films deposition. The different processes are regrouped in Fig. 4.

2.1 Deposition Kinetics

The CdS deposition rate variation has been extensively studied, by several authors, as
a function of different deposition parameters such as: bath temperature [34], deposi-
tion time [34], pH of the solution [35] and thiourea [36] or cadmium concentrations
[37]. Due to the different processes occurring during CBD thin film formation, the
growth kinetics may widely vary from one deposition condition to another.
Generally, films kinetic growth passes by three periods (as shown in Fig. 5):
• Induction (or incubation) time at the early stage of the process, where no clearly
deposit is detectable. This time corresponds to the chalcogenide concentration
rising.
• Linear growth. The deposition starts only when the chalcogenide CdS concen-
tration is high enough to permit the nucleation and the subsequent growth. Some
studies [38, 39] suggested that, during this step, the chemical process is the
rate-limiting growth rather than the diffusion process.

Fig. 4 Diagram of the CBD process. CdS film is formed by a mechanism ion by ion (blue) or a
cluster by cluster (red) or both simultaneously. Homogeneous precipitation in solution (green) and
heterogeneous precipitation on the substrate (blue and red).
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 57

Fig. 5 Variation of film

thickness as a function of
deposition time using CBD
technique

• Termination. During this step, the growth slows down and may stop due to the
reactants consumption. The terminal film thickness depends on the deposition
parameters.

2.2 Influence of Solution Temperature

The whole investigated temperature range in CdS deposition by CBD technique is

ranged between 50 and 90 °C. Lower temperatures do not promote the chemical
reactions necessary for film formation, while higher temperatures cause the solution
evaporation especially the ammonia generally used as complexing agent. As shown
Fig. 6, CdS film thickness and the deposition rate are sensitive to the solution bath
temperature. The temperature influence can be divided, at least, in three regions:
• Region I: Low temperatures range (<65 °C): In this range, the deposition rate
increases linearly as a function of the temperature bath. This is due to the thermal
activation of chemical reaction between species, contributing in films forma-
tion. The bath temperature may motivate, the thiourea decomposition, which is
responsible for sulfur chalcogenide ion (S2−) production:

SC(NH2 )2 + 2HO− → S2− + CH2 N2 + 2H2 O (10)

and on the other hand, it releases metal ions (Cd2+ ) by dissociation of complexing
compound Cd(NH3 )4 2+ according to the following equation:
58 M. S. Aida and S. Hariech

Fig. 6 Variations of CdS thin films thickness and growth rate as a function of bath temperatures

Cd(NH3 )4 2+ → Cd2+ + 4NH3 (11)

The formation of this compound is an intermediate reaction, necessary to control

(Cd2+ ) ions hydrolysis:

NH4 + + HO− → NH3 + H2 O (12)

CdSO4 → Cd2+ + SO4 2− (13)

 2+
Cd2+ + 4NH3 → Cd(NH3 )4 (14)

Consequently, the obtained free ions Cd2+ and S2− react between them by ionic
reaction (mechanism ion by ion) to form CdS film:

Cd2+ + S2− → CdS (15)

The calculated activation energy of film growth (insert Fig. 2), in this temperature
range, is equal to 0.72 eV (~71 kJ/mol), which is close to the formation enthalpy
74.2 kcal/mol of Cd2+ [30]. This may suggest that Cd2+ ions formation controls the
films growth. This comforts the fact that ammonia complexing agent is required for
Cd2+ ions slow release necessary for films growth control. In this temperature range,
the films growth is governed by ion-by-ion process. However, increasing the bath
temperature from 55 to 65 °C enhances the thiourea decomposition and Cd2+ ions
release. This leads to the free ions (Cd2+ and S2− ) concentrations increase in the bath,
which leads to the growth rate increasing.
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 59

• Region II (saturation): At 65 °C, the growth rate reaches its saturation due to the
fast and complete decomposition of thiourea and cadmium sulfate. The tempera-
ture of 65 °C can be considered as the critical temperature corresponding to the
appearance of a mixed growth mode where both ion-by-ion and cluster-by-cluster
mechanisms contribute in the films formation.
• Region III: (T > 65 °C): At this temperatures range, a fast formation of CdS
clusters is observed on the substrate surface as well as in the solution. Once the
reactants are depleted, the growth rate is reduced and stops. The films growth,
in this temperature range, is achieved through the cluster-by-cluster mechanism.
The film formation passes, at the beginning by an intermediate phase Cd(OH)2
production originating from the ammonium hydroxide dissolution according to
the following reactions:

 
nCd2+ + 2nHO− → Cd(OH)2 n (16)

and then by the replacement of HO− by S2− to form at the end the CdS deposit:
 
Cd(OH)2 n + nS2− → nCdS + 2nHO− (17)

Increasing the temperature from 65 to 75 °C yields to the growth rate reduction

(Fig. 2). This is due to the reactants depletion in the solution due to their consumption.
In fact, at very high temperatures (>65 °C), ammonia (NH3 ) starts to be evaporated
during chemical reactions. The presence of NH3 in the bath is essential chemical
reactions controlling in one hand for colloids creation in the solution prevention on
the other hand. Moreover, the evaporation of NH3 and therefore HO− formation in the
solution suggests that film growth is controlled by cluster as a dominant mechanism.
Moreover, the reduction of growth rate and film thickness may have other origins
such as:
• Dissolution of unstable nuclei adsorbed on film surface,
• Film peeling due to its thickness increase.
This variation shape is an intrinsic characteristic of CBD technique, by comparison
to other thin films deposition techniques of [19]. It is well argued that higher depo-
sition rates and higher thicknesses are usually accompanied by powder formation
[40].

2.3 Influence of Salt Molarity

CdS film growth is also sensible to the molarity of cadmium source. As reported
in Fig. 7 showing, the deposition rate variation as a function of Cd source molarity
in this example CdCl2 is the source of Cd. Increasing of CdCl2 molarity causes the
60 M. S. Aida and S. Hariech

Fig. 7 Variation of the

deposition rate as a function
of Cd salt molarity for two
deposition times

increase of the Cd concentration, which yields growth rate enhancement. Sasikala

et al. [41] have deposited CdS thin films using CdCl2 as source of Cd by varying
the molarity from 0.1 to 1 M and noticed deposition rate enhancement with the Cd
concentration.

2.4 Influence of Cd Salt Source

In CBD deposition, several Cd salts have been used. As can be seen in Fig. 8, the depo-
sition rate is Cd salt dependent. The deposition rate increases with changing the CdS
salt nature in the following order CdCl2 , CdSO4 , Cd(CO3 ), and Cd(CH3 COO)2 . Few

Fig. 8 Variation of CdS

films deposition rate as a
function of time for different
Cd salt sources
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 61

Table 2 Stability coefficient

Salt complex Stability constant (log scale)
of complex formed with
Cd[SO4 ]3 4− 2
different Cd salt source
Cd[CH3 COO]2 2.19
Cd[Cl]4 2− 2.93
Cd[I]4 2− 6.4
Cd[NH3]4 2+ 7

studies have been devoted to the influence of the Cd salt on CdS thin film properties
[42–44]. Khallaf et al. [43] have grown CdS film with four different sources. In their
study, they used several Cd salt sources with lower molarity of 0.2 mM, ammonia as
complexing agent and solution temperature equals to 70 °C. They ranked, from the
lowest to the highest achieved films’ thickness, the CdS salts in the following order:
CdI2 , CdCl2 , Cd(CH3 COO)2 , and Cd(SO4 ) (Table 2).
The influence of the salt nature on the deposition rate can be explained by consid-
ering the stability of Cd complex for each salt. In Table 1, we have reported the
stability of some Cd complexes formed in the salt bath during CBD deposition. The
rank of complex stability is as following CdI2 , CdCl2 , Cd(CH3 COO)2 , CdSO4 [43].
This is in the same order as the thickness of the deposited CdS films. The most stable
salt releases much slowly Cd ions to contribute in film formation and consequently
lower deposition rate.

3 Films Structure and Morphology

3.1 Structural Properties

From structural point of view, the most interesting feature in CdS thin films deposited
by CBD is their polymorphism. CdS structure can be either hexagonal (Wurtzite: α-
CdS phase), cubic (sphalerite or zinc blende: β-CdS phase), or mixed phase. The
distinction between these two phases is difficult; this is due to the fact that several
planes in both phases have the same diffraction angle. For example: the (111) in the
cubic phase and the (002) plane in the hexagonal one diffract at the same angle 26.6°.
Moreover, (110) plane in the hexagonal structure and (220) in the cubic one diffract
at the same angle 43.8°. The (004) plane in hexagonal phase and the (222) in cubic
phase have the same 53.78° diffraction angle. CdS wurtzite structure is the same as
that of ZnO material (Fig. 9). Each elementary cell has two CdS molecules, the two
Cd atoms occupy positions (0, 0, 0); (1/3, 2/3, 1/2), and the two S atoms occupy
positions (0, 0, 4); (1/3, 2/3, 1/(1 + u)) with u ≈ 3/8 [35].
In the case of the cubic structure (Zinc blend) (Fig. 10), each elementary cell
contains four CdS molecules, whose atoms occupy well-defined positions defined
by coordinates: 4 S atoms in positions: (0, 0, 0); (0, ½, ½); (½, 0, ½); (½, ½, 0); 4
62 M. S. Aida and S. Hariech

Fig. 9 Structure of CdS

(Wurtzite) crystal

Fig. 10 Zinc blend structure

of CdS crystal

Cd atoms in positions: (¼, ¼, ¼); (¼, ¾, ¾); (¾, ¼, ¾); (¾, ¾, ¼). In this structure,
each atom Cd has four neighbors S occupying the vertices of a regular tetrahedron.
Certain BII AVI compounds are transformed under the action of high external pres-
sures into the rock salt structure (NaCl), characterized by an octahedral arrangement
of the atoms, and although these phases are unstable under normal conditions, they
can sometimes remain at low temperatures [45, 46]. On the other hand, under a pres-
sure of 2.6–4.2 GPa, the hexagonal structure is transformed into a rock salt structure.
At a higher pressure of 60–86 GPa, the rock salt structure is transformed into a
distorted cubic structure of the rock salt [46].
The values of the parameters of CdS network are summarized in the following
Table 3.
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 63

Table 3 Crystallographic parameters of different crystalline structures of CdS

Compound Crystalline structure Network parameters (Å) Ref.
CdS Wurtzite (α-CdS) a = 4.16 and c = 6.75 [35]
Zinc blend (β-CdS) a = 5.83
Rock salt a = 5.32
Distorted rock salt a = 3.471, b = 4.87 and c = 3.399

Table 4 Crystallographic structure, grain size, and preferential orientation of CdS thin films
produced by different techniques
Technique Parameters Structure D (nm) (hkl)
studied
RF magnetron Power Hexagonal – (002)
sputtering (60–120 W)
Power RF Mixed C/H at low – C(111)/H(002)
75–150 W pressure
Substrate Hexagonal at high –
temperature: pressure (150 W)
100–250 °C
Annealing Hexagonal – (002)
Thermal Deposition time Hexagonal 54–62 (002)
evaporation Hexagonal 25 (002)
PLD Doping par C Hexagonal 52–72 (002)
ED Hexagonal 13–25 (002)
Spray Substrate Mixte à basse T 10–33 C(111)/H(101)(002)
temperature Hexagonal with the 15–30 (101)
increase of T
CBD Deposition time Cubic 26–34 (111)
Cadmium Hexagonal 10–12 (002)
concentration
Complexing Hexagonal – (002)
agent NTA
Solution Cubic 170 (111)
temperature
Substrate nature Mixed 50–300 (002)/(111)
hexagonal/cubic
Cadmium Mixed – (002)/(111)
source hexagonal/cubic
D Grain size, hkl Miller indices for the preferential orientation, PLD Pulsed laser deposition, ED
Electrodeposition
64 M. S. Aida and S. Hariech

Fig. 11 XRD spectra of CdS

films deposited by CBD: at
different temperatures.
Reprinted with permission
from [47]. Copyright © 2007
Elsevier B.V.

Table 4 summarizes the crystalline structure, grain size, and preferential orien-
tation reported in the literature of CdS films deposited by different deposition tech-
niques. In general, the binding in compounds II-VI is ionic as well as covalent but is
only ionic in those that have the structure of rock salt.
The crystal structure and physical properties of CdS thin films are sensitive to the
method and deposition conditions. Among all these structures of CdS, the hexagonal
is the most thermodynamically stable and thus the most common observed. Due to
its metastable character, the cubic phase can be transformed into hexagonal under
the effect of annealing temperature.
Several studies have confirmed the deposition parameters influence on the struc-
ture of CdS films deposited by CBD technique. These include bath temperature,
time, the nature and concentrations of the source solutions, the pH of the bath, the
nature of the substrate, and sometimes the agitation of the solution [45]. However,
at low temperature, CdS films are amorphous with a low crystallinity (hexagonal
and/or cubic) which can be improved with increasing temperature or prolonging the
deposition time, as shown in Fig. 11 [47]. The increase in temperature also favors
the transformation of the cubic structure to the hexagonal one.
The nature of both used cadmium source and complexing agent can be decisive
for the structure of the future film [45]. Table 5 reports the influence of Cd source
nature on the structure of the deposited CdS films by CBD at various temperatures
and baths.
Also, Table 6 shows the influence of used complexing agent on CdS films structure.
Saxena et al. [48] found that the crystal structure is cubic for all CdS films elab-
orated by CBD whatever the nature of Cd source precursor used in the bath. This
was confirmed by their DRX results shown in Fig. 12, which indicates that all films
deposited from different source solutions are polycrystalline with an orientation
preferential according to the plane (111) where the degree of texturing increases in
this order: CdCl2 , CdI2 , Cd (CH3 COO)2 , CdSO4 . It is worth noting that the nature
of the substrate and the deposition conditions change the structure as well as the
crystallographic orientation of the film.
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 65

Table 5 Influence of parameters: Cd source nature, pH values, and bath temperature on the structure
crystalline CdS
Cd source Precursors solution Bath pH Deposition Structure
temperature T crystalline
(°C)
CdCl2 CdAc2 a NH4 OH/NH4 Cl/Tub 11 80 Hexagonal
amorphe
CdCl2 NH4 OH/NH4 Cl/Tu 11.5 >40 Cubic
CdI2 NH4 OH/NH4 I/Tu – >60 Hexagonal
CdSO4 NH4 OH/Tu – 60–85 Hexagonal
CdSO4 NH4 OH/N2 H4 /Tu – 60 Mixed
CdSO4 NH4 OH/Tu 11–12 70 –
CdAc2 NH4 OH/NH4 Ac/Tu – 85 –
CdAc2 NH4 OH/NH4 Ac/Tu 9 50–90 Mixed
CdAc2 TEA + NH4 OH/Tu – 30–85 –
CdAc2 Na3 C6 H5 O7 /NH4 OH/Tu – 50–90 –
Cd(NO3 )2 NH4 NO3 /NaOH/Tu 7.8–13.5 20 Cubic
a Ac Acetate (CH3 COO)− , b Tu Thiourea SC(NH2 )2 , TEA Triethanolamine

Table 6 Influence of the

Nature of Cd complex Structure Refs.
nature of Cd complex on the
crystal structure of CdS films Halide, citrate Hexagonal [48]
Nitrate Hexagonal [50, 51]
Sulfate, acetate, chlorure, Cubic [48]
ammonium salt
Triethanolamine Mixed structure [48]

Figure 13 represents the XRD diffraction patterns variation as function of deposi-

tion time. The absence of peaks in the spectra of film deposited at low time suggests
that the deposited films in early stage are amorphous. Increasing deposition time
leads to a peak emergence at 28.2° assigned to the (101) plane of the hexagonal
structure. Further increase in the deposition time rends the peak assigned to the
plane (101), sharper and intense. Moreover, increasing the deposition time engen-
ders the emergence of a peak located at 58.2° originating from (202) diffraction plane
in the hexagonal structure. The preferential orientation in CdS is controlled by the
nucleation process associated to the low deposition rate [49, 50]. It is reported that
(002) and (111) planes are the generally observed preferential orientations in the
hexagonal and the cubic structure, respectively [30, 51], in CBD deposited CdS thin
films when using ammonia as complexing agent. While, in spray pyrolysis deposited
CdS films hexagonal (101) preferential orientation has been reported [52, 53]. The
grain sizes, calculated from XRD diffraction analysis, were 26 nm in films deposited
during 60 min and 40 nm in films deposited during 120 min.
66 M. S. Aida and S. Hariech

Fig. 12 XRD spectra of CdS films deposited using four different Cd source solutions. Reprinted
with permission from [43]. Copyright © 2009 Elsevier B.V.

Fig. 13 XRD diffraction

patterns of CdS films
prepared with different
deposition times
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 67

CdS thin film is well known as an important partner to fabricate CdTe or CuInSe2
heterojunction-based solar cells. Despite that CdS in hexagonal phase suffers from
the high lattice mismatch with CuInSe2 (1.2%) by comparison to CdS (0.7%) in
cubic phase, hexagonal structure is preferred. This is due to its higher stability by
comparison to the cubic structure [54, 55]. Several attempts have been made to deposit
CdS films with hexagonal structure by changing the deposition parameters such as:
Cd source salt [56, 57], solution temperature [47, 58, 59], or thermal annealing [60].
Actually, in CBD process, ammonia plays a key role in the film structure. Using
ammonia, as complexing agent generally, leads to cubic, hexagonal, or mixed phase.
While, films prepared without ammonia exhibit a hexagonal as well as a mixed phase
structures [54]. Hence, using ETA as complexing agent rather than the commonly
used ammonia is one procedure to prepare pure hexagonal CdS thin films, which
is recommended for photovoltaic applications. It has been claimed that ion-by-ion
process leads to a pure hexagonal or a mixture of cubic and hexagonal structure,
while cluster-by-cluster process leads only to a pure cubic structure [53, 61].

3.2 Films Morphology

CdS film morphology depends on the deposition. Figure 14a–d shows the AFM
images of CdS films morphology variation with the deposition time. As can be
seen, the films surface morphology evolves with deposition time. Thirty minutes of
deposition time lead to a rough film with a columnar and pyramidal structure. The
film morphology becomes smoother and denser after 60 min; the columnar structure
becomes ended by a spherical shape. Smooth, dense, and pinhole free film is formed
after 90 min of deposition. However, after 120 min of deposition time, pyramidal
quantum dots are formed on the film surface with a uniform spatial distribution.
CdS films morphology changes with the molarity of cadmium salt (Fig. 15a–d).
The films surfaces become rougher with increasing molarity.
With increasing Cd salt source molarity, the film became rougher (Fig. 15) regard-
less of the deposition time. The surface roughness increases by a factor of six with
increasing the molarity from 0.1 to 0.4 M when using CdSO4 source. In CdS thin
films deposited with cadmium acetate molarity as Cd source, Gopinathan et al. [62]
reported that the surface roughness increases from 9 to 18 nm with increasing the
molarity from 0.4 to 0.5 M. The variation of the surface roughness is the consequence
of the variation of the deposition mechanism. Actually, growth mechanism occurs
by ion mechanism at low cadmium salt molarity condition and by cluster by cluster
when higher cadmium salt is used. For this reason, the quasi-totality of CBD-CdS
thin films deposition studies use mainly low molarity of Cd salt [51, 52, 63].
The surface morphology is also sensitive to the salt nature. The AFM images of
CdS films deposited with different salts were shown in Fig. 16. The early stage of
film growth occurs through 3D mechanism (Volmer–Weber mechanism). This yields
films with high surface roughness. If the deposition rate is sufficiently low, the growth
68 M. S. Aida and S. Hariech

Fig. 14 AFM images of CdS thin films deposited at different times: a 30, b 60, c 90, and d 120 min

mechanism will be 2D growth leading to the formation of a smooth surface, and in

the termination stage, quantum dots are formed.
These structures have been observed in films deposited with CdCl2 and
Cd(CH3 COO)2 (Fig. 16a, b), However, Cd(SO4 ) and Cd(CO3 ) salts produce rough
films (Fig. 16c, d). This difference may originate from the difference in the growth
rate of each salt. As mentioned above, CdS formation with CdCl2 and Cd(CH3 COO)2
salts exhibits the lowest deposition rate. This favors the 2D growth at the termination
of growth stage. In the case of Cd(SO4 ) and Cd(CO3 ), the growth rate is too high, and
therefore, the solution is consumed before reaching the 2D growth. Khallaf et al. [43]
have prepared CdS thin films using two salts CdSO4 and CdCl2 . They have noticed
that the film deposited with CdCl2 source is smoother than the films deposited with
CdSO4 .
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 69

Fig. 15 AFM images of CdS thin films deposited with different salt molarity. a 0.1, b 0.2, c 0.3,
and d 0.4 M

4 Growth Model

Actually, thin film growth occurs through three models (i) Volmer–Weber model (3-
D mode) (ii) Frank–Van der Merwe model (2-D mode) and (iii) Stranski–Krastanov
model. A schematic diagram of these models is depicted in Fig. 17. Island growth
occurs when the stable nuclei formed on the substrate grow in three dimensions to
form islands. This growth mechanism occurs when the deposited atoms are tightly
bonded to each other than to the substrate. However, the layer-by-layer or planar
growth occurs when the atoms of the deposit are strongly bonded to the substrate
than to each other. The Stranski–Krastonov (S-K) growth model is an intermediate
combination of the two preceding models. In this case after the formation of one or
more monolayer subsequent layer, growth is not favorable leaving the formation of
islands. In fact, S-K growth mode is observed when the formed layer increases beyond
a critical thickness in a substrate–film lattice mismatched system. With increasing
the thickness, the relaxation of film strain is achieved by the formation of islands
through elastic relaxation without any dislocation in the islands [64, 65]. This may be
the case in our samples, due to the amorphous structure of the used glass substrates.
70 M. S. Aida and S. Hariech

Fig. 16 AFM images of CdS thin films deposited with different Cd salt: a CdCl2 , b Cd(CH3 COO)2 ,
c CdSO4 , and d Cd(CO3 )

Fig. 17 Different thin film

growth models:
a Volmer–Weber,
b Frank–van der Merwe, and
c Stranski–Krastonov
Cadmium Sulfide Thin Films by Chemical Bath Deposition Technique 71

Fig. 18 Schematic diagram

of the different steps of film
growth. a Coalescence and
3D growth, b column
coalescence and ripening,
c smooth plane formation,
d quantum dots formation

Based on the results of AFM images CdS thin film, growth model for CdS thin film
prepared by CBD was suggested by Jaber et al. [53]. In this model, the film formation
passes through different steps. The different steps of film formation through the
suggested model are depicted in Fig. 18.
1. The initial growth stage is achieved by the commonly known nucleation and
coalescence followed by a subsequent vertical growth (3-D Volmer–Weber)
as shown in Fig. 18a. The obtained films are characterized by a high surface
roughness.
2. With increasing deposition time, the grain becomes sharper and unstable due to
reduction of number of bonded atoms; thus, the grains reduce their surface energy
via their coalescence (Fig. 18b). This phenomenon is called Ostwald ripening
[54]. In this step, the surface film roughness is reduced.
3. The most characteristic feature in CBD technique, in contrary to other deposition
techniques such as sputtering, thermal evaporation, spray pyrolysis, chemical
vapor deposition, is the depletion of the feedstock of incoming species during the
film growth. Consequently, the film growth rate is slowed and the film thickness
is saturated. This termination stage depends on the starting solution purity and
its molarity. The scarce of incoming species causes a larger mobility to the ions
on growing surface. By this way, ions can reach the valley site characterized by
a lower energy, resulting in valley filling and a flat surface as seen in Fig. 18c.
4. The rarefaction of ions forming the films reduces the nucleation centers on the
formed plane; hence, the incoming species migrate on the film’s surface to join
a stable nuclei which grows vertically to form a pyramidal column or a quantum
dot as seen in Fig. 18d.
72 M. S. Aida and S. Hariech

5 Conclusions

Chemical bath deposition is a cost-effective and simple technique for Cds thin film.
It is mainly based on the metallic ions precipitation control in a solution containing
sulfide ions. In CBD technique, the film growth can be achieved via two different
mechanisms: (i) ion by ion (heterogeneous reaction) or (ii) cluster by cluster (homo-
geneous reaction). Currently, CdS thin film is mainly deposited by this technique;
this method avoids the contact between the user and the hazardous Cd atom. CdS
film morphology and structure can be controlled through several parameters such as
deposition time, solution bath temperature, Cd salt nature, and molarity.

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Development of the Concept
of a Spheroidal Shape Anode for a Solid
Oxide Fuel Cell

Bogdan Vasyliv and Viktoriya Podhurska

Abstract Stress and strain distributions in the YSZ–NiO spheroidal shape anode-
substrate for a solid oxide fuel cell (SOFC) under the pressure of an operating envi-
ronment were calculated using the finite element analysis. The features were then
compared with ones of the cylindrical shape anode. The radii ranges for the cylin-
drical and spheroidal (segments of a sphere) parts of the anode ensuring its improved
deformation resistance and more uniform stress distribution were suggested. Based
on the calculations, an anode of the cylindrical shape with top and bottom convex
surfaces (a spheroidal shape anode), with the spheroid to cylinder radii ratio R/Rc
in the range from 5 to 20 is suggested. Its specific volume V /S c is in the range
from 1 to 2.5 mm. The stresses in the most dangerous areas (i.e., along the axis and
the closed-loop fixing) and maximum strain, caused by the external gas pressure
on the anode working surface, are decreased by 10–30% and 20–40%, respectively,
as compared to an anode of the cylindrical shape of the same radius and volume
features. This increases the lifetime of a solid oxide fuel cell. A three-dimensional
curve of intersection of the surfaces of stress distribution in the anode along its axis
and the closed-loop fixing was approximated which displays the values of balanced
stresses depending on V /V c and R/Rc parameters. Also, the advantage of the spheroid
shaped SOFC anode-substrate over conventional flat one was substantiated using a
shape-dependent crack deceleration approach.

Keywords Solid oxide fuel cell · Cylindrical and spheroidal shape anodes · Finite
element analysis · Stress and strain distributions · Shape-dependent crack
deceleration approach · Lifetime

B. Vasyliv (B)
Department of Mechanics and Automation Engineering, Lviv Polytechnic National University,
12 S.Bandera str., Lviv 79000, Ukraine
e-mail: [email protected]
B. Vasyliv · V. Podhurska
Department of Structural Fracture Mechanics of Materials, Karpenko Physico-Mechanical
Institute, 5 Naukova str., Lviv 79060, Ukraine
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 77

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_4
78 B. Vasyliv and V. Podhurska

1 Introduction

A solid oxide fuel cell (SOFC) is an electrochemical conversion device that produces
electricity directly from oxidizing a fuel. Fuel cells are characterized by their elec-
trolyte material; the SOFC has a solid oxide (ceramic) electrolyte. The advantages
of this class of fuel cells include high efficiency, long-term stability, fuel flexibility,
low emissions, and relatively low cost. The largest disadvantage is the high oper-
ating temperature which results in longer start-up times and mechanical and chemical
compatibility issues.
Among the up-to-date versions of the SOFC design, the anode supported one
prevails which consists of the thick anode-substrate layer and comparatively thin
electrolyte and cathode layers. A porous cermet consisting of two solid phases (nickel
one and zirconia stabilized with scandia and ceria (or with yttria), i.e., ScCeSZ–Ni
or YSZ–Ni) and pores, is widely used as anode material for a SOFC [1–4]. To reach
required electrical conductivity of as-sintered ScCeSZ–NiO or YSZ–NiO ceramic
anode, it is subjected to a reduction in a hydrogenous environment at high temperature
(usually a few hundred degrees celsius). Due to the reduction of NiO particles, a nickel
network is formed in a ceramic (YSZ) skeleton of the anode.
In order to improve the lifetime of a SOFC and to lower the cost of electricity that
it produces, researchers work to optimize the structure of its components to prevent
degradation of the physical and mechanical properties and improve the structure of
the SOFC as layered macrocomposite [5–9]. For this reason, elementary (single)
SOFCs of various geometrical shapes (from flat to cylindrical) have been developed.
The operating surface area of an anode of tubular shape [10] is of maximum
possible value from the geometrical and structural points of view. However, the
length of a tubular SOFC is limited by the stresses which occurred at sealing the
environment supply system, as well as caused by the environment pressure.
An anode of truncated cone shape [11] has a large operating surface area, char-
acterized by a high value of the ratio of surface area to volume of the anode, which
is however lower by 20–25% than for the anode of tubular shape. Its shape provides
connecting the battery of elementary SOFCs in such a way that each next cell by its
wider part is imposed on the narrower part of the previous cell. However, to ensure a
large operating surface area, the angle at the top corner of the cone should be small
(2–10°). In this case, substantial tensile stress arises in a wider part of each cell during
the operation, causing the initiation of a network of microcracks at the cell edge that
reduces its lifetime.
A flat anode of rectangular shape with a plane work surface [12] is cheaper to
manufacture as compared to the abovementioned variants because of using a rela-
tively cheap technology of tape casting. In the same way, thin electrolyte and cathode
layers are formed on the anode-substrate. However, an operating surface area of such
a SOFC is limited because of the limited thickness of the anode and the stresses arising
when assembling elementary fuel cells in a stack. These stresses are not distributed
uniformly [13].
Development of the Concept of a Spheroidal Shape Anode … 79

Another variant of a flat anode-substrate with a plane work surface is of a round

shape (cylindrical anode) [14]. Due to the assembling of elementary fuel cells in a
stack, axially symmetric stresses arise in the anode-substrate. However, the diameter
of the elementary fuel cell, and consequently, its operating surface area is limited
by the thickness of the anode and the ultimate stress along the axis of the cell due
to this consolidation scheme. So the cylindrical anode does not provide the required
deformation resistance and, consequently, the required lifetime of a SOFC. These
factors affect the cost of electricity that it produces and fuel cell performance per
unit volume of the anode.
A new improved shape of a SOFC anode has been proposed recently [15]. The
anode of such spheroidal shape provides improved resistance to deformation.
The purpose of this work is to determine radii ranges for cylindrical and convex
(spheroidal) parts of the SOFC spheroidal shape anode based on stress and strain
parameters calculated and substantiate the anode potential to withstand deformation,
stress gradient, and crack growth under operational conditions.

2 Methods

2.1 Manufacturing Technique

Traditionally, the anode can be composed of a mixture of ScCeSZ powders (cubic

structured zirconia ZrO2 stabilized with 10 mol% Sc2 O3 and 1 mol% CeO2 ) with
addition of 20–50 wt% NiO, or also can be composed of a mixture of YSZ powders
(cubic structured zirconia ZrO2 stabilized with 8 mol% Y2 O3 ) with addition of 20–
50 wt% NiO. The mixture is compressed under a pressure of 16–20 MPa at a temper-
ature of 20 °C in a cylindrical mold with the concave bottom of the spheroidal shape,
with a punch of the same spheroidal shape of its contacting surface. As a result, a
cylinder shape pressed body with top and bottom convex surfaces is formed (called
a spheroidal shape anode). During 1–4 h of exposure at 800–1250 °C, preliminary
annealing of the body is performed which is followed by shrinkage and pore forma-
tion, and integrated material structure is formed. Finally, the body is sintered at
1350–1450 °C in air or inert gas during 2–5 h.

2.2 Characterization of the Software Used

To calculate stress and strain parameters of the anodes of the cylindrical and
proposed spheroidal shapes by finite element analysis, software for calculating three-
dimensional tasks Mechanical Desktop 6 Power Pack (MDPP) was used. The MDPP
finite element analysis consists of the following steps:
80 B. Vasyliv and V. Podhurska

1. Apply fixtures.
2. Apply load.
3. Define material of the part.
4. Analyze (run) the part.
5. View the results.
6. Optimize the part.
1. Applying fixtures. Fixtures let you define fixed restraints. Each restraint can
contain multiple faces. The restrained faces are constrained in all directions. You
must fix at least one face of the part to avoid analysis failure due to rigid body
motion.
When you select faces to fix in the graphics area, the fixture is added to the
“Fixtures” folder in the MDPP study tree and a check mark appears next to “Fixtures”
in the MDPP wizard.
2. Applying loads. “Loads” lets you apply force and pressure loads to faces of the
model. In MDPP, loads can be either force or pressure.
You can apply multiple forces to a single face or multiple faces. For this, you have
to select a direction to apply the specified force value to each face in the direction
of its normal, and then select the force units and enter the force value. The specified
force value is applied to each face. For example, if you select three faces and specify
a 50 N force, the program applies a total force of 150 N (50 N on each face). If
necessary, select “Reverse direction” to reverse the direction of the force.
The force appears in the “External Loads” folder in the MDPP study tree, and a
check mark appears next to “Loads” in the MDPP wizard.
You can apply multiple pressures to a single face or to multiple faces. The program
applies pressure loads normal to each face. For this, you have to select “Normal to
selected face” to apply the pressure in the direction normal to each selected face,
or “Use reference geometry” to apply the pressure in the direction of a selected
reference plane (here you need to select a reference plane in the corresponding feature
manager design tree), and then select the pressure units and enter the pressure value.
If necessary, select “Reverse direction” to reverse the direction of the pressure.
The pressure appears in the “External Loads” folder in the MDPP study tree and
a check mark appears next to “Loads” in the MDPP wizard.
3. Assigning material. The response of a part depends on the material assigned
to the part. MDPP must know the elastic properties of the material of the part. You
assign material to the part by picking a material from a material library. MDPP uses
the physical properties of the materials defined in the Mechanical Desktop Mate-
rial library. Materials can be isotropic, orthotropic, or anisotropic. MDPP supports
isotropic materials only.
To assign/modify the material to a part, in the “Material” dialog box, expand the
class of materials and select a material.
The material appears in the MDPP wizard and a check mark appears next to
“Material”. Also, the material appears next to the part’s name in the MDPP study
tree. If you select a material that does not have a yield strength, a message specifies
that the yield strength is not defined.
Development of the Concept of a Spheroidal Shape Anode … 81

If the material you want to assign to the part is not in the Mechanical Desktop
Material library, you can create a custom material. When you create a custom mate-
rial, start with an existing material similar to the material you want to create. To create
a material, in the “Material” dialog box, in the material tree, select the material on
which to base the custom material. Then, select Copy, and in the material tree, select
a category in a custom library. You can use the Custom Materials library or a library
you created. Select Paste. To rename the material, right click the material and select
Rename. Edit properties of the material and click Save. Click Apply.
4. Analyzing the part. MDPP prepares the model for analysis and then calculates
displacements, strains, and stresses. To analyze the part, you can use the default mesh
settings or change them.
To accept the default mesh settings (default element size and tolerance values),
click “Run Simulation”. When the simulation is complete, a drawing of the deformed
part is displayed. Review the drawing and determine whether the loads and fixtures
are applied properly, then click “Continue”.
When the simulation is complete, a check mark appears next to “Run” and
“Results” in the MDPP wizard.
To change mesh settings, in the “Mesh” Property Manager, adjust the mesh by
dragging the slider. Drag the slider to the right for a finer mesh (more accurate) or to
the left for a coarser mesh (quicker), then remesh the model. After that, click “Run
Simulation” and repeat the abovementioned steps of analyzing the part.
Mesh failure diagnostics. The meshing of a solid model consists of two basic
phases. In the first phase, the mesher places nodes on the boundary. This phase is
called surface meshing. If the first phase is successful, the mesher starts the second
phase where it creates nodes in the inside, fills the volume with tetrahedral elements,
and places mid-side nodes on edges.
Failure can occur in either of the two phases. When the meshing of a part fails,
MDPP opens the mesh failure diagnostics tool to help you locate and resolve meshing
problems. The tool lists the faces and edges that caused the failure. To highlight a
face or an edge that failed to mesh, select it from the list.
5. Viewing the results. After completing the simulation, you can view results.
The “Results” folder in the MDPP study tree contains the results for the current
geometry, material, fixtures, and loads. MDPP calculates stresses, displacements,
deformation, and strains, and places them in the “Results” folder.
To view the stress distribution in the model, click “Show von Mises stress”. The
equivalent stress (von Mises stress) plot is displayed.
To view the displacement distribution in the model, click “Show displacement”.
The resultant displacement plot is displayed.
The deformation scale refers to the scale factor that the program uses to scale the
deformed shape of the model. The value of the scale factor depends on the model’s
largest dimension and the calculated deformations.
For example, a scale factor of 50 means that the largest deformation calculated by
MDPP is shown as 50% larger than the largest dimension of the smallest boundary
box that surrounds the model.
82 B. Vasyliv and V. Podhurska

A larger deformation scale factor helps you visualize deflections that are a lot
smaller compared to the original dimensions of the model.
6. Optimizing the part. After completing a stress analysis, you can perform an
optimization analysis to find the optimal value for one model dimension while satis-
fying a specified criterion. For example, you can find the optimal length of a part
such that the von Mises stresses do not exceed a specified value.

3 Results and Discussion

3.1 The Classic Stress–Strain Approach

Formulation of the task. Stress and strain parameters of the anodes of the cylin-
drical and proposed spheroidal shapes (Fig. 1) were calculated by the MDPP finite
element analysis. Initial conditions were as follows: material of ZrO2 –Y2 O3 –Ni
system; average value of the ultimate fracture stress σf = 110 MPa; Young’s modulus
E = 1.5 × 105 MPa; Poisson’s coefficient ν = 0.3; the fixing pressure n = 1 MPa
along the closed-loop fixing of inner radius Rp = 10.5 mm; the external gas pressure
p = 1 MPa on the anode working surface; the radius of the cylindrical part of anodes
Rc = 12 mm; the spheroid radii, R, were 240, 60, and 36 mm, respectively.
Stress and strain features of the anodes. Corresponding faces of the model were
fixed and loads were applied (Fig. 1). Then, the material was assigned and the default
mesh setting (default element size and tolerance values) was used to analyze the part.
After completing the simulation, we obtained results. Such procedure was repeated
for each separate case of spheroid radii and the anode hight starting from 0.5 mm
with a step of 0.5 mm.
To compare stress and strain features of the anodes of the cylindrical and
spheroidal shapes, the following parameters were calculated:
volume V c of an anode of the cylindrical shape

Vc = π · Rc2 · h (1)

where h is a hight of a cylinder;

volume V s of two convex parts (spherical caps) of an anode of spheroidal shape

2
Vs = π · H 2 (3R − H ) (2)
3
where H is a hight of a convex part (spherical cap) of the anode;
volume V of an anode of spheroidal shape

2
V = π · Rc2 · h + π · H 2 (3R − H ) (3)
3
Development of the Concept of a Spheroidal Shape Anode … 83

Fig. 1 Diagrams of application of the fixing pressure, n, along the closed-loop fixing of the inner
radius, Rp , the external gas pressure, p, on the anode working area, the reaction force, F, along the
closed-loop fixing, the stress distribution, σ, along the axis (items 1 and 3), and the closed-loop
fixing (2 and 4) in the anode of a cylinder radius, Rc , with (a) parallel working surfaces and (b)
convex ones of a spheroid radius, R

area S c of the base of the cylindrical part of the anode

Sc = π · Rc2 (4)

ratios V /S c and V c /S c ;
surface area increment S (in %) of an anode of a spheroidal shape
 
2R · H
S = 100 · − 1 (5)
Rc2

ratio V /V c of the spheroidal shape anode volume to the volume of an anode of the
cylindrical shape;
84 B. Vasyliv and V. Podhurska

ratio V /V c1 of the spheroidal shape anode volume to the volume of an anode

of the cylindrical shape, where V c1 = 452 mm3 is the calculated volume of the
cylindrical anode of radius Rc = 12 mm and of hight 1 mm fabricated for industrial
applications [7].
The range of values of R/Rc ratio from 20 to 5 corresponds to a noticeable incre-
ment of anode surface area S (up to 1%, see Fig. 2). For this range at slight working
surface convexity, the ratio V /V c1 is small (from 1.31 to 2.20). For the R/Rc range
from 3.5 to 5 increment of anode surface area, S is from 1 to 2% but a steep increase
of anode volume occurs due to the excessive convexity (V /V c1 from 2.20 to 2.75),
that does not provide the conditions for reactions to be passed in the fuel cell.
The volumes V and V c , the area S c , and V /S c ratio were calculated as functions
of parameters R, Rc (Rc = 12 mm) and variable anode hight (its increment step was
0.5 mm). For each partial case, the stress distribution and maximum strain were
calculated by finite element analysis. Then, the stresses in the most dangerous areas
[i.e., along the axis (items 1 and 3, see Fig. 1) and the closed-loop fixing (2 and 4)]
and maximum strain, εmax , along the axis versus V /S c ratio dependences were plotted
(Fig. 3).
The dependences show that for an anode of the cylindrical shape the stresses along
the axis are higher than ones along the closed-loop fixing (Fig. 3a, curve 1 contrary to
curve 2). In contrast to this, for an anode of spheroidal shape even of slight convexity
(R/Rc = 20), the stresses along the axis and the closed-loop fixing, caused by the
external gas pressure on the anode working surface, are already balanced at the value
of V /S c over 1.5 mm (Fig. 3a, curves 3 and 4), and the maximum strain is decreased
by 10–30% as compared to an anode of the cylindrical shape (Fig. 3b, curve 10
contrary to curve 9).
For an anode of spheroidal shape with the ratios of R/Rc in the range from 5 to
20 and V /S c from 1 to 2.5 mm, the stresses in the most dangerous areas [i.e., along

Fig. 2 A graph of calculated values of the area increment, S, of a spheroidal shape anode (curve
1, an ordinate axis is on the left) and the ratio V /V c1 of the anode volume to the volume of the
in-production cylindrical shape anode of a radius of 12 mm and of 1 mm thickness (curve 2, an
ordinate axis is on the right) depending on the spheroid-to-cylinder radii ratio, R/Rc
Development of the Concept of a Spheroidal Shape Anode … 85

Fig. 3 Change in the values of (a) the ordinary to fracture stresses ratio, σ /σ f , along the axis (curves
1, 3, 5, and 7) and closed-loop fixing (2, 4, 6, and 8) as well as (b) maximum strain, εmax , along
the axis (9–12) caused by the fixing pressure and the external gas pressure on the anode working
surface which are calculated using the finite element analysis, depending on the anode volume to
its cylinder base area ratio, V /S c , for cylindrical shape anodes with parallel (curves 1, 2, and 9) and
spheroidal working surfaces having the spheroid to cylinder radii ratio, R/Rc , of 20 (curves 3, 4,
and 10), 5 (5, 6, and 11), and 3 (7, 8, and 12), respectively

the axis (items 1 and 3, see Fig. 1) and the closed-loop fixing (2 and 4)], and the
maximum strain, caused by the external gas pressure on the anode working surface,
are decreased by 10–30% and 20–40%, respectively, as compared to an anode of the
cylindrical shape of the same radius and volume features.
Based on the FEA calculations performed for spheroidal anodes with Rc = 12 mm
and various values of R (Fig. 4), the surfaces of stress distribution along their axes
and closed-loop fixing were plotted. As a result of the graphic intersection of these
surfaces, a three-dimensional curve was created (Fig. 4, surfaces 1 and 2, respectively,
and curve 3). The curve displays the values of balanced stresses depending on V /V c
and R/Rc parameters. A domain of this curve was also defined.
Projections of the curve on the coordinate planes [V /V c ; R/Rc ], [σ/σf ; R/Rc ], and
[σ/σf ; V /V c ] were approximated by the corresponding lines (Fig. 4, curves 3 , 3 ,
and 3 , respectively). Curve 3 for the ranges 0.065 < (σ /σ f ) < 0.460, 1.20 < (V /V c )
< 1.58, and 10 < (R/Rc ) < 32 was described by an equation:
86 B. Vasyliv and V. Podhurska

Fig. 4 Surfaces of stress distribution along the axis (surface 1) and closed-loop fixing of anodes
(surface 2) as well as their three-dimensional intersection curve (3) with its projections on the
coordinate planes [R/Rc ; V /V c ], [σ /σ f ; R/Rc ], and [σ /σ f ; V /V c ] (curves 3 , 3 , and 3 , respectively).
Curves 4 and 5 (located on surfaces 1 and 2, respectively) show levels of stresses in anodes with a
1 mm thick cylindrical part and a variety of R/Rc (V /V c ) ratios

V
= 0.00000547(R/Rc )5 − 0.0005109(R/Rc )4 + 0.01829(R/Rc )3
Vc
− 0.313(R/Rc )2 + 2.525(R/Rc ) − 6.1085 (6)

Curve 3 for the ranges 0.065 < (σ/σf ) < 0.430 and 7.5 < (R/Rc ) < 22 was described
by an equation:
σ
= 0.000022(R/Rc )4 − 0.00126(R/Rc )3 + 0.0275(R/Rc )2
σf
− 0.2454(R/Rc ) + 0.7774 (7)
Development of the Concept of a Spheroidal Shape Anode … 87

Curve 3 for the ranges 0.065 < (σ/σf ) < 0.280 and 1.20 < (V /V c ) < 1.47 was
described by an equation:
σ
= 549.26(V /Vc )4 − 2961.15(V /Vc )3 + 5973.1(V /Vc )2
σf
− 5343.51(V /Vc ) + 1789.15 (8)

Based on Eqs. (1) and (3) for the volumes of the cylindrical and spheroidal shape
anodes as well as their ratios, it can be noted that for a certain R/Rc ratio range
(approximately from 3 to 50) curve 3 for anodes with a radius of the cylindrical part
Rc > 12 mm (see Fig. 4) will be shifted towards lower values of V /V c while curve 3
will be shifted towards higher values of σ/σf , and curve 3 will be shifted towards
lower values of V /V c and higher values of σ/σf .
Thus, a spheroidal shape anode allows the stress distribution to be changed and a
level of maximum strain in a fuel cell to be lowered. Therefore, it allows resistance
to its deformation, and the lifetime of a fuel cell to be increased. This reduces the
cost of electricity that the cell produces, and thus increases the efficiency of a solid
oxide fuel cell with an anode-substrate of spheroidal shape as compared to the fuel
cell comprising an anode-substrate of the cylindrical shape.

3.2 A Shape-Dependent Crack Deceleration Approach

A short history of a chevron profile. Chevron-notched specimens (Fig. 5) are gaining

widespread use for fracture toughness testing of ceramics, rocks, high-strength
metals, and other brittle materials [16–20]. They are small (5- to 25-mm thick),

Fig. 5 Various chevron-notched fracture specimen configurations: (a) a bend bar with an unsym-
metrical chevron notch [17]; (b) a bend bar with a chevron notch symmetrical about the center line
of the specimen [19]
88 B. Vasyliv and V. Podhurska

simple, and inexpensive specimens for determining the plane-strain fracture tough-
ness. Because they require no fatigue precracking, they are also well suited as quality
control specimens.
The unique features of a chevron-notched specimen, over conventional fracture
toughness specimens, are: (1) the extremely high stress concentration at the tip of the
chevron notch, and (2) the stress intensity factor passes through a minimum as the
crack grows. Because of the high-stress concentration factor at the tip of the chevron
notch, a crack initiates at a low applied load, so costly precracking of the specimen
is not needed. From the minimum stress intensity factor, the fracture toughness can
be evaluated from the maximum test load. Therefore, a load-displacement record,
as is currently required in the ASTM E399 plane-strain fracture toughness (K Ic ) test
procedure, is not needed.
In 1964, Nakayama [17, 18] was the first to use a bend specimen with an unsym-
metrical chevron notch. His specimen configuration is shown in Fig. 5a. He used
it to measure fracture energy of brittle, polycrystalline, refractory materials. All
previous methods which had been developed for testing homogeneous materials
were thought to be inadequate. This specimen is unique in that a crack initiates at
the tip of the chevron notch at a low load, then propagates stably until catastrophic
fracture. Because of the low load, the elastic stored energy in the test specimen and
testing apparatus was small so that the fracture energy could be estimated from the
area under a load-time history record.
Tattersall and Tappin [19] in 1966 proposed using a bend bar with a chevron notch
symmetrical about the center line of the specimen, as shown in Fig. 5b. They used this
specimen to measure the work of fracture on ceramics, metals, and other materials.
The work of fracture was determined from the area under the load-displacement
record divided by the area of the fracture surfaces.
Pook [20] used the stress intensity factor solution for a three-point bend bar with
a straight-through crack [21] and a side-groove correction proposed by Freed and
Kraft [22] to obtain approximate solutions for various shape chevron notches. The
stress intensity factor for a chevron-notched specimen, K CN was given by
 1/2
B
K CN = K STC (9)
b

where K STC is the stress intensity factor for a straight-through crack in a bar having the
same overall dimensions. The unique stress intensity factor solution for a chevron-
notched specimen compared to a straight-through crack specimen is illustrated in
Fig. 6.
The dashed curve shows the normalized stress intensity factors for the straight-
through crack as a function of a/W. This curve is a monotonically increasing function
with crack length.
The solid curve shows the solution for the chevron-notched specimen. For a =
a0 , the stress intensity factor is very large but it rapidly drops as the crack length
increases. The minimum value is reached when the crack length is between a0 and
Development of the Concept of a Spheroidal Shape Anode … 89

Fig. 6 Comparison of normalized stress intensity factors for chevron-notched and straight-through
crack specimens. Here, K is the stress intensity factor and P is the applied load

a1 . For a > a1 , the stress intensity factors for the chevron-notched specimen and
for the straight-through crack specimen are identical because the configurations are
identical.
A concept of variable length of the crack front. We assume that at first approxi-
mation, the crack profile of arbitrary shape can be replaced by a similar trapezoidal
profile [23]. So there can be a unified approach for estimating the dynamics of crack
growth in ceramic parts of various shapes [24] by using developed earlier procedure
of crack initiation and propagation in a ceramic specimen with the oblique front of
a notch, and corresponding formulae for compliance calibration [24–26].
A compact specimen with a chevron notch monotonically loaded by wedging
the edges of a notch on a testing machine (Fig. 7) can be used for modeling the
dynamics of crack growth. For this purpose, the notch mouth in a specimen and a
loading wedge were sharpened to the same angle β. The proposed loading mode is, to
a greater extent, strain-controlled than eccentric tension mode, and guarantees stable
crack growth in the case where the load applied to the specimen increases stepwise.
The experimental procedure can be described as follows: A specimen is mono-
tonically loaded by moving the wedge with a speed of 10 μm/s up to the attainment
of an empirically specified load level, held for 30–120 s until the initiation of a
90 B. Vasyliv and V. Podhurska

Fig. 7 Schematic diagram of loading a compact chevron-notched specimen. Here, the values of
L 10 and L 30 correspond to the profile angle θ of 10° and 30°

0.10–0.15 mm long incipient crack, and then unloaded. The procedure is periodi-
cally repeated, each time under a higher maximum load guaranteeing the attainment
of an increment of crack length of about 0.05–0.25 mm with subsequent termination
of the crack growth. In the course of the tests, current values of the crack length,
load, and displacements of the notch edges are recorded. The growth of a crack is
observed with an optical microscope.
The stress intensity factor K CN at the crack tip in a compact specimen with a
chevron notch can be determined by using the formulae [20, 22, 27–29]
  
P corr(e) π α1 − α0 0.5
K CN = X · ySTC (10)
B W α − α0

ySTC = 16.7 α 1/2 − 104.7 α 3/2 + 369.9 α 5/2 − 573.8 α 7/2 + 360.5 α 9/2 (11)
Development of the Concept of a Spheroidal Shape Anode … 91

where PXcorr(e) is the corrected value of applied load, B is the thickness of the specimen
(1.5 mm < B < 4.5 mm), a is the crack length, W is the width of the specimen, α =
a/W (0.2 < α < 0.6), a0 is the distance from load line to the tip of chevron notch, α 0
= a0 /W (0.2 < α 0 < 0.45) (see Fig. 7);

k1 k2 P
PXcorr(e) = (12)
2(tan β)

where P is the applied load, β is the angle of loading wedge (see Fig. 7),
 0.5
B
k1 = (13)
B0

B0 = 1 mm;
     0.5  0.25 
B B0 α1 − α0
k2 = λn0 exp (−1) 0.1α02 + (14)
B0 B α − α0

where n is changed in the range 0.3 < n < 1.2 and the corresponding value of α0n is
changed in the range 0.169 < α0n < 0.569 for the experimental curves obtained on
the specimens of various thicknesses.
In the case of applying certain load P using the wedging scheme, we can calculate
the current value of K I = K CN for a certain profile with corresponding profile angle
θ (Fig. 8c). This angle is an average one for either the concave (Fig. 8a) or convex
profile (Fig. 8b), as well as for combined variants.
In general, crack growth behavior depends on the profile angle (Fig. 9). Having
calculated the values of the parameter K I in time, we will obtain the dependence K I
= f (t) which can be different for different crack profiles (Fig. 10).
Schematically, we can present the main cases of the profile angle θ depending
crack growth behavior (Fig. 9a, c, e, g) and fracture (Fig. 9b, d, f, h).
Also, we can present corresponding shapes of the basic K I –da/dt curve (Fig. 10a,
c, e, g) and of K I = f (t) curve (Fig. 10b, d, f, h) for the range from threshold (K Ith )
to critical level (K Ic ), for the cases of applying load P causing certain starting value

Fig. 8 Diagrams of (a) the concave, (b) convex, and (c) symmetrical chevron profiles in a ceramic
part of arbitrary shape, having the same average profile angle θ. For each case, a hatched area
corresponds to a crack running along the direction indicated by an arrow
92 B. Vasyliv and V. Podhurska

Fig. 9 Diagrams of the crack profiles in a ceramic part of arbitrary shape which correspond to the
profile angle θ depending crack growth behavior: (a, b) crack deceleration, (c, d) quasi-equilibrium
crack growth, and (e–h) its acceleration. For each case, a hatched area corresponds to a crack
running along the direction indicated by an arrow
Development of the Concept of a Spheroidal Shape Anode … 93

Fig. 10 Basic K I –da/dt curves (a, c, e, g) and K I = f (t) curves (b, d, f, h) for ceramic parts
of arbitrary shape which correspond to the profile-depending crack growth behavior: (b) crack
deceleration, (d) quasi-equilibrium crack growth, and (f, h) its acceleration. The arrows along
curves indicate the direction of change of the corresponding parameters while running cracks in
the profiles. K Ith and K Ic are the threshold and critical stress intensity factors, respectively, K Ix is
a certain starting value of the stress intensity factor, t th is the time during which K Ix to K Ith stress
state change occurs, and t f is the time during which K Ix to K Ic stress state change occurs
94 B. Vasyliv and V. Podhurska

Fig. 11 A diagram of the indentation crack profile in a ceramic part of arbitrary shape, and corre-
sponding basic K I –da/dt (b) and K I = f (t) (c) curves, showing a particular case of the crack
deceleration conditions. Hatched areas (a) correspond to perpendicular cracks running along the
direction indicated by an arrow. The arrows along curves (b, c) indicate the direction of change of
the corresponding parameters while running cracks in the profile. K Ith and K Ic are the threshold
and critical stress intensity factors, respectively; t th is the time during which K Ic to K Ith stress state
change occurs

K Ix : descending K I = f (t) curve (Fig. 10b) for comparatively big angles θ (Fig. 9a,
b), horizontal one (Fig. 10d) for smaller angles θ (Fig. 9c, d), and then ascending
curve (Fig. 10f, h) for rectangular (θ = 0) and especially reverse (θ < 0) profiles
(Fig. 9e–h).
As a particular case of the crack deceleration conditions in a ceramic part of
arbitrary shape, the indentation crack profile [30, 31] can be presented (Fig. 11a),
along with the basic K I –da/dt and K I = f (t) curves (Fig. 11b, c).
This profile has the angle θ = 180° which is the biggest one among the profiles
causing the crack deceleration (see Fig. 9). This behavior is demonstrated by a very
steep slope of the descending K I = f (t) curve (Fig. 11c).
Determination of the crack running moment. The abovementioned profile-
dependent features of crack advance have been taken into account when constructing
multiple M x –a curves for symmetrical profiles with various profile angles. For this
purpose, the crack running moment M x applied to a specimen with symmetrical
chevron crack profile can be determined by transforming Eq. (10):
√  
K CN · B W · a α1 − α0 −0.5
M X = PX · a = √ · (15)
ySTC · π α − α0

where Px is the eccentric tension load, a is the crack length, α = a/W is the relative
crack length, K CN is the stress intensity factor at the crack tip, B and W are the
thickness and width of a specimen, respectively, a0 is the distance from load line to
the tip of chevron notch, α0 = a0 /W , a1 is the distance from load line to the point
where chevron notch intersects specimen surface, α 1 = a1 /W (see Fig. 7); ySTC is
determined according to Eq. (11).
Development of the Concept of a Spheroidal Shape Anode … 95

In the beginning, we can analyze the behavior of dimensionless constituents of

Eq. (15) to understand the feature of “M x versus a” dependences. For this reason, let
us introduce the following notation:
√
K CN · B W · a
MX = √ · k1 k2 (16)
π

where
1
k1 = (17)
ySTC
 −0.5
α1 − α0
k2 = (18)
α − α0

Also, we can use additional mathematical operations for this purpose:

 
1 α1 − α0 −0.5
k3 = k1 k2 = · (19)
yST C α − α0
 
a α1 − α0 −0.5
k4 = k3 a = · (20)
ySTC α − α0

Now we can analyze graphically behaviors of corresponding curves (Fig. 12a, c,

e). We can see for all three particular cases presented in the figure (the thickness B
= 1 mm; the width W = 12 mm; α 0 = 0) that values of k 1 decrease gradually with
increasing relative crack length α (curve 1), while values of k 2 increase (curve 2).
Thus, we obtain the maximum value of k 3 (the peak of curve 3) corresponding α =
0.2877 for all three cases of the profile angle θ, namely 5°, 10°, and 15° (Fig. 12a, c,
e).
With increasing the specimen thickness no change in position of curves and their
peaks occur except a slight increase in peak values. Also, when the width is increased
twice (W = 24 mm), the tendencies for the mentioned curves remain the same (a
slight increase in peak values) with the same position of the peak of curve 3 (α =
0.2877) for all three cases of the profile angle θ (Fig. 12b, d, f).
Similarly to this, at α 0 = 0 we can see the peak of k 4 (curve 4) corresponding α =
0.5016 for the cases of the profile angle while α 1 > 0.5016 (Fig. 12a). The magnitude
of maximum k 4 value only depends on the constants in Eq. (15). Also, a sharp kink
in line 4 is observed for these cases at the positions corresponding α 1 where the
cracks put out of the chevron profiles. It is because of k 2 values which are equal to
1 after curve 2 reaches the position of α 1 . When the width is increased twice (W =
24 mm), the kink in line 4 is shifted toward lower values of α because of α 1 < 0.5016
(Fig. 12b, d, f).
So we can conclude that independently of the profile angle of a specimen, its geom-
etry parameters, and fracture toughness of tested material, the position of maximum
96 B. Vasyliv and V. Podhurska

Fig. 12 Dimensionless constituents k 1 , k 2 , k 3 , and k 4 [according to Eqs. (17)–(20)] versus the

relative crack length α dependences for analyzing the parameter-depending tendencies of change
of the crack running moment M x for the cases of the specimen width 12 mm (a, c, e) and 24 mm
(b, d, f), and the profile angle θ of 5° (a, b), 10° (c, d), and 15° (e, f). The specimen thickness for all
the cases is 1 mm. Curves 1–4 correspond to the constituents k 1 –k 4

crack running moment M x (in case of α0 = 0 and α1 > 0.5016) is strictly at α =

0.5016. When α 0 > 0, then curve 2 and its kink are shifted towards higher values
of α. Respectively, the peaks of curves 3 and 4 are shifted in a similar way. These
changes in positions of curves 2–4 are followed by a slight lowering of their peak
values.
Now we have to evaluate the conditions of crack growth in specimen profiles
of a certain material. In the beginning, we can take into account a range of the
fracture toughness K Ic of 1.9–3.4 MPa m1/2 for the YSZ–Ni cermet presented in [1].
Assuming the conditions of crack growth when the stress intensity factor K CN is equal
to critical one, i.e., K CN = K Ic (for the boundary conditions of the YSZ–Ni cermet
behavior we select K Ic = 1.9 MPa m1/2 ), corresponding data sets of the crack running
moment, M x , and the actual crack length, a, for the YSZ–Ni compact specimens of
symmetrical chevron cross sections with the profile angle θ in the range 5°–60° were
calculated according to Eq. (15). Then, corresponding dependences were plotted for
three particular cases of the specimen thickness, B, equal to 1 mm, 2 mm, and 3 mm
(Fig. 13a–c, respectively; the specimen width W = 12 mm; α 0 = 0).
Development of the Concept of a Spheroidal Shape Anode … 97

Fig. 13 Crack running moment, Mx , versus the actual crack length, a, dependences for chevron
notched compact specimens of the thickness 1 mm (a), 2 mm (b), and 3 mm (c). The specimen
width is 12 mm, and the distance from the load line to the tip of chevron notch a0 = 0 for all the
cases. Curves 1–9 correspond to the symmetrical chevron profile angle θ of 5°, 7.5°, 10°, 15°, 20°,
30°, 40°, 50°, and 60°, respectively. Curve 10 corresponds to the conditions of crack growth behind
the chevron profile

It was revealed that the values of M x increase gradually with increasing the profile
angle θ (Fig. 13a–c). The higher is the specimen thickness, B, the higher is the value
of M x . There exist the peaks of M x corresponding α = 0.5016 for the cases of the
profile angle while α 1 > 0.5016. The magnitude of maximum M x value only depends
on the constants in Eq. (15). In fact, the kinks in “M x versus a” lines corresponding
positions of α 1 where the cracks put out of the chevron profiles, are observed for all
the cases (Fig. 13a–c). However, in contrast to the abovementioned profiles with α 1
> 0.5016, there are no maxima of the curves corresponding to the position of α =
0.5016 for the cases of α 1 < 0.5016.
Based on the constructed curves one can estimate a safe level of the applied
moment for manufactured pieces of a certain geometry, which allows their reliable
operation without a risk to be put out of order.
Regularities of the crack retardation kinetics. The shape-dependent crack decel-
eration approach [24] was used to evaluate the crack growth resistance of SOFC
anode-substrate of a certain shape. Diagrams (Fig. 14) of the crack initiated at the
edge of an anode-substrate with (a) parallel working surfaces (the profile angle θ
= 0) and (b) convex ones (θ > 0) allow modeling crack growth in both the profiles
using corresponding parameters of geometry and load.
If accidentally, a crack is initiated at the edge of an anode, it may advance
depending on the crack profile geometry and loading conditions. One can eval-
uate the stress intensity factor K at the crack tip depending on the loading mode.
For the case of the external gas pressure p = 1 MPa and the fixing pressure n =
1 MPa applied to the cylindrical shape anode of radius 12 mm and thickness 1 mm
(see Fig. 14), we assume that these forces cause K III mode of crack growth (tearing
or out-of-plane shear mode), and this parameter can be defined using approximate
98 B. Vasyliv and V. Podhurska

Fig. 14 Diagrams of the crack initiated at the edge of an anode-substrate with (a) parallel working
surfaces (the profile angle θ = 0) and (b) convex ones (θ > 0). The notation is the same as in Fig. 1.
A dashed line marks the crack front, and a horizontal arrow indicates the direction of crack advance
for each case

correlation between K I and K III modes as K III = αK I , where α is a correlation factor

in the range of 0.2–0.6 [32].
We can use minimum value 0.2 of this factor to estimate ultimate stress arising in
the material of an anode at equivalent conditions corresponding K I mode:

K III p+n
KI = or, σu = (21)
α α

i.e., σu = 1+1
0.2
= 10 MPa
In case of a certain crack length a = 1.5 mm, we can calculate an equivalent
value of K I using a conventional formula [33] for eccentric tension of a compact
precracked specimen with a straight-through notch:
Development of the Concept of a Spheroidal Shape Anode … 99
√
K I = σu π · a, (22)
√
i.e., K I = 10 0.0015π = 0.7 MPa m1/2 .
Taking into account a range of the fracture toughness K Ic of 1.9–3.4 MPa m1/2 for
the YSZ–Ni cermet presented in [1], we can conclude that calculated above the value
of K I parameter does not reach this range. That is, an initiated crack may advance
subcritically at these conditions [24].
Similarly to the cylindrical shape anode, we can estimate crack growth behavior
in a spheroidal shape anode. For the last having similar crack initiated at the edge,
conditions of crack growth also depend on its profile and applied load. In particular,
the same K III value (corresponding to an equivalent value of K I ) is reached when a
crack approaches the length of crack front 1 mm; i.e., values of the crack front length
become the same for both the cylindrical and spheroidal shape anodes.
But in the case of spheroidal shape anode, a crack is already decelerated if the
current value of the crack profile angle is about 10° [24].
In order to study a process of crack retardation in detail, its behavior was modeled
using various R/Rc ratio, namely 3, 5, 15, and 20 (at constant Rc = 12 mm), which
allows constructing anode-substrates of four various shapes with convex working
surfaces. Circumscribed figures were also drawn outside these shapes. Such modeling
figures are rectangle ones with symmetrical chevron cross sections having the profile
angle θ of 41.2°, 25.26°, 9.56°, and 7.55°, respectively (Fig. 15a). These profile angles
correspond to the initial ones measured for the four various shapes.
The modified formula for calculating stress intensity factor K CN at the crack tip
in a chevron specimen can be as follows [24]:
  
PX π α1 − α0 0.5
K CN = · ySTC (23)
B W α − α0

where Px is the applied tensile load, B and W are the thickness and width of a
specimen, respectively, a1 is the distance from load line to the point where chevron
notch intersects specimen surface, α 1 = a1 /W, a0 is the distance from load line to
the tip of chevron notch, α 0 = a0 /W, a is the crack length, α = a/W is the relative
crack length (see Fig. 7); ySTC is determined according to Eq. (11).
The crack running load Px applied to a specimen with symmetrical chevron crack
profile was determined by transforming Eq. (23):
√  
K CN · B W α1 − α0 −0.5
PX = √ · (24)
ySTC · π α − α0

Having calculated values of Px for the four profile angles, we constructed the crack
running load, Px , versus the crack length, a, dependences (Fig. 15b) for the modeling
figures (dashed lines) with cracks of a certain length of their fronts (Fig. 15a).
Then, the stress intensity factor ratio, K I /K Ic , versus the crack length, a, depen-
dences (Fig. 15c) were plotted at Px = const for corresponding shapes pointed out
100 B. Vasyliv and V. Podhurska

Fig. 15 Diagrams of (a) anode-substrates with cracks of a certain length of their fronts, and
corresponding dependences of (b) the crack running load, Px , versus the crack length, a, and
(c) the stress intensity factor ratio, K I /K Ic , versus the crack length, a. The positions 1–4 (solid
lines) correspond to the anodes with convex working surfaces, with the initial profile angle θ of
41.2°, 25.26°, 9.56°, and 7.55°, respectively, and parallel working surfaces (θ = 0, position 5, solid
lines). The positions 1 –5 (dashed lines) correspond to circumscribed figures drawn outside the
abovementioned shapes. Curve 6 marks the boundary positions where corresponding cracks put out
of the chevron profiles. A horizontal line (c) marks the start value of the K I /K Ic ratio equal to 1,
which corresponds to certain start values of Px (b). The stress intensity factor ratio, K I/ K Ic , versus
the crack length, a, dependences (c) are plotted at Px = const for corresponding shapes
Development of the Concept of a Spheroidal Shape Anode … 101

Fig. 16 Stress intensity factor ratio, K I /K Ic , versus the crack length, a, dependences for anode-
substrates of various shapes (notation is the same as in Fig. 15). A horizontal dashed line marks the
start value of the K I /K Ic ratio, and arrows indicate the tendencies of its change while Px = const
for corresponding shapes

above, starting from a value K I /K Ic = 1 which corresponds to certain start values of

Px (Fig. 15b).
Also, approximated curves for actual anode-substrate shapes (Fig. 15b, c) were
constructed (solid lines) which allow predicting behavior of an initiated crack in
such products. Curve 6 (Fig. 15c) marks the boundary positions where corresponding
cracks put out of the chevron profiles. It can be noted that the curves for the actual
shapes differ slightly from ones for the modeling figures.
When studying crack behavior at the start value of K I /K Ic equal to 0.37 (a particular
case described above, K Ic = 0.7 MPa m1/2 ), one can note general tendencies of the
curves for corresponding profiles (Fig. 16).
Based on Figs. 15 and 16, it can be concluded that in the case of a spheroidal
shape anode, crack retardation occurs when the current value of the crack profile
angle is about 10° (Fig. 15c, curve 3) or more.
So the spheroid shaped SOFC anode-substrate has a higher resistance to crack
advance as compared to a conventional flat one.
Thus, a shape-dependent crack deceleration approach is a successful tool for
evaluation of the resistance to crack advance in the SOFC anode-substrate of various
shapes.

4 Conclusions

In this work, the improved shape of an anode-substrate for a solid oxide fuel cell has
been suggested. Using the finite element analysis, the stress and strain distributions in
YSZ–NiO anodes of the cylindrical and spheroidal shapes were calculated. Based on
the calculations, dimensions and their ratios ranges were defined which correspond
102 B. Vasyliv and V. Podhurska

to improved stress and strain characteristics of an anode. According to this, an anode

of the cylindrical shape with top and bottom convex surfaces (a spheroidal shape
anode), with an R/Rc ratio in the range from 5 to 20 is suggested. Its specific volume
V /S c is in the range from 1 to 2.5 mm. The stresses in the most dangerous areas (i.e.,
along the axis and the closed-loop fixing) and maximum strain, caused by the external
gas pressure on the anode working surface, are decreased by 10–30% and 20–40%,
respectively, as compared to an anode of the cylindrical shape of the same radius
and volume features. This increases the lifetime of a solid oxide fuel cell. A three-
dimensional curve of intersection of the surfaces of stress distribution in the anode
along its axis and the closed-loop fixing was approximated which displays the values
of balanced stresses depending on V /V c and R/Rc parameters. The advantage of the
spheroid shaped SOFC anode-substrate over conventional flat one was substantiated
using a shape-dependent crack deceleration approach.

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31. Pouvreau, C. (2007). Dissertation, Ecole Polytechnique Federale de Lausanne.
32. Pook, L. (1985). The fatigue crack direction and threshold behavior of mild steel under mixed
mode I and III loading. International Journal of Fatigue, 7, 21–30. https://doi.org/10.1016/
0142-1123(85)90004-0.
33. ASTM STP 381 (1965). Stress analysis of cracks. Philadelphia: American Society for Testing
and Materials.
Advances in Nano-Materials Used
in Photovoltaic/Thermal Systems

Ali H. A. Al-Waeli and Hussein A. Kazem

Abstract The key step for using nanoparticles for heat transfer applications is to
prepare nanofluids, either through the one-step or two-step method. Among appli-
cations of nanofluids in heat transfer are to use them as working fluid for hybrid
photovoltaic thermal (PV/T) systems. PV/T systems combine photovoltaic modules
and solar thermal collectors to produce hot water and electricity simultaneously.
This chapter presents classifications of PV/T systems, principles, and performance.
Moreover, detailed introduction to nano-material is used for PV/T systems and related
parameters such as volume fraction (%) and mass flow rate. Furthermore, the chapter
provides a case study of three different PV/T systems which are nanofluid and nano-
phase change material (nano-PCM)-based PV/T, a water-based PV/T with a PCM
tank, and water-based PV/T with water tank. The findings show an overall improve-
ment in thermo-physical properties as nanoparticles are added to base fluid (water)
and phase change material (PCM). Moreover, the highest performance is attributed
to the nanofluid and nano-PCM-based PV/T system.

Keywords Nanofluid · Nano-SiC · Nano-PCM · PV/T · Collectors

1 Introduction

Human population growth is expected to peak at around 9 billion in 2050, according

to the predictions of the United Nations’ population division [1]. With this continuous
rise in the population, so does the energy demand. This is because energy is simple a
proactive agent in raising the standard of living and prompting change in the social
conditions as well [2]. World energy use is projected to increase from its current value

A. H. A. Al-Waeli · H. A. Kazem (B)

Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor,
Malaysia
e-mail: [email protected]
H. A. Kazem
Faculty of Engineering, Sohar University, PO Box 44, 311 Sohar, Oman

© Springer Nature Switzerland AG 2020 105

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_5
106 A. H. A. Al-Waeli and H. A. Kazem

of 9000 million tonnes of oil equivalent to around 21,000 Mtoe/a as the population
increase from 6 to 12 billion people in the twenty-second century.
Energy sources such as coal, oil, and gas or also known collectively as fossil
fuels take up around 80% of global energy sources [3]. The remaining are renewable
energy sources, except for uranium. The mass production and consumption of fossil
fuels by human activity were known as contributor to climate change, making it a
concern, as well as the depletion of fossil fuels [4]. On the other hand, renewable
energy exhibits favorable characteristics as energy resources. Hence, many countries
have shifted their energy policy to adopt renewable energy technologies investment
and utilization for industrial, commercial, and residential purposes. Among these
countries are China, the EU, and the USA.
Among renewable energy technologies is the solar cell, or photovoltaic (PV),
which is the most commonly implemented by residential users. This is attributed to
its relatively cheap cost, low weight, and zero noise during operation. The projected
solar (PV) capacity growth from 2017 to 2022 is around 438 GW [5].
Photovoltaics are semiconductor devices that convert the sunlight into electricity
by utilization of sunlight photon energy. Solar cells, PV, are made of different semi-
conductors including silicon such as CdS/CdTe and CIGS. PV does not utilize the
infrared part of the solar spectrum; hence, the PV cell temperature increases across
time of operation. Internal losses due to manufacturing and heat gained through
surrounding environment lead to an increase in the cell temperature which results in
a reduction in the open-circuit voltage. This means the electric power produced by
this device will decrease as a result of the device heating up. Hence, every increase
of 10 °C causes a decrease in PV efficiency of around 5% [6]. This is particularly
the issue in hot climate and high solar irradiance areas. Moreover, this leads to short-
ening the lifetime of the device. Hence, several researchers and scientists have recom-
mended the removal of the heat from the device using cooling fluids. This would
involve a channel to carry a fluid which removes the temperature from the solar cell
and utilize it in other applications. This design is known as photovoltaic/thermal
(PV/T) hybrid collector. The heating of fluids is the function of the solar thermal
collector. Hence, PV/T is essentially composed of a photovoltaic module and a
solar thermal collector, attached for heat transfer purposes. The PV module will
then be cooled, while fluid within the thermal collector will be heated. The type
of fluid that runs through a PV/T collector is a critical factor. Given that, different
fluids have different thermo-physical properties. PV/T collectors are usually classi-
fied depending on the type of base fluid [7]. Figure 1 shows the classifications of
PV/T collectors.
According to Fig. 1, the types of PV/T include air-based, water-based, combi
(air and water), phase change material (PCM)-based. The classifications are deter-
mined either with the number of passes within the collector, shape of pipe, type of
concentrator or reflector used to maximize efficiency and working fluid.
The air-based design is considered the cheapest because of the simplicity of the
system. Moreover, the use of air instead of a liquid leads to eliminate the risk of
freezing, boiling, and damage (due to leak). On the other hand, the thermal perfor-
mance of this type of collector is considered the lowest. This is because of its low
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 107

Fig. 1 Classifications of photovoltaic thermal (PV/T) collector

Fig. 2 a SiC image at 2 μm, b SiC image at 200 nm

heat capacity, which leads to a low heat transfer. On the other hand, water has better
thermal capacity and hence better heat transfer. While water-based PV/T does exhibit
better thermal performance, it is more expensive and with more risks. Water-type is
most suitable for hot-water demand. Water circulates through the pipes and is supplied
to the user [8]. Bi-fluid design which combines water and air is useful for cooling
PV module and extracting heat. The design could be made to be thermally biased or
electrically biased, depending on the consumer’s needs, and/or limitations. Different
refrigerants could be used for the system, e.g. R134a, such as those employed for
heat pump cycles. Heat pipes on the other hand use different base fluids according to
the wall and wick of the heat pipe, which are designed to operate for longer periods
and minimal maintenance.
Because of the effect of base fluid thermo-physical properties on heat transfer,
nanofluid was introduced as a base fluid for PV/T collectors. Nanofluids are mixtures
of base fluids and nano-material.
This chapter introduces nano-material’s used in PV/T collectors and provides the
description of the advances of these nano-materials and PV/T collectors, mixing
108 A. H. A. Al-Waeli and H. A. Kazem

process to produce nanofluids and their effect on thermal and electrical efficiencies
of PV/T. Along with referenced works in the literature, actual experiments are carried
out by the authors of this chapter to examine different types of nanofluids.

2 PV/T Principle and Performance

Photovoltaic component of PV/T produces electricity, while solar thermal component

provides the function of cooling the PV and heating up the working fluid. Each device
has an efficiency based on its output. Efficiency is a great indicator of the system’s
functionality and performance.
The PV efficiency is simply the ratio of its output electric energy to input solar
energy. Equation (1) illustrates the electrical efficiency of PV cell [9]:

Pmax
ηel = (1)
Ac × G

where Pmax is the maximum electrical power, Ac is the collector area, and G is the
solar irradiance (W/m2 ). On the other hand, the thermal efficiency of solar thermal
collector is given in Eq. (2) [10].

Qu
ηth = (2)
Ac × G

where Qu is the heat gain of solar collector.

The efficiency for a whole day can be calculated by integration of the solar irradi-
ance and output power (both for electrical and thermal). As the hybrid PV/T combines
both components, the efficiency of PV/T is given in Eq. 3 [11].

ηtot = ηth + ηel (3)

where ηtot is the total efficiency of PV/T. The energy-saving efficiency offers a more
accurate description of how much energy is actually produced by dividing electrical
efficiency by the efficiency of the electric power generation of a conventional power
plant. The power generation efficiency is usually taken as 40%.
The performance of the PV/T is affected by multiple factors including solar irra-
diance, ambient temperature, climate conditions, type of working fluid, mass flow
rate of working fluid, and type of thermal collector material. Majority of these factors
are displayed by the literature provided.
Shahsavar and Ameri [12] used air-based direct-coupled PV/T collector to inves-
tigate the effect of a thin aluminum sheet suspended at the middle of air channel.
This sheet was employed to increase the heat transfer surface. The system was tested
experimentally and validated with a theoretical model. Moreover, the system was
tested for natural and forced convection. For the forced, various fans operating in the
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 109

model were used. The study concludes that there are an optimum number of fans to
achieve maximum electrical efficiency and that increase in mass flow rate leads to
better heat transfer. Finally, authors confirm that glazed PV/T has higher efficiency
than unglazed. These findings are important for understanding the effect of mass
flow rate, glazing, and heat transfer area has on PV/T performance.
Sopian et al. [13] performed a comparative study between double- and single-pass
PV/T collectors. The study concludes that double pass exhibits higher efficiency than
single. Moreover, the study affirms that increase of mass flow rate, up to a level, leads
to electricity efficiency enhancement. Beyond the appropriate mass flow rate, the
efficiency will in fact decline. Aside from mass flow rate, number of fluid channels
has a significant effect on collector performance. Chow [14] also investigated the
effect of PV/T parameters on its performance, e.g. flow rate. The investigation was
carried out using an explicit dynamic model which allows for performance analysis.
Chow believes that PV/T is dynamic, and that steady-state models are not favorable.
Main concern for the authors is inability of steady-state model to predict PV working
temperature, and heat-removal during fluctuations in irradiance and/or fluid flow.
PV/T is heavily influenced by its design. Certain design modifications could lead
to higher heat transfer and hence overall total efficiency. Kumar and Rosen [15]
added fins, vertical extension surfaces, to thermal collector of a double-pass PV/T
system. Design, climate, and operation parameters were taken into consideration, as
they have direct impact on device efficiency. Significant reduction in PV cell temper-
ature, attributed to the addition of fins, was observed with around 16 °C drop. The
design aspect is also investigated by Zondag et al. [16] where different designs were
compared in terms of performance. Massive heat losses are observed for uncovered
sheet and tube collector which caused the poorest performance among collectors. Fall
of electrical efficiency of a sheet and tube with two covers, due to further reflection at
the second cover. Authors state the importance of calculating optical efficiency as well
as thermal. Hence, reducing heat losses to surroundings could be attributed to glass
covers, but also reduction of energy absorption, by reflection, which is explained by
Sandnes and Rekstad [17] as well. Authors see a 10% reduction in energy absorption,
which is significant.
The configuration of the PV/T plays a role as well. It is important to do more
research in that area. Dubey and Tiwari [18] analyzed water-based PV/T connected
in series, using theoretical and analytical methods. They utilized energy balance
equations to develop the analytical expression of N number of collectors. Changing
the number of collectors connected in series and viewing its effect on exergy and
also analyzing electrical and thermal energy, for five different cities in India. The
electrical efficiency of four PV/T collectors connected in series was found to be
higher than 10 connected in series.
A steady-state conditions model was used by Dupeyrat et al. [19] to study thermal
and electrical performance of several glazed, water-based PV/T flat plates. The single
package lamination method was used for the experiments. The focus of the exper-
iments was on heat transfer and optical performance. With regard to optical tools,
linear Fresnel concentrators are also investigated in the literature. With this type
110 A. H. A. Al-Waeli and H. A. Kazem

of collectors, along with a 2D axis tracking, Rosell et al. [20] achieved an overall
combined efficiency above 60% when the ratio of the concentration was above 6.
The literature in PV/T collectors is vast, and there are numerous works on the
subject. This is attributed to the different fields this technology is linked to, and the
number of factors associated with PV and solar thermal collectors. Table 1 shows a
summary of the aforementioned research studies to provide an impression of general
research in the area. It is very important for research in this field to be limited in scope.
Considering, every aspect of the collector would cause too many complications to
the study. It is noteworthy to mention that Table 1 does not reflect on the research
field of PV/T, nor it is used as a sample representation.
Table 1 shows the year, location, type of investigated PV/T, method of investiga-
tion, investigated parameters, and the achieved maximum efficiency (theoretical or
measured). The general trend in this table is the use of both experimental and theo-
retical modeling. Almost every single research includes investigation into mass flow
rate, which is a critical factor in thermal performance of this collector. The highest
thermal efficiency is around 75%, while the highest electrical efficiency 16%. These
two values are merely mentioned to give an impression of the electrical and thermal
outer range. Overall, the water-based PV/T designs exhibit higher thermal efficiency
and better thermal performance. Optical efficiency seems to be a recurrent topic of
discussion and consideration. The discussed literature proves the importance of each
aspect of PV/T in terms of design, operation, and weather conditions. As explained in
the introduction, nanofluids have better thermo-physical properties than water [21–
25]. Hence, it is very reasonable to employ nanofluids in PV/T collector to enhance
the heat transfer process. The next section provides introduction to nano-material,
in-depth analysis of their thermo-physical properties and application in PV/T cooling.

3 Nano-Materials Used for PV/T Cooling

Nano-materials are nano-sized particles with a diameter between 10 and 100 nm

(nano-scale). The origin of the word nano is Nanos which is Greek for dwarf, which
historically implies small size. Hence, nano is commonly used as an abbreviation of
nanotechnology. Nanoparticles are a product of this technology and are used for many
purposes and exist in different types. Among these types are metals, alloys, semi-
conductors, ceramics, glasses, polymers, and inorganic carbon-based material. These
nanoparticles exhibit better properties due to its high surface area-to-volume ratio,
compared to large particles. This means that nano-materials will be more chemically
reactive [26].
The applications of nano-materials, of different types, are immense. The following
are different applications of nano-materials for different industries.
1. Template material
2. Electronics
3. Solar cells
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 111

Table 1 Summary of studies on photovoltaic thermal collectors

Reference Year Location Type of Method of Investigated Max.
investigated investigation parameter Efficiencies
PV/T
Shahsavar 2010 Iran Direct-coupled Experimental, Glazing, mass flow Thermal:
and air type and modeling rate, natural and around 60%
Ameri forced convection Electrical:
[12] Around 10%
Sopian 1996 Malaysia Single and Theoretical Packing factors, Highest by
et al. [13] double-pass modeling mass flow rate, double pass
air-based PV/T absorber length, Electrical:
pass 7.5%
Thermal:
33%
Chow 2003 China Water-based Experimental Mass flow rate, Thermal:
[14] PV/T with and solar irradiance 60%
tube pipes Numerical Electrical:
10%
Kumar 2011 Canada Double pass, Theoretical Inlet air Electrical:
and air-based PV/T modeling temperature, mass 16%
Rosen with/without flow rate, Solar Thermal:
[15] fins irradiance, fins, 64%
packing factor,
depth of air
channel
Zondag 2003 The Free flow, Theoretical, Collector design Electrical:
et al. [16] Netherlands two-absorber, refers to some type, covers, 7.9% (Tube
channel, tube experimental insulation, and sheet)
and sheet, studies opaque/transparent Thermal:
PV/T designs PV 39%
two-absorber
insulated
Sandnes 2002 Norway Water-based Experimental, Collector Electrical:
and PV/T and analytical configuration, inlet 13.4%
Rekstad model fluid temperature Thermal:
[17] 70%
Dubey 2009 India Water-based Theoretical Number of Electrical:
and PV/T flat plate collectors series 10.7%
Tiwari connection, solar Thermal:
[18] intensity, mass 62%
flow rate For 4
collector in
series
Dupeyrat 2011 Germany Glazed, 2D theoretical Packing factor, Thermal:
et al. [19] water-based model and inlet fluid and 75%
PV/T flat plate experiments ambient Electrical:
temperatures 10.9%
Rosell 2005 Spain linear Fresnel Experiments, Fresnel Thermal:
et al. [20] concentrator and concentration, 65.8%
with a channel theoretical mass flow rate Electrical:
PV/T collector model 13.5%
112 A. H. A. Al-Waeli and H. A. Kazem

4. Biological sensors
5. Gas sensing nanoprobes.
There are many more applications to different nanoparticles. Heat transfer is a
very important application in industry.
Nanofluids are suitable for heat transfer processes. Nanofluids are nanoparticles
mixed with a base fluid. The synthesis of these nanoparticles is classified into two
methods which are physical and chemical. The most popular physical method is
the inter-gas evaporation technique [27]. Other physical methods include sputtering
technique and mechanical deformation. The chemical method of synthesis can be
divided into two:
1. Thermal and ultrasound decomposition methods.
2. Reduction methods.
However, the main issue associated with the chemical method is the chemical
homogeneity of the final product.
On the other hand, the base fluid to mix with the nanoparticles is also important.
There are different types of base fluid’s depending on the application, final product
intended. Most common base fluids used are (1) water and (2) ethylene glycol.
Water is common because it possesses the highest heat capacity per unit mass
of all substances. Moreover, it is abundant and cheap. Ethylene glycol (EG) is a
dihydric alcohol that is composed of two-hydroxyl-groups, making it highly soluble
in water, and is connected to both sides of an aliphatic carbon chain. In addition, it
can easily mix with many polar solvents. Both fluids, water and EG, are similar in
being odorless, colorless, and clear [28].
Several mechanisms affect the nanoparticles as they travel through base fluid,
including gravity, Brownian motion, and thermophoresis. In order to understand these
concepts, it is important to understand what they affect, which is the thermo-physical
properties of the produced nanofluid, or base fluid.
Thermo-physical properties are simply material properties which vary with
temperature without altering the chemical identity of the material. This term is
commonly used to describe the properties associated with transfer and storage of
heat [29]. These properties will include thermal conductivity, viscosity, and density.
Thermally, it also includes diffusivity, heat capacity, thermal expansion, and thermal
radiative properties, as well as mass and thermal diffusion coefficients.
All properties are of interest in the field of nanofluids. This is because nanofluids
are commonly used to transfer heat. Nanofluid-based PV/T collectors are effective
due to the thermo-physical properties of the working fluid. Thermal conductivity is
basically the property of a material to conduct heat. It is expressed with the general
formula given by Eq. (4):
−
→
q = −k ∇ T (4)

−
→
where q is the heat flux, k is the thermal conductivity, and ∇ T is the temperature-
gradient.
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 113

Viscosity of a fluid is a measure of its resistance to gradual deformation by shear

stress or tensile stress. It can be tested using different types of viscometers and
rheometers. The shear viscosity formula is expressed in Eq. (5).

Fy
μ= (5)
Au
where μ is the dynamic viscosity, F and y are the applied force into the separation
distance, respectively. A and u are the area of each plate and speed, respectively.
Density of a material is its ratio of mass per volume. Equation 6 describes the
density.
m
ρ= (6)
v
where ρ is the density, m and v are the mass and volume, respectively.
The effect of these thermo-physical properties is immense for solar heaters and
PV/T collectors. They can affect parameters such as the heat transfer coefficient,
which is the constant of proportionality between the heat flux and the thermodynamic
driving force for the flow of heat. The coefficient is expressed in Eq. (7):
q
h= (7)
T
where h is the heat transfer coefficient, and q is the heat flux.
An example of the effect of thermo-physical properties is thermal conductivity’s
effect on the heat transfer coefficient. This is expressed in Eq. (8):

k
h= (8)
l
where h is the heat transfer coefficient of an object, k is its thermal conductivity, and
l is the thickness of that object. Nanofluids have higher thermal conductivity and
viscosity than water [30]; Meaning, systems utilizing nanofluids will have a better
heat transfer coefficient.
Nanofluid preparation can be classified into two methods: 1-step method and the
2-step method. The most common due to its relatively cheap price is the 2-step
method. The nano-materials are imported in powder form and then mixed with the
base fluid. The mixing process usually involves shaking, spinning, and applying
temperature. Most researchers utilize ultrasonic baths when preparing nanofluids for
PV/T systems. Type, size, and volume fraction of the nano-material play major role,
along with type of base fluid, in the resultant nanofluid’s thermo-physical properties.
Volume fraction (ϕ i ) is the volume of a constituent (V i ) divided by the volume of
all constituents of the mixture V prior to mixing. This is expressed in Eq. (9) [31]:
114 A. H. A. Al-Waeli and H. A. Kazem

Vi
ϕi =  (9)
j Vj

Wang and Xu [32] studied the effective thermal conductivity of alumina (Al2 O3 )
and copper oxide (CuO) nanofluids with diameters of 28 nm and 23 nm, respec-
tively. This was done by mixing the nano-material with different base fluids and
measuring the thermal conductivity using steady-state parallel-plate method. The
authors [32] found an increase in thermal conductivity of all base fluid’s as a resultant
of mixing them with nanoparticles. Moreover, the authors [32] state the decrease in
the nanoparticle size leads to increase in the thermal conductivity. Finally, the disper-
sion method is acknowledged as an important contributor to thermal conductivity.
The authors [32] used three methods for mixing the nanoparticles and base fluids:
mechanical blending, coating particles with polymers, and filtration. The blending
was executed using an ultrasonic bath. The filtration method resulted in the highest
increase in thermal conductivity, 12% with 3 vol% particles in water, for Al2 O3
nanofluid. However, the thermal conductivity of the same nano-material mixed with
ethylene glycol, at same volume fraction, is higher. From this research, done by the
authors [32], the importance of volume fraction, type and size of nano-material is
highlighted, along with importance of base fluid.
According to Prasher et al. [33], increase in the viscosity is greater than thermal
conductivity enhancement for nanofluids which is observed in the literature. The
letter reports increase in nanofluids viscosity corresponding to increase in its volume
fraction, across different types of base fluids. Moreover, the authors [33] illustrated
that relative viscosity does not vary significantly with temperature. Another element
to consider in the preparation of nanofluids is the stability, which is heavily linked
to the type of surfactant employed, and the quality of mixing process.
Drzazga et al. [34] prepared Al2 O3 and CuO nanofluids using the two-step method,
with different stabilizers, SHMP and acetic acid, to investigate the effect of the prepa-
ration method, and stabilizers on nanofluid stability for both types. Good stability
of CuO-water nanofluid was obtained for 1% mass of SHMP while poor stability of
γ-Al2 O3 -water nanofluid was received for all investigated stabilizers.
The density of nanofluids decreases with the increase of the volume fraction,
as illustrated by Prakash et al. [35]. The study investigated two types of nanofluids,
CuO-water and TiO2 -water. Density of TiO2 nanofluid is significantly lower than that
of CuO nanofluid, for the same volume fraction. Moreover, increase in viscosity and
thermal conductivity was observed, corresponding to increase in nanofluid volume
fraction, for both fluids.
A common method to understanding the nano-material implemented is to utilize
different scanning methods such as field emission scanning electron microscope
(FESEM), X-ray diffraction (XRD) or energy-dispersive X-ray spectroscopy (EDX).
FESEM images a sample surface by raster scanning over it with a high-energy beam of
electrons. It allows for the characterization of size, size distribution, and measurement
of height and lateral dimensions. It provides a correlation between surface appearance
and morphology. Figure 1 shows an FESEM image of SiC nanoparticles at the 2 μm
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 115

range and the 200 nm range. Among important information to surmise from FESEM
is the uniformity of particles or observing change in the morphology of the particles.
X-ray diffraction is a technique that is used for the structural characterization of
solid and fluid materials in different ranges including the nanometer (nm) range. This
method can be used to test and identify the crystallite size, shape, lattice distortions,
and faulting. Also, the composition variations, orientation and phase composition
[36]. Figure 3 shows XRD results for the same nano-material, SiC, used in Fig. 2.
Various research works for nanofluid-based PV/T collectors were conducted in
the past decade [37–41] which addressing the nanofluid-related parameters [42, 43],
PV/T design and material parameters [44, 45], and the operational parameters [46,
47]. Different system designs of nanofluid-based PV/T collectors are proposed and
tested [48, 49]. The different designs include flat plate [50], nanofluid impingement
jet [51], and nanofluid spectral splitting filter [52].
Yousefi et al. [53] examined the viability of Al2 O3 nanofluid as a heat absorber
medium for a flat-plate solar collector. The study investigates the impact of mass
flow rate and mass fraction of nanoparticles on thermal efficiency of the collector.
The mass flow rate varies from 1 to 3 L per minute for two mass fractions, 0.2% and
0.4%, respectively. The results obtained showed increase in efficiency corresponding
to increase of mass flow rate, at constant nanofluid concentration.

Fig. 3 X-ray diffraction of SiC

116 A. H. A. Al-Waeli and H. A. Kazem

Zeinali Heris et al. [54] performed a numerical investigation on the convective

heat transfer of three types of nanofluids. The channel of flow had a square cross
section, with a laminar flow. The study focused on adjusting diameter and volume
fraction of the nanoparticles and observing the effects on the fluid. The finds show
an enhancement in heat transfer for two conditions. The first, when decreasing the
nanoparticle size and fixing the volume fraction for all fluids. The second, when
increasing nanoparticle volume fraction and keeping the particle size fixed.
Hwang et al. [55] also investigated multiple nanofluids in terms of conductivity.
The nanofluids are multiwall carbon nanotubes (MWCNT), CuO, SiO2 . All with
water is as the base fluid. The study reports a significant increase in fluid thermal
conductivity (the conductivity increased more than 150% when small—about 1% of
nanoparticles was added).
Sardarabadi et al. [56] experimentally studied an SiO2 nanofluid-based PV/T.
The study aimed to assess the impact different weight percentages, 1% and 3%, had
on the electrical and thermal efficiencies. The authors [56] performed an uncertainty
analysis to measure the inaccuracy. Adding 1% and 3% nanoparticles to water caused
an increase in PV/T energy efficiency by 3.6% and 7.9%, respectively. This was done
by converting produced electric power into equivalent thermal energy. As for thermal
efficiency, it was increased by 7.6% and 12.8% for 1 wt% and 2 wt%, respectively.
The total exergy was compared to a water-based PV/T and a conventional PV. Water-
based PV/T, 1%-SiO2 -nanofluid, and 3%-SiO2 -nanofluid led to an increase in total
exergy by 19.36%, 22.61%, and 24.31%, respectively.
Other methods of cooling or maintaining PV module temperature were intro-
duced in this field. Among these methods is the use of phase change material (PCM).
Organic PCM has been used to store and release temperature. PCMs are stable, non-
toxic, recyclable, non-reactive, non-corrosive and available for wide phase change
temperature selection. Simply, according to the required application, paraffin wax
PCM is used for thermal storage to maximize thermal efficiency for PV/T collectors.
PCM-based PVs and PV/Ts have massive potential for development. Ma et al. [57]
presented a comprehensive review on PCM use in PV systems, for thermal regula-
tion and electrical efficiency improvement. Various systems and emerging concepts
were discussed in detail including aspects such as system development, performance
evaluation, materials selection, heat transfer improvement, and numerical models.
The study raises a concern on the economic-feasibility in enhancing PV efficiency
only. PV/T systems utilizing PCM has a better potential, giving that the thermal
storage could be extracted using a working fluid. Preet et al. [58] performed an
outdoors experimental investigation of a water-based PV/T with and without PCM
and compared the collectors to conventional PV system. The authors [58] integrated
copper pipes to carry the water. Paraffin wax (RT-30) was used as the PCM. The study
used three mass flow rates, which are 0.013 kg/s, 0.023 kg/s, 0.031 kg/s to investi-
gate effect of mass flow rate on thermal and electrical efficiencies. The authors [58]
found that overtime, the electrical efficiency of the PV/T with PCM becomes higher,
while thermal efficiency of the PV/T without PCM becomes higher, which seems
like a trade-off that must be taken into consideration. Nano-PCMs are preferred due
to having higher heat release rates, compared to base fluids, which is attributed to
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 117

Fig. 4 a Top-view, b side-view drawings of the proposed PV/T

increase of thermal conductivity and reduction of latent heat. Fan and Khodadadi
[59] performed both experimental and theoretical investigations to study freezing
nano-PCM in container in vertical configuration. The experiments were used to vali-
date the theoretical model established using a modified 1-D Stephan model. The
solidification process was studied by Khodadadi and Hosseinizadeh [60] numeri-
cally using a square cavity which stores nano-PCM and is differentially heated. The
results of the study show how higher rates of heat are released by the nano-PCM
over the typical PCM medium and mainly attributed those outcomes to increase and
reduction of thermal conductivity and latent heat, respectively.
The evolution of nano-material in PV/T systems continues to provide more inno-
vative systems with better overall performance. In 2017, the authors of this work,
Al-Waeli et al. [61], introduced a novel method and design of a hybrid nanofluid and
nano-PCM-based PV/T. The collector was designed for maximum PV-cooling and
thermal production. The concept was to increase the thermal conductivity of PCM
by employing nanoparticles, or else known as nano-PCM. Nanofluids were added
for optimum extraction of heat. The side-view and top-view drawings are given in
Fig. 4.
The system was designed for optimum heat transfer. This was achieved by
employing high thermal conductivity material such as nanofluids and nano-PCM.
Moreover, as Fig. 4 shows, the system utilizes galvanized steel and copper as well.
The copper pipes are emerged into a layer of nano-PCM which is stored at the back of
PV module. The nanofluid will flow within these copper pipes. To ensure higher heat
transfer, glass wool was implemented for thermal insulation. The system consisted
of the proposed PV/T collector, a heat exchanger, a nanofluid tank, an expansion
tank, the proper sensors, and control devices. In-between the PV and the nano-PCM
tank, silicon oil was implemented to avoid air-gaps for better heat transfer. Moreover,
the tank covered the whole area on the back of the PV for better cooling and heat
transfer. Figure 5 shows the schematic diagram of the combined system.
The operation of the system is dependent on the nanofluid cycling through the
PV/T, extracting heat, and the heat exchanger, transferring heat to water. By the start
of every cycle, the nanofluid must be cooled-down for maximum heat transfer. The
118 A. H. A. Al-Waeli and H. A. Kazem

Fig. 5 Schematic diagram of the nanofluid and nano-PCM-based PV/T

nanofluid itself must be made so that it has high thermal conductivity and viscosity.
This is done by performing accurate mixing and shaking of nanoparticles in the
base fluid. The nano-PCM must be prepared effectively as well. Figure 6 shows the
preparation of the nano-PCM.

Fig. 6 Preparation of nano-PCM using ultrasonic bath

Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 119

Various mass flow rates were implemented ranging from 0.00833 to 0.0175 kg/s.
The system was tested outdoors for Malaysia’s tropical climate. The sensors used
include flow meter, k-type thermocouples, pyranometer, and multimeter for nanofluid
mass flow rate, surface temperature, solar irradiance, and electrical components—
voltage and current, respectively. A data acquisition device was used to collect the
data and transfer it to a portable computer. All pipes and containers were well isolated
to avoid heat escape. Moreover, the proposed PV/T was compared to a water-based
PV/T, a PCM-water-based PV/T, and a conventional PV.
The next section will present results from the outdoor experiments of the nano-
PCM and nanofluid-based PV/T from our published works [61–64].

4 Results and Discussions

SiC nano-material was used for the nanofluid and the nano-PCM, while organic
paraffin wax was used as PCM. The FESEM image and XRD analysis of the nano-
PCM can be viewed in Fig. 7, while the EDS scan is provided in Fig. 8.
Figure 8 shows the map sum spectrum of the nano-PCM or SiC-Paraffin sample.
It clearly shows traces of silicon (Si) and high content of carbon (C). Hydrogen (H)
is not shown because it is a light element and cannot be routinely analyzed using
EDX.
Four systems are considered in the results which are:
1. Nanofluid and nano-PCM-based PV/T/abbreviated (PVT cell.pcm.n.nf)
2. PCM tank, water-based PV/T/abbreviated (PVT cell.pcm.w)
3. Water tank, water-based PV/T/abbreviated (PVT cell.w)
4. Conventional PV.
To reduce the number of tests required, the experiments began with an investiga-
tion of optimum mass flow rate by testing various nanofluid flow rates. Water-based
PV/T with a PCM tank was used for these tests. Figure 9 shows the observed change
in PV module temperature across various flow rates throughout the day.
To form a better understanding of the system, Fig. 9 shows the recorded temper-
ature of the PV, the solar irradiance, and time. The solar irradiance and ambient
temperature behaviors are displayed in the black (diamond marker) and orange lines
(square marker), respectively.
From Fig. 9, it can be observed that temperature of the PV module has decreased
with increase of mass flow rate from 0.0833 to 0.175 kg/s. These results agree with
the theory and literature, where increase of mass flow rate causes increase in heat
exchange and enhanced heat transfer from hot to cold mediums. More increase to
mass flowrate could be made, but a vibration in the PV/T system was noticed. Hence,
it is important that the mechanical design works well with operational parameters.
Hence 0.175 kg/s shows better cooling and is suitable for the system, and it was used
for the remaining experiments. The temperature distribution across the four systems
investigated and is provided in Fig. 10.
120 A. H. A. Al-Waeli and H. A. Kazem

Fig. 7 a FESEM of SiC-paraffin, b XRD of SiC-paraffin

It is noticeable that temperature of all modules starts higher than the ambient. This
is because measurements were taken after sunrise. As expected, the conventional PV
module had the highest temperature throughout the experiments; as no method of
cooling or thermal regulation was implemented. The second highest in temperature
was the water-based PV/T with a water tank, then the water-based PV/T with a
PCM tank. The lowest PV temperature is clearly the nano-PCM and nanofluid-based
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 121

Fig. 8 EDS of SiC-paraffin

sample

Fig. 9 Effect of mass flow rate on collector temperature for the tested systems

PV/T. Nanofluid has lower specific heat than water, but it does have higher thermal
conductivity and so it led to higher reduction in PV module temperature. Using
nano-PCM allowed for better utilization of PV temperature to produce more thermal
energy. The nano-PCM has the advantage in heat storage as it acquired temperature
and transferred it to the nanofluid more quickly. The thermal energy and thermal
efficiency of the systems are provided in Figs. 11 and 12, respectively. The fourth
collector, conventional PV, was excluded from these two figures given that it does not
capitalize on thermal energy. Although the electricity produced can be converted into
thermal energy for the sake of comparison, however, it would be counterproductive to
do so, and employing a solar thermal collector would be more suitable. It is needless
122 A. H. A. Al-Waeli and H. A. Kazem

Fig. 10 Temperature distribution of all systems

Fig. 11 Thermal energy of the PV/T collector

Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 123

Fig. 12 Thermal efficiency of the PV/T collector

to say that other environmental variables have some effect on the performance of the
module and may lead to some irregularities which are expected in tropical climate,
for example, wind speed and direction, diffused and reflected solar irradiance, air
mass and position of the sun.
Clearly, the highest thermal energy is produced by the nano-PCM and nanofluid-
based PV/T which is mainly attributed to design material. Increase of heat transfer
due to employing nano-material is the main key to this process. The better heat
transfer occurs the better cooling of the module happens and hence maintaining
electrical performance close to the standard conditions. It is important to note that
instantaneous change of solar irradiance leads to temperature fluctuations which are
dampened, or even eliminated, if PCM is used. The use of a nanofluid is particularly
crucial at later time, throughout the day, typically 4–6 PM, where it is important to
extract heat from the PCM or the nano-PCM as fast as possible to avoid heat returning
to the module; given that module surface temperature begins to drop considerably.
Because nano-PCM has higher thermal conductivity than water and PCM, it stores
the heat for a longer time and hence discharges without acquiring new heat, which
explains the thermal efficiency of the nanofluid and nano-PCM collector. As for
thermal efficiency, Fig. 12 shows the efficiencies for the three proposed systems over
time.
At the start of the testing, all three systems had similar efficiencies as not enough
heat was transferred to the working fluids. Since the highest thermal efficiency is
achieved by the nano-PCM and nanofluid-based PV/T, it is clear that it causes the
most reduction in PV module temperature, which in turn will affect its electrical
efficiency, as it is shown in Fig. 16. In general, the curves are similar with exception
124 A. H. A. Al-Waeli and H. A. Kazem

Fig. 13 Electrical voltage of PV/T collector

Fig. 14 Electrical current of PV/T collector

Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 125

Fig. 15 Electrical power of PV/T collector

Fig. 16 Electrical efficiency of PV/T collector

126 A. H. A. Al-Waeli and H. A. Kazem

to that of the proposed system which shifts due to its ability to store heat better. This
heat could be utilized in many applications ranging from residential water cooling to
industrial pre-heating for steam generation [65]. This system although has significant
thermal efficiency, and there are multiple risks that need to be studied and considered
for large-scale.
Firstly, it is the type of nanofluid and the preparation process. The performance
of the system itself may vary according to the nanofluid and nano-PCM employed.
Good mixing and preparation of the nanofluid and nano-PCM would lead to better
thermal conductivity, while bad mixing would change that result.
Secondly, it is also important to ensure accurate pouring of nano-PCM into the
nano-PCM container, or tank, to avoid gaps in the tank. Moreover, the stability
analysis of the employed nanofluid over long period of times must be considered as
well. Good welding of the design material must be ensured, and leaks of both liquid
and heat must be avoided. Complete covering of the PV module is important to cover
more area of the collector for heat transfer.
To assess the electrical performance of the collector, it is preferable to state the
general properties of the PV module. The PV power, open-circuit voltage, short-
circuit current, and efficiency at standard testing conditions (STC) are 120 ± 3%
W p , 21.5 V OC , 7.63 I SC, and 14%, respectively. The elements affecting the system
are solar irradiance, ambient temperature, and mass flow rate. Remaining elements
such as atmospheric pressure, wind speed, and age of the PV were neglected. A
source meter was used to measure the output of the module. Figures 13 and 14 show
the electrical voltage and current of the different collectors, respectively.
Both figures, of voltage and current, are with respect to solar irradiance and
temperature. The voltage waveform of the PV is more affected by variations in
solar irradiation, given that it would affect the potential barrier of the cell itself
and cell temperature. However, current waveform is consistent with solar irradiance.
Given continuous changes in instantaneous solar irradiance, fluctuations, and spikes
appear for both the voltage and current, as shown in Figs. 13 and 14. The highest
voltages for the systems were around 18–20 V and 20–21 V for the PVT.pcm.w and
PVT.pcm.n.nf, respectively. Moreover, the average voltages are around 19.7 V and
20.6 V, respectively. The current curve is highly affected by solar irradiance curve.
The current increased with the increase of cell temperature, which is consistent
with the theory; however, for all PV modules the current fluctuated throughout the
experiments but the change is insignificant. The electric power and efficiency of the
systems are presented in Figs. 15 and 16, respectively.
From Fig. 15, the highest production of electric power during the experimental
period is achieved by the nano-PCM and nanofluid-based PV/T. The instantaneous
peak power generation of the systems is 61.1 W, 85.7 W, 116.1 W, and 119.5 W
for the PV, PVT.w, PVT.pcm.w, and PVT.pcm.n.nf, respectively. These values are
subject to uncertainty of 3%.
Moreover, the electrical efficiency follows, as Fig. 16 shows the electrical effi-
ciency, which is also a success domain for the PVT.pcm.n.nf which achieved peak
instantaneous efficiency at around 13.7% that is very close to that of standard testing
conditions. However, instantaneous efficiency should not be a representation of the
Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 127

PV performance throughout the day, nor overtime. The second-highest efficiency is

achieved by PVT.pcm.w with around 11.3%, followed by 8.6% for PVT.w, respec-
tively. The lowest electrical efficiency is found for the typical PV module that may
seem shocking; however, it is very reasonable under tropical climates. It is note-
worthy to mention that one pyranometer is used in-between all four-system collector;
meaning slight variation of incident solar irradiance occurs from the one shown in
graph. Moreover, changing pyranometer tilt angle can affect the measurement as
well. The modules are installed at a tilt angle, and the hence difference between
recorded solar irradiance and actual irradiance received by PV can differ slightly.
The thermal and electrical efficiencies of the proposed system effectively show-
case the importance of nano-material for solar energy development. Nano-PCMs
have a massive potential for these systems. It is important to note that the water-
based PV/T with a water tank is not very common, as most research only employed
direct pipes with water or flat-plate designs. PV module can decrease in efficiency up
to a substantial margin due to environmental elements such as heat, humidity, dust,
and inner device losses [66]. Irregularities, spikes, and discontinuity are major issues
associated with PV modules and need to be addressed. Establishing PV/T for cooling
and heat extraction is a cost-effective method and has great potential for success in
the field.
Voltage and current of the PV are majorly affected by the cell temperature as
established by Figs. 13 and 14. Hence, cell temperature is the main link between
PV and solar thermal to forming PV/T. Figure 13 shows an inversely proportional
relationship between voltage and cell temperature. In Fig. 16, the electrical efficiency,
partially as a product of PV cell temperature, is shown to be high for the proposed
system in comparison with other designs. The results displayed in this section are
summarized in Table 2.
It is important to differentiate between the results displayed in Table 2, maximum
values, and average operational values. For comparison with other systems, the type
of PV at STC must be unified for far comparison. However, in terms of thermal
collector it is not necessary to compare it to a similar type, for thermal compar-
ison. The claim is to compare the proposed type to other types of thermal collec-
tors, of PV/T to see which holds the highest efficiency. The main challenges of this

Table 2 Summary of electric/thermal behavior of different PV/T systems

System Peak PV Peak output Max. Maximum Max. total PV/T
temperature cooling fluid thermal electric efficiency (%)
(°C) (°C) energy efficiency
(kW) (Wp)
PV 68.3 – – 77.6 7.11 (no
thermal)
PVT.W 45.22 49.72 9.51 85.1 45.32
PVT.PCM.W 42.22 52.52 10.5 107.4 62.82
PVT.PCM.N.NF 39.52 58.62 13.8 119.5 85.7
128 A. H. A. Al-Waeli and H. A. Kazem

configuration are mainly in preserving the stability of produced material for repeated
cycles and establishing cheaper and simpler methods for preparing the end-product
nanofluids and nano-PCM for the end-consumer. Discharging process after sunset
is also considered an issue given that more power is spent to ensure no temperature
revert to the PV module. Finally, the use of PCM will lead to increased weight and
hence further construction costs.

5 Summary and Conclusions

This chapter presented advances of nano-material utilized in photovoltaic thermal

(PV/T) collectors. The chapter introduces solar energy, PV and solar thermal, and
PV/T collectors. The concepts and classifications of PV/T are explained, and the
literature work is reviewed as well. Nano-material and nanofluids were introduced
and explained as working fluids for PV/T systems. PCM and nano-PCM were also
introduced as thermal regulation mediums for PV and PV/T systems. The evolution
of nano-material use in PV/T collectors is further summarized in Fig. 17 [61, 67,
68].
With regard to nano-material, the following conclusions summarize the informa-
tion presented in this chapter:

Fig. 17 Summary of PV/T classifications with nano-material innovative solutions

Advances in Nano-Materials Used in Photovoltaic/Thermal Systems 129

1. Nano-materials are special materials produced at nano-scale which have

favorable properties for various industrial applications (e.g. electronics).
2. Nano-materials have a high surface area-to-volume ratio which makes them
more chemical reactive than normal-sized material.
3. Nano-material synthesis is extremely important to produce them for the desired
application and is classified into physical and chemical methods.
4. Nanofluids are nano-materials mixed with a base fluid. They exhibit better
thermo-physical properties than water, or ethylene glycol. Hence, they are used
for heat transfer applications.
5. Nanofluid preparation is a critical stage to obtain stable nanofluids.
Mixing/shaking process and nano-material mass fraction have significant effect
on the fluid’s thermal conductivity, viscosity, and density.
6. Higher mass fraction of nano-material leads to higher thermal conductivity and
lower density. However, an offset would be the cost associated with adding
more nano-material.
7. The biggest issue associated with nanofluids is agglomerations and sedimenta-
tions which are bound to occur but could be minimized.
8. Stability, particle structure, and morphological properties are among character-
izing factors which can be examined using various scanning methods such as
FESEM, EDS, and XRD.
9. Nanofluids are considered Newtonian fluids and are affected by gravity and
Brownian motion.
10. Nanofluids are used for different types of PV/T collectors, spectral splitting
filters, jet impingement, and flat-plate designs.
Phase change materials (PCM) are effective tools for maintaining and thermal
regulating the temperature of the PV modules. However, they lack thermal conduc-
tivity. Hence, employing nano-materials will affect this process, yielding ‘nano-
PCM.’
The implementation of nanofluids has massive effects on thermal and electrical
behavior of PV/T systems. Highlighted below are important factors associated with
nanofluid-based PV/T:
1. Nanofluid-based PV/T has higher thermal and electrical efficiency than water-
based PV/T.
2. PCM-based PV and PV/T have higher thermal efficiency than conventional PV
modules.
3. Nano-PCM has higher thermal conductivity than PCM and is more suitable for
heat transfer applications.
4. Increase of nanofluid mass flow rate leads to better cooling and heat extraction,
up to a certain point.
5. Thermal isolation and elimination of air-gaps are crucial to the successful design
of PV/T.
6. Higher solar irradiance leads to higher electrical efficiency when cooling the PV
modules.
130 A. H. A. Al-Waeli and H. A. Kazem

Currently, the main challenges facing this technology are the high costs for
producing nanofluids and nano-PCM. Other challenges extend to stability of
nano-material and accurate methods of measuring latent heat change.
The design described in the results and discussion sections can be improved for
future research with consideration of the following points:
1. Using the photovoltaic module frames as the nano-PCM tank buy simply placing
a sheet at their back to cover it. Also, this will eliminate the need for silicon oil
in the design.
2. Varying the design of the pipes to examine different configurations for improved
performance.
3. Employing concentrated CPC PV/T with the nano-PCM and nanofluids to test
the effect of concentration on thermal and electrical power generation.
Further, research investigations must be conducted to examine various environ-
mental conditions and PV/T system configurations using nano-material for efficiency
enhancement and offering cost-effective solutions for consumers.

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Si Quantum Dots for Next-Generation
Solar Energy Harvester

Mrinal Dutta

Abstract Over the last two decades, semiconductor quantum dots have attracted
considerable research interest for a wide range of applications such as photovoltaics,
light-emitting devices, nanoelectronics and markers for biomedicine. Among these,
non-toxic silicon quantum dots (Si QDs) have grown intensive worldwide research
interest because of their exciting physical properties and prospects in future electronic
and optoelectronic devices. Tuning the band gap through quantum confinement by
tuning the QD size and tuning the surface-related luminescence properties from UV to
NIR range allow fabrication of optimized tandem photovoltaic devices in one growth
run. This chapter focuses on the progress and growth of Si QD-based photovoltaic
devices with the synthesis techniques as well as the broad range emission properties
of these Si QDs. The issues related to p-type and n-type doping of these QDs are
also discussed in this context. The performances of several photovoltaic devices
reported in the literature are summarized. Finally, several routes for optimizing the
performance of these Si QD cells by resolving the doping issue and other structural
improvements are discussed.

Keywords Si quantum dot · Non toxic · Solar cell · Energy harvester · Multi
exciton generation

1 Introduction

In the last two decades, intensive research has been focused on the synthesis of semi-
conductor quantum dots (QDs) having color-tunable emission properties for their
potential applications in light-emitting diodes (LEDs), lasers, thermoelectric devices,
solar cells and biomedical imaging [1–5]. The synthesized QDs for these applica-
tions should be compatible with the existing mature device processing technology,

M. Dutta (B)
Inorganic Photovoltaic Devices Group, Advanced Materials Device Division, Council of
Scientific & Industrial Research (CSIR)-National Physical Laboratory, K.S. Krishnan Marg,
Pusa, New Delhi 110012, India
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 135

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_6
136 M. Dutta

cost-effective and environment friendly to be used in long run. The conventional

direct bandgap semiconductor QDs such as CdS, CdSe and PdS QDs. are efficient
emitters, and their emissions can be tuned in a long range by changing QD size only.
However, they are toxic in nature and do not properly fit with the existing semi-
conductor processing technology, and moreover, they are not as much cost-effective
as per need. The semiconductors that have all these advantages such as silicon and
germanium are indirect bandgap semiconductors and have poor absorption and emis-
sion properties. The top of the valance band and the bottom of the conduction band
are not at the same point in the Brillouin zone. Due to this, they are inefficient emit-
ters as the radiative recombination across the band gap needs phonons to conserve
crystal momentum [1, 6]. In 1991, Cullis and Canham for the first time showed the
path and raised the hope to obtain visible emission from indirect bandgap semicon-
ductor like Si by using porous form [7]. They showed that quantum confinement
could remove this inefficiency in emission of indirect bandgap semiconductors. The
report of this pathbreaking discovery in 1991 started a new dawn of production of
Si nanostructures with good emission property. Bandgap enhancement and indirect-
to-direct conversion of indirect bandgap semiconductors are ascribed to quantum
confinement [8]. Bandgap tuning is possible in different forms of Si nanostructures
such as Si nanowires, porous Si, Si nanocrystals and Si QDs.
Right after the discovery of luminescence from porous Si and up to the middle
of the last decade, intensive research was focused on the synthesis of various forms
of luminescent Si nanostructures and established the possible mechanism of this
luminescence property. These various efforts include reports on the light emission
from textured bulk Si, porous Si, electrochemically etched Si, Si nanocrystals or
Si QDs embedded in dielectric (SiO2 , SiN, SiC) matrix etc. [9–12]. Here, it is to
be mentioned that Si nanocrystals having size less than exciton Bohr radius are
usually called Si QDs [13]. Among various nanostructures of Si, Si QDs exhibit
strong quantum confinement effects. As a result electrical, optical and photovoltaic
properties can be tuned by changing size, surrounding matrix, doping and crystalline
structure [14–19].
However, when compared to the other luminescent Si nanostructures, colloidal Si
QDs offer the highest quantum yield, full solution processing, good mechanical and
chemical stability and easily tailorable optoelectronic properties. Because of these
properties, research on the synthesis of high quantum yield Si QDs has been shifted
to the forefront of research in Si from the middle of the last decade. The colloidal
stability of the QDs has attained by surface modification and using ligands of various
compositions.

2 Synthesis

Only some of the conventional Si QD synthesis techniques will be discussed in this

chapter. Interested readers are referred to the review articles of Askari et al. [20],
Ghosh et al. [21] and Dogan et al. [22] the references therein.
Si Quantum Dots for Next-Generation Solar … 137

2.1 Bottom-up Approach

2.1.1 Atmospheric Pressure Plasmas

Synthesis of Si QDs by atmospheric pressure plasma technique offers simplicity,

low cost and versatility. Here, gas discharge occurs between electrodes where at
least one electrode dimension should be less than 1 mm. The discharge could be
powered by use of direct current or by use of capacitive discharge in which gas
temperature should be less than 0.2 eV with an electron temperature up to 10 eV
[23]. Sankaran et al. [24] used direct-current (DC) microplasma for the first time to
synthesize Si QDs. 30% quantum efficiency for the Si QDs with blue luminescence
at room temperature was reported. The discharge was carried out in a metal tubing
as anode in which a metal capillary was configured as cathode and powered with a
DC power supply (power density was measured for the plasma as ~ 5000 W cm−3 ).
This approach could be considered as an important step toward synthesis of Si QDs,
however, subjected to the limitations of high-scale production and scaling up in large
surface area. Later, Barwe et al. [25] using a fast camera imaging find out that the
plasma was not located inside the hollow cathode. The plasma was appeared to be
moving filamentary microplasma between cathode and anode, and only a part of the
gas flow was interacting with the plasma. This observation could explain the reason
behind the low throughput of the process. Nozaki et al. [26] in an attempt to improve
this method changed precursor chemistry as well as reactor configuration. Instead of
silane, silicon tetrachloride was used as precursor, and radio-frequency (144 MHz)
atmospheric-pressure microplasma sustained by two ring electrodes was used in
place of micro-hollow cathode configuration. With time, the two ring configurations
(Fig. 1) have been proved to be more effective in production of Si QDs at high rate.
HRTEM and dark field analysis show that synthesized QDs are very well separated
and have a very narrow distribution (~ 2 nm in diameter) with good crystallinity [27].
With the progress of research work more easily, scaled-up reactor configuration has
come out. The geometry of such a modified configuration, called ‘cross-flow’ as
termed by its inventors, uses the electric field across the electrodes placed normal to
the direction of the flow on the contrary of the two previous configurations [28].

2.1.2 Microwave Plasma

Operating power in microwave plasma varies from hundred to thousand watts

where microwave cavities decompose precursor gas and generate plasma. Wiggers
group [29–32] has successfully produced crystalline Si nanocrystals with sizes 3–
30 nm using Ar/H2 /SiH4 gas mixture. Just after entering into the plasma zone, SiH4
completely dissociates from free Si atoms and nucleation process starts from this
supersaturated Si atoms. After formation of small Si nanoparticles, they start to sinter
and reach larger sizes. However, agglomerated Si nanocrystals are formed in the cold
downstream zone. The gas temperature drops quickly when Si nanocrystals go out
138 M. Dutta

Fig. 1 a Schematic diagram of the ‘two-ring’ configuration microplasma reactor; b photo of the
plasma inside the quartz tube; c representative TEM image of the silicon QDs Reproduced with
permission from [27], Copyright (2014) AIP Publishing

of plasma zone after growth. In this process, the size of the Si nanocrystals can be
controlled by changing SiH4 concentration, total gas pressure in the reaction chamber
and the residence time. Increase of SiH4 concentration and total pressure increases
the number of primary nanocrystals and helps in growing larger size nanocrystals by
increasing their sintering rate, while increase in residence time allows more time to
grow nanocrystals. In view of high scalability, microwave plasma is very attractive
as it could produce in one hour of processing as high as 10 g of Si nanocrystals [3].

2.1.3 Non-Thermal Plasma

Non-thermal plasmas are composed of ‘hot’ electrons having energy between 2 and
5 eV, and colder ions and neutral species. In the experimental setup, two copper
rings are used to produce RF power (~ tens of watts) to generate a plasma for the gas
mixtures of Ar/SiH4 [33–39] or Ar/SiCl4 [40, 41] flown through a narrow quartz tube
Si Quantum Dots for Next-Generation Solar … 139

Fig. 2 Schematic diagram

of the non-thermal plasma
system together with a photo
of the plasma Reproduced
with permission from Ref.
[37]. Copyright (2005)
American Chemical Society

placed within these rings (Fig. 2). Dissociation of the precursor gas by hot electrons
produces mainly radicals and negative ions. In non-thermal plasmas, Si nanocrystal
formation occurred mainly by anion–neutral reactions. By controlling the residence
time (~ <10 ms) of the nanocrystals in the plasma, size control is achieved [37, 41].
A narrow size distribution of the nanocrystals within the range of 2–20 nm could be
achieved in this way. With this, partial pressure also has effect in controlling the sizes
of these Si nanocrystals [37]. Using non-thermal plasma, it is possible to produce
fully amorphous or fully crystalline nanoparticles by controlling the power coupled
in the plasma [38, 41].

2.1.4 Thermal Plasma

Si nanocrystals could be produced in thermal plasma zone at very high rate ~ 300
gm/hour, that is, almost highest among all plasma synthesis process [42]. At high
power discharges (from a few to hundred kWs having electron and gas temperature
above 1 eV) and close or at atmospheric pressures, synthesis of Si nanocrystals has
been reported using both RF and DC sources [42–46]. In thermal plasma region,
micrometer-sized solid particles also can be used as precursor material. With the
vapor phase condensation from a supersaturated vapor of Si atoms within the thermal
plasma zone, nucleation occurs also in the downstream where the gas temperature
is less than 0.4 eV by means of coagulation and co-condensation [42, 44]. Size
control of Si nanocrystals with sizes of 5–20 nm could be synthesized by varying
substrate-to-nozzle distance and the residence time [43–45].
140 M. Dutta

2.1.5 Solution Phase Oxidation/Reduction

This method is most popular method to prepare nanocrystals. Heath [47] first used
this method in 1992 to synthesize Si nanocrystals. The synthesis was done at high
pressure and high temperature (~385 °C) in a nonpolar organic solvent in which
reduction of silicon tetrachloride and RSiCl3 (R = hydrogen atom or octyl group)
was done by sodium metal. Use of trichlorosilane resulted nanocrystals in broad size
distribution (5 nm to 3 µm), whereas use of trichlorooctylsilane provided a good
control on size distribution, and the average size of the Si nanocrystals was estimated
as 5.5 ± 2.5 nm. Dhas et al. [48] used sonochemical method by reducing reaction
temperature and pressure of the above procedure. Ultra-sound induced reduction of
tetraethyl orthosilicate at 70 °C in toluene by sodium has used to produce porous
silicon nanoparticles within size range from 2 to 5 nm having an emission maximum
at around 680 nm. Synthesis of alkyl-capped Si QDs has been reported by the reduc-
tion of SiCl4 in appropriate solvents by using Zintl compounds like potassium silicide
(KSi), sodium silicide (NaSi), etc. [49, 50]. These QDs showed strong NUV–blue
luminescence property, and their sizes were measured to be in the range of 2–5 nm
[50]. Later, metal silicides were replaced by sodium biphenylide and sodium naph-
thalenide to reduce SiCl4 [51]. Chloride-capped QDs obtained through this reduc-
tion process had average size of 5.2 ± 1.9 nm. Due to slightly polar characteristic,
sodium naphthalenide was found to be more useful for complete purification. In this
process of alkoxylation, surface of QDs was capped with halide atoms that help
in efficient surface passivation. Samara group [52, 53] used reverse micellar cage to
effectively control the size of Si nanocrystal in the range of 1.8–10 nm. The nanocrys-
tals produced by the reduction of SiCl4 by LiAlH4 in this method were further size
selected by using high-performance liquid chromatography. Tilley et al. [54] prepared
highly monodisperse nanocrystals using the above method using tetraoctylamonium
bromide (TOAB) as a surfactant.

2.2 Top-Down Approach

2.2.1 Laser Ablation

In 1991, Okada and Iijima first reported the production of almost spherical Si particles
within diameter 20–500 nm by laser ablation [55]. High-resolution transmission
electron microscopic (HRTEM) studies confirmed a crystalline core surrounded by
1–2 nm amorphous oxide layers. Laser ablation was done under argon or oxygen
environment by using a Si wafer as target. Later, in 1994, by modifying this process,
Si QDs within 2–3 nm size range with emission in red region were produced [56].
Very low pressure ~ 10−8 Torr was used to carry out this abalation process. After this
success in the synthesis of luminescent Si nanocrystals by laser ablation technique,
several different types of modified approaches have been used [57–59]. Si QDs with
emission in the range 1.34–1.79 eV due to change in the size of the nanocrystals
Si Quantum Dots for Next-Generation Solar … 141

were reported by Orii et al. [60] by changing the parameters of ablation in helium
gas environment. Laser ablation also carried out successfully in liquid environment
instead of using gaseous ambient. Surface-passivated freestanding Si QDs could be
fabricated in a one-step approach by using reactant as a solvent (liquid medium)
in laser ablation [61]. The colloidal Si QD solution prepared from same Si target
emitted 2.9 and 3.5 eV light when prepared by pulsed laser ablation using water and
hexane as reactant solvent, respectively [62].

2.2.2 Electrochemical Etching

Synthesis of Si QDs by electrochemical etching of Si wafer used as anode of the

electrochemical process also had been used extensively. The first observation of
synthesis of Si nanocrystals by this method was reported by Heinrich et al. [63]. In this
method, to produce colloidal suspension of Si nanocrystals, n-type or p-type Si wafers
are made porous after electrochemical etching and ultrasonicate in solvents like water,
methanol, methylene chloride, toluene, etc. Ultrasonically dispersed nanocrystals by
this method are irregular in shape, and their sizes vary from nanometer to micrometer
scale. To improve this size distribution, the thin section of the wafers was started to
ultrasonicate for long time, and later, Kauzlarich group used a 20 nm sieve to filter
out large size nanocrystals [64]. This process helps to separate Si nanocrystals with
a very narrow size distribution within 2–11 nm.

3 Properties

Properties of crystalline bulk silicon are found to be uniform in size ranging from
some tenths of nanometers up to centimeters. However, the properties of Si-QDs
found to be strongly dependent on size; the interface between matrix and QDs could
influence the properties, and in case of the electrical transport, strong dependence on
the distance between the QDs is observed.

3.1 Optical Properties

Due to indirect bandgap nature of Si, bottom of the conductance band and top of the
valence band are not aligned in k-space. By using the effective mass approximation,
the effect of the confinement on the bandgap energy can be given as [65],
 
E gap = E gap_si - bulk + 2 π 2 /2 1/L 2x + 1/L 2y + 1/L 2z [1/m e ∗ +1/m h ∗] (1)

where E gap_si-bulk is the band gap in bulk silicon (1.12 eV), L x , L y , L z are the dimen-
sions of the nanostructure and me * and mh * are the effective masses of electron
142 M. Dutta

and hole in bulk silicon. In a first approximation, the hole mass is essentially half
of the electron mass. This simple model predicts that the shifting of the valence
band should be twice that of the conductance band. Figure 3 shows the effect of
size reduction on band gap (measured from photoluminescence transition energy)
[66]. Effect on band gap becomes vital by reducing the size below 5 nm, and for
2 nm size of QDs, it is predicted to be as high as 2 eV. This shifting of conduc-
tion and valance band well agrees with effective mass approximation and could be
measured experimentally by x-ray and UV absorption techniques (such as x-ray or
UV photoelectron spectroscopy) [67]. In addition to change of bandgap energy, the
quantum confinement also influences the transition probabilities. Localization of the
carriers (excitons) takes place in a very small volume due to quantum confinement,
and this effect relaxes the k-selection rules, thus increasing the quasi-direct transi-
tion probabilities. Brus et al. [68, 69] investigated theoretically and experimentally to
understand the size-dependent confinement effect and also surface passivation effect
on photoluminescence property of Si QDs within size range 3–8 nm. They observed
that the emission within 600 nm to 900 nm could be tuned by varying the size of
the crystalline core of Si, and oxide passivation could lead to red shift of band gap,
relatively high PL and low radiative rates. This group further suggested that the QDs
have indirect band gaps by studying the broad absorbance near 3–4 eV.
Proper surface passivation by organic molecules or silica shells drastically
increased the PL quantum yields (QYs) up to 40–50% [70, 71]. Holmes et al. [72]

Fig. 3 Variation of
transition energy with the
size of the nanostructures
Reproduced with permission
from Ref. [66]. Copyright
(2009) Canadian Science
Publishing
Si Quantum Dots for Next-Generation Solar … 143

reported high PL QY up to 23% using organic monolayers for the passivation of the
silicon surface. QYs reached up to 60% when plasma-synthesized Si QDs surface
was passivated by organic ligands under strict exclusion of oxygen [72]. However,
for hydrogen-terminated Si QDs, maximum PL QYs reached up to 10% and decayed
with ambient conditions. It is proved by both theoretical and experimental studies
that the surface properties of QDs play a dominant role in controlling the band gap
and the radiative decay time [73, 74]. Naturally occurring surface oxide generates
oxygen-related surface/interface states inside the band gap. This causes slow relax-
ation of e–h carriers. Use of different ligands also creates different emissions [75].
In a study, average lifetime found to decrease from 42 to 33 µs as the emission peak
maxima changed from 715 to 596 nm [75]. This blue shift could be explained by size
reduction effect of QDs. Again, when green-emitting or green–yellow-emitting QDs
were exposed to ambient air, red shift of luminescence occurred [33]. Surface-related
states are responsible for this red shift observed in ambient air. Finally, a series of
factors affects the PL properties of Si QDs like (i) differences in fabrication process,
(ii) defect states or active centers at the surface of QDs or at the interface between
QDs and matrix or at the matrix, (iii) different surface passivation processes and (iv)
the presence of strain and stress at the interface between QDs and matrix. The last
factor has been well confirmed and studied in a series of experiments [76–78].

4 Doping

To fabricate Si QD solar cell, it is necessary to dope the QDs by n- and p-type dopant.
However, doping in Si QDs is totally different issue than it is for bulk Si. Direct quan-
titative characterization and tracking of this type of doping in nanometer resolution is
really a challenge. Other some extreme difficulties include high impurity formation
energy and kinetically unfavorable conditions of such type of doping. To get high
power conversion from Si QD solar cells, it is necessary to gain information about the
concentration of dopant impurity atoms and their positions at nanoscale. The existing
characterization tools like x-ray photoelectron spectroscopy (XPS), secondary ion
mass spectrometry (SIMS) and Auger electron spectroscopy are not adequate for this
purpose. XPS cannot able to detect low concentration of impurity dopants. Using
SIMS, relative concentrations of impurities can be estimated [79]. However, atom
probe tomography, scanning transmission microscopy, electron paramagnetic reso-
nance and high-resolution XPS might be useful for this purpose [80]. In spite of
such difficulties, some research groups have succeeded in doping impurities like
boron [81, 82], phosphorus [18, 83], antimony [84], etc. Impurity doping in Si QDs
films has been done by using PECVD, sputtering, ion implantation, etc. [19, 85–87].
Co-sputtering of Si, SiO2 and P2 O5 has used to dope phosphorus atom in Si QDs
[87]. A seven order of magnitude decrease in resistivity was noted for 0.1 atm.%
phosphorous concentration. To calculate both the resistivity and the temperature
dependence of the resistance (R), transfer length measurements of the resistance
were used (Fig. 4) [88]. The activation energy Ea was calculated from the relation
144 M. Dutta

Fig. 4 Resistance obtained by transfer length measurements for different values of P and B doping
concentrations using Si QDs of 5 and 4 nm sizes, respectively: a resistivity versus P doping level;
b resistance versus temperature (P doping) (Reproduced with permission from Ref. [86]. Copyright
(2009) Elsevier); c resistivity versus B dopant level; d resistivity versus temperature (Reproduced
with permission from Ref. [88]. Copyright (2009) Elsevier)

R ≈ exp(Ea /kT). The activation energy decreases from 0.527 to 0.101 eV when the
P doping level increases from 0 to 0.1 atm.%. However, more increase of P doping
up to 0.35 atm.% increased activation energy up to 0.149 eV and increased resis-
tivity by three orders of magnitude. In a similar way, boron doping of 0.5 atm%
resulted in six orders of magnitude decrease in resistivity. Transfer length resistivity
measurement of such doping is shown in Fig. 3c. 13.4% power conversion efficiency
has been achieved by depositing B-doped Si QDs/SiO2 multilayer on n-type c-Si
substrate [79]. In addition, some adverse effects of doping on the growth of Si QDs
were also noted [89–92]. Acceleration in the phase separation in silicon-rich oxide
layers was noted by phosphorus doping, and it also improves the crystallization of
Si [90]. Doping of P atoms also enhances Si crystallization rate and phase separation
in Si rich SiNx films [92]. On the contrary, B doping slows down Si crystallization
rate and has almost no effect on QD size [89]. Ni doping affected Si nanocrystal
growth rate in a different way. Yoon et al. [92] have studied effects of such kind
doping by thermal annealing of Ni-implanted SiOx films. Moderate amount of Ni
Si Quantum Dots for Next-Generation Solar … 145

favors the growth of Si nanocrystals. However, high amount of Ni accelerates the

formation of NiSi2 nanocrystals. Voitovych et al. [91] have studied the effect of Sn
doping on the growth of Si nanocrystals in an amorphous SiOx (x = 1.15) thin film.
It was found that the presence of Sn favors the crystallization process by lowering
the crystallization temperature by 200 °C and also lowering the size of nanocrystals.
Doping of Sn also increases the crystalline phase to amorphous phase ratio.

5 Photovoltaics of Si QD Solar Cell

Use of QDs in fabricating solar cells has been shown the path to increase power
conversion efficiency much higher than the present value which exists in today’s
state-of-the-art solar structures. To reach this goal by using quantum confinement
effect in Si QDs, some distinct approaches have been taken by different research
groups around the globe [93–100], such as (i) spectral conversion, (ii) all-Si QD
solar cells, (iii) tandem or multi-junction solar cells, (iv) non-radiative energy transfer
(NRET)-based solar cells, (v) organic/inorganic hybrid.

5.1 Spectral Conversion for Si Photovoltaics

Spectral conversion is a process design for more utilization of short wavelength (e.g.,
blue region) photons for which solar cell quantum efficiency is low. The spectral
converters act by two basic mechanisms either by producing more than one low-
energy photons by absorbing one high-energy photon or by shifting high-energy
photons to a lower-energy photon. Down-conversion process minimizes thermaliza-
tion losses in solar cells, and for c-Si solar cells, the maximum power conversion
efficiency improvement was estimated to be 38.6% by placing spectral converter on
the top of the solar cell [101]. In downshifting process for Si QD, a high-energy
(blue–green region) photon is absorbed by the QD and re-emitted at lower energy
(red–infrared region) that involves a radiative energy transfer from Si QD to Si solar
cell underneath [64]. This process is depicted in Fig. 5. This process is a three-step
process. First, a high-energy photon is absorbed by the QD, and a fast non-radiative
relaxation takes place between the highest excited level and the intermediate level.
Then, the emission of this lower energy photon (only one) has occurred through
the radiative recombination of the electron from the intermediate level to the lowest
level. Thus, with the help of this luminescence process of QDs, incident high-energy
photon downshifted to lower energy high wavelength photon for which the internal
quantum efficiency (IQE) of cell is high. For c-Si solar cell, IQE is very high in the
range 500–1000 nm while low below 450 nm due to surface recombination. So, a
downshifting of UV–blue photons to the region red–NIR could result in enhanced
short-circuit current (I sc ). However, the open-circuit voltage (V oc ) and fill factor (FF)
146 M. Dutta

CB

1 3 4 Eg

VB

QD Solar cell

Fig. 5 Schematic for a radiative energy transfer from Si QD to Si solar cell underneath. 1. Absorp-
tion process of high-energy photon. 2. Non-radiative transition in lower energy level. 3. Radiative
trasition (re-emission of lower energy photon). 4. Absorption of low-energy photon by solar cell

will not change as by downshifting. Also, there will be no effect on electronic prop-
erty and resistance of the device. Simulation shows that QDs with an emission at ~
600 nm could increase the I sc of multicrystalline solar cell by nearly 10% [102]. The
first reported experiment with Si QDs as a down-converter was performed in 2004
[103]. This measurement was done by applying spin-on-glass antireflecting SiO2 -
based solution containing Si QDs on c-Si solar cell. This modification was increased
the I sc by 0.4%. However, the conclusion drawn in this study remains controversial.
In a later study by a different group, it was suggested that the previous enhancement
was due to the improved optical coupling of the incident light by Si QDs embedded
in the spin on glass at the solar cell surface [104], and it was the porous nature of
the QD film that was the origin of the performance enhancement of the cell because
porous Si layer can act as antireflection layer [105]. So, the downshifting effect of
Si QDs was put on doubt. The later group obtained a 0.6% efficiency improvement
and proposed to use Si QD-based ink to determine the downshifting effect. By using
Si QDs dispersed in organic solvent, improvement of 2.3% was observed for Isc .
Finally, by depositing Si QDs with either strong blue emission (1 nm diameter) or
orange–red emission (2.85 nm) directly on industrial polycrystalline solar cell, effi-
ciency improvement up to 70% using blue light and 10% improvement using visible
light was obtained in 2007 [106].
Si Quantum Dots for Next-Generation Solar … 147

5.2 All-Si QD Solar Cells (p–n or p–i–n Junction Solar Cells)

Devices containing Si QDs in forms of n-type Si QDs/p-type c-Si heterojunction, p-

type Si QDs/n-type c-Si heterojunction or p–i–n junction have been reported. Table 1
summarizes the solar cell parameters of such photovoltaic devices with Si QDs.
Table 1 shows that the performance of these Si QDs-based solar cells is inferior
except a few. The PV device with 3 nm n-type Si QDs embedded in 2 nm thick 15

Table 1 Photovoltaic properties of Si QD-based solar cells

Device structure V oc (mV) J sc /I sc FF (%) Efficiency Effective Ref.
(%) area
p-type Si QDs in 463 19 mA/cm2 53 4.66 – [110]
SiC/n-type c-Si
p-type 282 0.339 mA/cm2 [109]
a-SixC1-x /intrinsic
Si QDs in
SiC/n-type
a-SixC1−x
n-type Si QDs in 510 4.96 mA 20.5 – 1 mm2 [17]
Si3N4/p-type c-Si
n-type 518 0.34 mA/cm2 51 – – [111]
poly-Si/intrinsic Si
QDs in SiC/p-type
hydrogenated a-Si
p-type Si QDs in 492 0.02 mA/cm2 2.2 mm2 [108]
SiO2 /intrinsic Si
QDs in SiO2 /n-type
Si QDs in SiO2
p-type Si QDs in 373 0.12 cm2 [107]
SiO2 /intrinsic Si
QDs in SiO2 /n-type
Si QDs in SiO2
p-type Si QDs in 410 – – – 2–10 mm2 [112]
SiO2 /n-type Si
QDs in SiO2
n-type 532 24.1 mA/cm2 48.9 6.28 0.8 cm2 [111]
a-Si/intrinsic Si
QDs in SiC/p-Si
n-type Si QDs in 500 26.5 mA/cm2 65.2 8.6 1 cm2 [113]
Si3 N4 /p-type c-Si
n-type Si QDs in 556 29.8 mA/cm2 63.83 10.58 [85]
SiO2 /p-type c-Si
n-type Si QDs in 555.6 29.8 mA/cm2 63.8 10.6 – [114]
SiO2 /p-type c-Si
p-type Si QDs in 525 37.7 mA/cm2 78.5 13.4 [79]
SiO2 /n-type c-Si
148 M. Dutta

layers of SiO2 produced J sc ~ 29.8 mA/cm2 , V oc ~ 555.6 mV and FF ~ 63.8 with

an overall PCE 10.6% [114]. The best one among such reports used p-type Si QDs
with boron (B) concentration of 4 × 1020 cm−3 to fabricate p-type Si QDs/n-type Si
heterojunction solar cell with PCE 13.4% (with J sc 33.7 mA/cm2 , V oc 525 mV and
FF 78.5%) [79]. The cause of such inferior performances in other structures could be
the poor charge transport properties among the QDs that lead to small J sc values. The
other noticeable point is that the V oc values are not high as expected by incorporating
higher bandgap Si QDs as active absorption layer in the solar cells. In these devices,
it also becomes a challenge to estimate contribution in the PCE from only Si QDs as
the performance of Si QDs is masked by that of the Si substrates. However, there are
few reports where Si QD solar cells are made on insulating substrates. Figure 6 shows
p–i–n PV device fabricated on quartz substrate [107] with an active area 0.12 cm2 .
SIMS observation reveals that huge inter-diffusion of B and P occurred in the i-layer
after high-temperature annealing and the structure changed to p–n junction. After
annealing, this device showed V oc around 373 mV. Later, the same group reported
a photovoltaic device with same structure but with device area of 2.2 mm2 with V oc
~ 492 mV and J sc 0.02 mA/cm2 [108]. This low J sc was ascribed to high series
resistance 28 k cm2 . In another attempt to estimate the contribution of only Si QDs
layer, Si substrate was locally etched using chemical method, and the rest in form of
a membrane was encapsulated after solid-phase crystallization of Si QDs to form p–
i–n device structure [109]. Using doped amorphous silicon carbide (a-Six C1−x :H) as

Fig. 6 SIMS profiles of annealed (dotted line) and as-deposited (solid line) p–i–n structure. Inset
shows schematic of the device (p–i–n) structure Reproduced with permission from Ref. [107].
Copyright (2009) American Institute of Physics
Si Quantum Dots for Next-Generation Solar … 149

electron and hole selective contacts, this device structure showed a V oc ~ 282 mV, J sc
~ 0.339 mA/cm2 . This low J sc was resulted due to the presence of high recombinative
defects in the depletion region.

5.3 Non-radiative Energy Transfer-Based Solar Cells

In recent years, non-radiative energy transfer (NRET) has successfully demonstrated

for hybrid nanostructures combining absorbing components (e.g., quantum dots) with
high-mobility semiconducting transport channels (e.g., Si). Exploiting the NRET
process by using colloidal semiconductor, nanocrystals have opened new possibili-
ties in light harvesting that provides the benefit of absorbing the solar spectrum in
a wider range than Si layers are able to [97, 115–117]. Limitation of low-charge
transfer efficiency in charge transfer-based devices could be overcome in NRET-
based devices. In NRET process, long-range dipole–dipole interaction goes beyond
that involved in both radiative energy transfer and the short-range charge transfer
process. The highest NRET efficiency could be as high as ~ 65% where energy
transfer occurred to the adjacent Si layer as revealed by time-resolved photocurrent
measurements, and the increase in photocurrent could be as large as three times [118,
119]. Using energy transfer from nanocrystalline-Si (nc-Si) QDs (emitting in near red
region and absorption in blue region), efficient exciton harvesting has been achieved
in underlying radial p–n junction SiNW arrays [97, 120]. An increase of 18.5% in
J sc value has reported for this nc-Si QD-modified SiNW solar cells. Using time-
dependent photoluminescence decay experiments, it was demonstrated that NRET
rate was ~ 1.6 times faster than the radiative energy transfer rate.

5.4 Multilayer Tandem Solar Cells

Tandem solar cells are basically stacking of p–n or p–i–n diode with different bandgap
materials and connect them either in series or in parallel, so that a major part of the
solar spectrum could be absorbed. Hence, increasing the cell performance rapidly
compare to single-junction cells. Performance limitations of the tandem cells have
been studied extensively by Meillaud et al. [121]. For a single-junction radiative
efficiency, limit for silicon cell is 30%, whereas for double and triple junction, this
is 42.5% and 47.5%, respectively. The optimal bandgap requirement of top cell for
maximum performance under an AM1.5G solar spectrum is ∼ 1.7 to 1.8 eV for a
2-cell tandem with a Si cell as bottom cell and 1.5 and 2.0 eV for the middle and
upper cells for a 3-cell tandem. Figure 7 shows a 3-cell tandem stack. For the upper
cell, the choice of material should be a high bandgap material, so that high-energy
photon (blue region of solar spectrum) could be absorbed, whereas for the bottom
cell, the choice material should be such that it can absorb well the infrared portion
150 M. Dutta

Fig. 7 Stacking of three p–n junctions to utilize three different regions of AM 1.5 solar spectrum.
Reproduced with permission from Ref. [65]

of the spectrum, i.e., low-energy photons. For a series connection, these cells are
connected through tunnel diodes.
In fabrication of all-Si tandem solar cells, Si QDs might be useful with the addition
of Si thin-film technology. By changing the size of QDs, band could be varied from
high to low which will allow fabricating from top cells to bottom cell. If the QDs
could be patterned in a superlattice stack, the charge carriers can tunnel from one
QD to another. So, by varying the size of the QDs and using quantum confinement
effect in addition to the thin-film technology, all-Si tandem cell could be achieved
by stacking Si QD layers from higher band gap to lower band gap as shown in the
Figure.

5.5 Si QDs-Organic Hybrid Solar Cell

Since the first report on organic/Si heterojunction photovoltaics in 1984 where pyrene
was used as the organic compound, several attempts have been done and power
conversion efficiency reaches as high as 13.6% [122, 123]. The literature shows two
types of such solar cell structures: (i) hole conductor and electron acceptor-based
organic bulk heterojunction (OBHJ) solar cell. The mixture poly (3-hexylthiophene):
1-(3-methoxycarbonyl) propyl-1-phenyl [6, 6] C61 (P3HT: PCBM) and PEDOT:PSS
is currently the most prominent material system in such organic photovoltaic, (ii) the
Si Quantum Dots for Next-Generation Solar … 151

Fig. 8 a Energy band diagram of a Si nanocrystal/P3HT solar cell. The dotted lines represent the
valence and conduction bands of bulk Si, while the solid lines are representation of 4 nm nanocrystal.
b Schematic of a hybrid solar cell Reproduced with permission from Ref. [125]. Copyright (2009)
American Chemical Society

dye-sensitized solar cell (DSSC). Use of Si QDs in such devices could increase short-
circuit current and the external quantum efficiency. Characteristics of Si QDs with
conducting polymer had been studied by Dietmueller et al. [124] in detail, where the
charge transfer between Si QDs and the component of bulk heterojunction solar cells
(P3HT and PCBM) was reported. Liu et al. reported a hybrid solar cell fabricated
by spin coating blends of silicon nanocrystals (Si NCs) and poly-3(hexylthiophene)
(P3HT) polymer together on PEDOT:PSS-coated ITO glass (Fig. 8) [125]. V oc and
I sc were found to be dependent on Si nanocrystals size due to changes in the band
gap and surface-area-to-volume ratio. The best performance device made with 35
wt% Si NCs 3-5 nm in size showed 1.15% power conversion efficiency.

6 Future Outlook and Challenges

Few photovoltaic devices using Si QDs in the device structure of Si QDs/opposite

polarity c-Si p–n (hetero) junctions and p–i–n junctions have been reported (Table 1).
Some all-Si tandem cells are also reported using the size-dependent quantum prop-
erties of these Si QDs [121]. The most efficient Si QD cell with power conversion
efficiency of 13.4% so far reported was fabricated by depositing a p-type Si QDs
with B concentration of 4 × 1020 cm−3 on n-type c-Si [79]. Although the device
performance (I sc 33.7 mA cm−2 , V oc 525 mV and FF 78.5%) is not comparable
to commercial crystalline Si solar cell, yet this shows a path toward realization of
all-Si tandem solar cells based on Si QDs in near future. Cell performance of the Si
QD-based devices constrained mainly due to the difficulty in charge transfer between
the QDs and the formation of tunnel junctions which has direct effect on I sc values.
Again, the V oc obtained from these solar cells is much lower than the expected value.
Another difficulty is that Si QDs alone contributing how much to the photovoltaic
performance of the device cannot be estimated as the Si substrates also contribute.
Fabrication of Si substrate-free Si QD solar cells is also reported [107]. These types
152 M. Dutta

of cells are discussed in Sect. 5.2. However, preparation of these type of cells is not
easy as one has to deposit layer of Si QDs embedded in dielectric matrix. To improve
device performance of such kind of solar cells, it is necessary to optimize Si QDs
growth condition, i.e., film deposition conditions, and improve interface engineering,
light trapping and passivation techniques as the Si QDs layers are very thin.
However, in a futuristic approach, use of Si nanocrystals-based energy selective
electrodes could have an important potential to improve the power conversion effi-
ciency of hot carrier solar cells (HCSCs). The experiment in this regard was done
by Conibeer et al. [126] where they used a QD-based layer (with a discrete energy
level) embedded between two insulating layers. This structure consists of a 4 nm
thick Si-nc layer sandwiched between two 5 nm SiO2 layers as barrier. Control over
the nanocrystal size was maintained by controlling the thickness of the layer. Thus,
the specific discrete energy levels could be created inside the double barrier.
The appearance of differential resistance (NDR) feature in the I-V curve at room
temperature is very encouraging though it is weak (Fig. 9). This experiment has
started a series of experiments on HCSCs based on Si nanocrystals layers with
energy selective electrodes.

Fig. 9 a Schematic of selected energy contact structure and b I–V curves of this structure showing
NDR at 300 K for two mesa devices on one wafer Reproduced with permission from Ref. [127].
Copyright (2008) Elsevier
Si Quantum Dots for Next-Generation Solar … 153

Femtosecond transient absorption spectroscopic studies on different sizes of

colloidal Si QDs showed that multiple exciton generation (MEG) occurs with much
higher efficiency in Si QDs as compared to bulk Si [127]. Reports confirmed that a
threshold exists for Si QDs with diameter 9.5 nm to be 2.4 ± 0.1 E g with exciton
quantum yield of 2.6 ± 0.2 excitons per absorbed photon at 3.4E g . In a contrary
to the negative impact of indirect bandgap nature of Si for photonic applications,
it turns out to be beneficial for MEG-based photovoltaic applications. Because the
relatively long exciton lifetime in Si QDs simplifies energy extraction compared to
the direct bandgap semiconductor QDs.

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Progress in Growth and Development
of Perovskite Single Crystals and Their
Potential Use in the Future Devices

Mrinal Dutta and Aishik Basu Mallick

Abstract Single crystals of organic–inorganic hybrid halide perovskites (MAPbX3 ;

MA=CH3 NH3 + , X=Br− , I− or FAPbX3 where FA (formamidinium) NH2 CH=NH2 + ,
X=I− or Br− ) have shown remarkably low trap density, high carrier mobility, large
light absorption coefficient, low non-radiative recombination, and long carrier diffu-
sion length. As a result of these properties, perovskite single crystals could be antic-
ipated to overcome the drawbacks and bottleneck problems faced by polycrystalline
perovskite thin films in several optoelectronic and photovoltaic applications. This
chapter focuses on the progress and development of growth techniques of these
perovskite single crystals and their applications in photovoltaics and different detec-
tors. Finally, the enormous challenges face by the fabrication processes and possible
new techniques to face the problems of this emerging field are also included.

Keywords Perovskite · Single crystal · Growth · Crystallization · Single crystal

photovoltaics · Single crystal detector

1 Introduction

Technologies that have potential for higher power conversion efficiencies

with lower production costs could replace silicon (Si) technology for future
processing. Organic–inorganic hybrid perovskites (MAPbX3 or FAPbX3 where MA
(methylamonium)=CH3 NH3 + , FA (formamidinium) NH2 CH=NH2 + , X=I− or Br− ),
a group of materials having layers of organic and inorganic elements in alternating
form, are considered as potential material for future device applications for their

M. Dutta (B)
Inorganic Photovoltaic Devices Group, Advanced Materials Device Division, Council of
Scientific & Industrial Research (CSIR)-National Physical Laboratory, K.S. Krishnan Marg, Pusa,
New Delhi 110012, India
e-mail: [email protected]
A. B. Mallick
Department of Energy Engineering, Central University of Jharkhand, Ranchi, Jharkhand 835205,
India

© Springer Nature Switzerland AG 2020 159

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_7
160 M. Dutta and A. B. Mallick

cheap production. Some key features of these perovskite materials are broad and
high solar light absorption, low non-radiative recombination rates with easy fabrica-
tions process. Use of these organic–inorganic hybrid perovskite materials for solar
energy conversion comes with the prospect of high conversion efficiency at low
fabrication cost that has grown in an exponential manner in the last few years to
reach efficiency up to 25.2% [1–5]. These types of materials also have widely been
used in photodetectors [6], lasing [7], and light-emitting diodes [8]. However, this
fascinating material has some major drawbacks. Among this, environmental impact
of using such materials has to be considered first as lead has remains to be the main
constituent of high performing perovskite materials. Also these materials show rapid
degradation when exposed to environment. State of art up to now shows stability
for thousands of hours. However, for commercial production, stability should be
minimum for 10 years. Zhou et al. have reported stability for 2000 h in dark at room
temperature in air ambient for mesoporous TiO2 /CH3 NH3 PbI3 /C device structure
[9]. Again, for temperature higher than 60 °C, rapid degradation of active material
as well as devices occurs that could find its route in either fading or new types of
reactions accelerating degradation. External factors like water vapor, temperature,
oxygen, UV light, etc., and internal factors such as interfacial and within lattice
ion migration, electro-migrations are considered as major causes for degradation
[10]. In terms of stability, relaxation should come in the form of single crystals of
hybrid halide perovskites that have shown remarkably low trap state densities, long
carrier diffusion lengths, and large absorption coefficient. In addition, the as-prepared
perovskite single crystals exhibit a narrower band gap than the corresponding films,
which means improved photocurrent generation and broader light absorption. These
properties are comparable to the best photovoltaic candidate silicon (Si) [11, 12].
Different techniques have been used to produce hybrid perovskite single crystals
with different cation (like MA or FA for organic cation and Pb or Sn for inorganic
cation) and anion (like I or Br or Cl) in organic and inorganic parts [11, 13–26].
Fabrication of inorganic perovskite single crystals is also reported [17, 27]. These
different single crystals are varied in size and growth rate depending on the method
iused to grow them. Even monocrystalline perovskite films are also reported that are
best suited for the fabrication devices [28, 29]. The electronic and optical properties
of these perovskite single crystals and monocrystalline perovskite films are also well
studied [15, 30–43]. These studies revealed long carrier diffusion lengths as a result
of low trap state density for these hybrid perovskite single crystals that opens the
path for the production of reliable and stable optoelectronic devices.
This chapter intends to provide recent research on the growth of perovskite single
crystals, especially, different growth techniques and elaborated discussion on the
fascinating properties of these single crystal perovskites that will follow by their
applications in energy harvesting and high energy radiation detection.
Progress in Growth and Development of Perovskite Single … 161

2 Crystal Structure

Perovskites materials are described by common nomenclature formula ABX3 , where

A and B are cations (size of A is bigger than B) and X is an anion. B resides at the
body center position of a cubic unit cell surrounded by six anions X (face centered
position) forming an octahedral [BX6 ]4− cluster while A cation resides at the eight
corners of the cube [44]. Crystallographic structure and stability of the perovskite
structures could be realized by using Goldschmidt tolerance factor (t f ) defined as

(RA + RX )
tf = (1)
{2(RB + RX )}−1/2

where RA , RB, and RX are the ionic radii of the A cation, B cation, and X anion,
respectively.
For hybrid perovskites of present interest, the larger cation A is organic; such as
MA (CH3 NH3 + ) with RA = 0.18 nm, FA (NH2 CH=NH2 + ) with RA ~ 0.19–0.22 nm
[13, 45–47]. Cation B is Pb (RB = 0.119 nm) or Sn (RB = 0.11 nm) and anion X is
generally halides (Br, I or Cl with RX = 0.196, 0.22, and 0.181 nm, respectively). For
0.9 < t f < 1, ideal perovskite crystal structure with cubic phase is formed. However,
for lower values in the range 0.7 to 0.9 (i.e., with smaller A or larger B), orthorhombic,
rhombohedral or tetragonal crystal structures are formed. For t f > 1, layered crystal
structures are found to form for larger A.

3 Perovskite Single Crystal Growth Techniques

A few techniques so far have been proposed such as top and bottom seeded solution
growth, inverse temperature crystallization, anti-solvent vapor-assisted crystalliza-
tion, etc., for the growth of perovskite single crystals. Few of them are based on
conventional crystal growth processes. The single crystal growth rates as well as
sizes of crystals are varied from one type of growth technique to other. Table 1 shows
a collection of these data as available in literature so far. For more details about these
particular perovskite single crystal growth techniques, readers are suggested to go
through the references cited therein.

3.1 Temperature-Lowering Method

The temperature-lowering method is one of the appropriate techniques for the growth
of organo metallic halide perovskite single crystal. It is simple and convenient for
the growth of high quality large size single crystals perovskite MAPbX3 (X=Cl, Br,
I). By reacting an organic halide salt and an inorganic metal salt, saturated aqueous
162 M. Dutta and A. B. Mallick

Table 1 Different size and type of perovskite single crystals grown by different techniques and
their application area
Perovskite single crystal Crystal growth Crystal size Application References
technique
MAPbI3 Bottom-seeded 10 × 10 × 8 mm3 – [13]
solution growth
MAPbI3 Top-seeded solution 10 mm (length), – [15]
growth 3.3 mm (height)
ASnI3 (A=CH3 NH3 or Top-seeded solution – [16]
CH(NH2 )2 ) growth
MAPbBr3 , MAPbI3 Inverse temperature – – [19, 48]
crystallization 1 mm (length)
(CH3 NH3 )Pb(Br1−X ClX )3 Inverse temperature – – [49]
crystallization
FAPbX3 (X=I or Br) Inverse temperature 3 mm for X=I – [21]
crystallization 5 mm for X=Br
FAPbI3 Cooling solution and – – [24]
inverse temperature
crystallization
CsPbBr3 and CsSnI3 Bridgman growth – – [17, 27]
MAPbI3 arrays in Droplet-pinned – – [52]
microscale crystallization
MAPbBr3 and MAPbI3 Anti-solvent – – [11]
vapor-assisted
crystallization
(benzylammonium)2 PbCl4 Slow evaporation 5 × 10 × 2 mm2 – [26]
MAPbBr3 monocrystalline Cavitation triggered – Photovoltaic [28]
film asymmetrical devices
crystallization
MAPbCl3 Inverse temperature 2 × 4 × 4 mm3 Photodetector [20]
crystallization
MAPbCl3 Bottom-seeded 12 × 12 × 7 mm3 Photodetector [14]
solution growth
MAPbBr3 , MAPbI3 Temperature-lowering – Self-powered [36, 37]
method photodetector
MAPbI3 , FAPbI3 and Inverse temperature 0.3–1 cm Solid state γ [42]
I-treated MAPbBr3 crystallization ray detector
MAPbBr3 Anti-solvent 2–3 mm X-ray [25]
vapor-assisted detector
crystallization
MAPbI3 – – X-ray photon [43]
detector
MAPbI3 Inverse temperature Large size wafer – [29]
crystallization
Progress in Growth and Development of Perovskite Single … 163

perovskite precursor is prepared at first step. With change in temperature, the solu-
bility of the organic halide perovskites in their corresponding halide solvents varies
considerably. However, it is moderate at room temperature. Decrease in the solution
temperature induces saturation of the solute. This saturation leads to the development
of perovskite single crystals.
This method could be divided in two methods depending on position of the seed
crystal in crystal growth vessel: top-seeded solution growth (TSSG) and bottom-
seeded solution growth (BSSG). Easy control and stable growth are the main advan-
tages of these two methods. However, this method is not suitable for low solubility
materials at high temperature region.

3.1.1 Bottom-Seeded Solution Growth Method (BSSG)

This crystal growth technique was developed for crystals that are grown from heated
solutions. Figure 1a shows the schematic of a typical crystal growth system. In this
process, the seed crystals were formed first by spontaneous crystallization. Opti-
mization of the crystal growth condition was achieved by accurate control of the
temperature and selecting of a high quality seed crystal; in the middle of the crystal
holding tray, the seeded crystal was fixed. With the help of an electric motor, this tray
along with the seed crystal was rotated during the crystal growth process. Growth
of large (~centimeter size) bulk single crystal of MAPbI3 by bottom-seeded solu-
tion growth (BSSG) method was first reported by Dang et al. [13]. For this, the
temperature of the saturated solution was cooled down slowly from 65 to 40 °C and
thus, the single crystal of MAPbI3 (dimensions of 10 mm × 10 mm × 8 mm) was
formed in a month. The growth rate for this crystal was found to be ~26 mm3 per day
(~1 mm3 /h). This crystal had two natural facets {100} and {112}. Lian et al. [14]
also utilized same technique to grow bulk single crystals by lowering the temperature
of the growth solution from 100 to 57 °C. In this process, a seed crystal was fixed to
a platinum wire (Fig. 1b) and the dimensions of the grown crystals were ~ 12 mm ×
12 mm × 7 mm as shown in Fig. 2.

(a) (b)
Motor

Higher Platinum
Temperature wire
Crystal holder
Crystal
Crystal

Heat
Solution
Lower
Temperature
Solution
Heat Heat

Fig. 1 Schematic representation of the bottom-seeded solution growth method

164 M. Dutta and A. B. Mallick

Fig. 2 Photographs of
bottom-seeded solution
grown bulk MAPbI3
perovskite single crystal.
Reproduced with permission
from Ref. [14]. Copyright
2014, Nature

3.1.2 Top-Seeded Solution Growth Method (TSSG)

Growth of bulk single crystals of MAPbI3 by using the top-seeded solution growth
(TSSG) method was reported by Dong et al. [15]. During the growth process, a silicon
(Si) substrate holds the seed crystal at the top of the solution as shown in Fig. 3. This
Si substrate was air cooled on the part outside of the tube and the seed crystal remains
suspended in the solution. Using the temperature discrepancy between the bottom
and top of the solution and dissolution of small seed crystals at the bottom, super
saturation was induced. This condition leads the growth of bulk MAPbI3 single
crystals with size of 10 mm (length) and 3.3 mm (height).
In recent time, the same group has reported for the first time the growth of high
quality bulk hybrid ASnI3 perovskite (A=CH3 NH3 or CH(NH2 )2 ) single crystals by
using the top-seeded solution growth (TSSG) method [16].

Fig. 3 Schematic
representation for MAPbI3
single crystal growth by
Silicon
TSSG method Lower Substrate
Temperature

MAPbI3 Super saturated

Single crystal soluon
PbAc:HI:MA Higher
Soluon Temperature

Oil bath

Heat
Progress in Growth and Development of Perovskite Single … 165

3.2 Inverse Temperature Crystallization (ITC)

The inverse temperature crystallization (ITC) method is used for the particular mate-
rials whose solubility decrease with increase of temperature in specific solvent and
compare to other methods, the rate of crystal growth by this method is an order of
magnitude faster [11, 15, 17, 18].
Figure 4 shows the schematic of the crystal growth process. Precursor solution
is kept in a bottle and the bottle is kept inside an oil bath. The temperature of the
oil bath is raised. After a certain temperature, crystallization starts at the bottom of
the bottle. This growth is reversible one as the crystal could dissolve in the solution
when temperature of the solution again comes down to room temperature. Based on
the inverse temperature or retrograde solubility of organic–inorganic hybrid halide
perovskite in particular organic solvents, ITC was initially proposed by Bakr et al.
[19–22]. This type of inverse solubility induced crystallization and growth occurs
within several hours. So, it is widely used to grow bulk single crystal rapidly as
compared to temperature-lowering method [20, 22–24].
Basically, in ITC method, the crystal growth process is a balance of dissolution and
precipitation. At low temperature, concentration of unbound perovskite molecules is
low as most of them are bound by molecules of the solvent. For this reason, concentra-
tion of perovskite molecules does not reach saturation. The bonding energy depends
on temperature in inverse proportion. For this reason, with increase of tempera-
ture, more and more perovskite molecules are free to increase concentration of free
perovskite molecules in solution. With increase of temperature at some point, super
saturation occurs that enunciates nucleation and crystal growth starts. Single crystal
growth by this method depends on the choice of solvent. For the growth of hybrid
halide perovskites crystals solvents like g-butyrolactone (GBL), dimethylsulphoxide
(DMSO) and N,N-dimethylformamide (DMF) are the most widely used. There is lot
of variations in solubility of PbX2 and MAX in these solvents. It has been found that
MAPbI3 crystallized more aptly from GBL while MAPbBr3 crystallized better from
DMF [11].
First, MAPbI3 and MAPbBr3 single crystals were grown by the rapid ITC method
(Fig. 5a–c) [19, 48]. In later works, Zhao group [49] succeeded to grow mixed halide
perovskite (CH3 NH3 )Pb(Br1−X ClX )3 single crystals.

PbX2/MAX Oil bath

Heating to certain
temperature

Fig. 4 Schematic for ITC method for growth of MAPbX3 single crystals
166 M. Dutta and A. B. Mallick

(a)

(b)

(c)

Fig. 5 Inverse temperature crystallization growth of a MAPbI3 and b MAPbBr3 single crystals at
different time intervals. c Continuous growth of MAPbBr3 single crystal by transferring the crystal
into a larger vessel containing a fresh growth solution. Reproduced with permission from Ref. [19].
Copyright 2015, Nature

Bakr group [21] also synthesized FAPbX3 single crystals using the ITC method
by using proper solvent. 0.8 mol L−1 GBL solution was used to reach super saturation
and starts crystallization at 115 °C for the growth of FAPbI3 single crystals. Crack
and grain boundary-free black FAPbI3 single crystals were grown in 3 h. 1:1 (v/v)
DMF:GBL solution (1 mol L−1 ) was used in the growth of FAPbBr3 single crystals
using ITC method. Crystallization was found to occur at 55 °C. Yang’s [24] group
also reported growth of FAPbI3 single crystal (5 mm in size) with some modification
in ITC process. First, FAPbI3 seed crystal was grown by a cooling solution method.
This seed crystal was used to grow larger crystal by ITC method.

3.3 Bridgman Growth Method

The Bridgman growth technique is a melt crystal growth method that is mostly used
to grow large-sized crystal inside the sealed ampoules [50, 51]. Organic compounds
become chemically instable and attained high vapor pressure around their melting
point. Single crystal of perovskite materials having definite melting point could be
grown using this property. For this, a quartz ampoule was initially filled with all
of the raw reactants and then sealed under the vacuum. At definite temperature,
crystallization starts at the tip of the ampoule. Growth of CsPbBr3 single crystals
and CsSnI3 polycrystalline ingots has reported by Kanatzidis group using Bridgman
growth method [17, 27]. By varying the size of the ampoules, large-sized crystals
could be grown by using this growth method. This method has only one limitation
Progress in Growth and Development of Perovskite Single … 167

that is come from the stress between the surface of the crystal and the ampoules. This
stress could induce cracks and small grain boundaries in the crystals. Again as the
crystals comes in touch of the crucible wall during growth, impurity level increases
in the crystals grown by this method.

3.4 Droplet-Pinned Crystallization Method (DPC)

Droplet-pinned crystallization (DPC) method is used to grow micro-scale MAPbI3

single-crystalline arrays and could be used to grow single-crystalline thin films
[52]. In this process, first MAPbI3 precursor solution is dropped on PEDOT: PSS-
coated ITO glass. Over it, a small piece of Si wafer was placed. MAPbI3 starts
to disperse along the diminishing direction of the droplet with the evaporation of
solvent. Annealing induces formation of rectangular MAPbI3 single crystal arrays
within minutes.

3.5 Anti-solvent Vapor-Assisted Crystallization (AVC)

In the year 2014, Seok and Chang group has shown the anti-solvent-assisted crys-
tallization method which is also known as fast crystallization deposition [53] and
solvent engineering [27] to produce high quality and dense perovskite thin films. The
methods are based on the similar principle: different solubility of MAPbX3 (X=Cl,
Br, I) in different solvents [53–55]. The anti-solvent vapor diffusion method comes in
handy to grow materials that are highly soluble in a good solvent but have poor solu-
bility in different class of solvents. To support the above statement in general, hybrid
halide perovskites show good solubility in DMF, DMSO, and GBL, while they show
nonsolubility or low solubility in chlorobenzene, diethylether, benzene, etc. (the poor
solubility solvents here referred as anti-solvent). The anti-solvent could accelerate
the crystallization of these perovskites during spin coating and facilitates to attain
uniform film formation. Using this same strategy, the Bakr group [11] developed
a new method to grow large-sized millimeter-scale MAPbBr3 and MAPbI3 single
crystals.
Figure 6 shows the schematic of crystal growth arrangement. Powders of PbBr2
and MABr (molar ratio 1:1) were dissolved in DMF to form the precursor solution.
Dicholoromethane (DCM) as an antisolvent and the precursor solution (yellow color
in Fig. 6) was sealed in a closed vessel and stored. Slowly, the evaporation of DCM
occurs and its vapor will diffuse into the precursor solution because the DCM mixes
well with DMF. The diffusion of DCM in DMF will consume some DMF solvent.
Since MABr and PbBr2 cannot dissolve in DCM solvent, the consumption of DMF by
DCM will result an increase in the concentration of MABr and PbBr2 in the solution.
And finally lead to the formation of MAPbBr3 crystals. Huang group found that it
was difficult to get high quality MAPbBr3 with a 1:1 mol ratio of MABr and PbBr2
168 M. Dutta and A. B. Mallick

Fig. 6 Schematic
representation of the
anti-solvent vapor-assisted
crystallization process
PbX2/MAX Time

An-solvent
MAPbX3
Single crystals

because of their different solubility’s in DMF [25]. PbBr2 and MABr molar ratio of
0.8 can produce high quality crystals with higher carrier mobility and lifetime.

3.6 Slow Evaporation Method

Slow evaporation technique in solution growth processes is a simple method for

obtaining single crystals. Xiong et al. [26] have reported growth of hybrid perovskite
in analogous (benzyl ammonium)2 PbX4 (X=Cl, Br) materials. In this process, a stoi-
chiometric mixture of benzylammonium chloride and PbCl2 in a concentrated HCl
aqueous solution was prepared. Upon slow evaporation of N,N-dimethylformamide
(DMF) solution at 90 °C bulk crystals size ~(5 mm × 10 mm × 2 mm) were obtained.
In spite of simplicity and efficiency in crystal growth by slow evaporation method,
sometimes, it becomes hard to accurately control.

3.7 Cavitation-Triggered Asymmetrical Crystallization

(CTAC)

Gorwth of monocrystalline hybrid perovskite films by using CTAC method was first
proposed by Bakr group [28]. This group has shown growth of monocrystalline
perovskite films on various types of substrates such as Si wafers, ITO-coated glass,
FTO-coated glass, and sputter-coated metal on silicon. Ultrasound has been used in
crystal growth process since 1927 [56, 57]. Without seed crystal, only the use of
ultra sound promotes nucleation under a low super saturation level. The basic idea
of this growth process lies in the fact that if successive cycles of compression and
rarefaction sound waves are sending through a solution, then these waves creates
and collapse cavities repeatedly inside the liquid. Release of ultrahigh energy during
the collapse of these cavities could induce nucleation by overcoming nucleation
barrier by increasing local pressure, accumulation of energy, and rapid cooling [58].
High-speed jets of fluid called microjetting occur through the asymmetric collapse
of cavities near a solid surface [59]. Due to the induced strong shearing force, this
Progress in Growth and Development of Perovskite Single … 169

process has been used in film thinning and reducing the particle size from long
past [60]. In the growth of monocrystalline perovskite thin film, this force plays
a major role. Thickness of the perovskite films depends on the concentration of
the precursor solution. When ultrasonic pulses are targeted toward supersaturated
precursor solution, excessive nucleation occurs that results in the growth of plenty
amount of tiny crystals.

4 Optical and Optoelectronic Properties

Morphology strongly affects the carrier diffusion length in organometal trihalide

perovskite material. Charge carrier diffusion lengths >100 nm in the hybrid poly-
crystalline perovskite (e.g., MAPbI3 ) are necessary and vital for the fabrication of
high efficiency solar cells. However, recently Dong et al. [15] has reported more
than 175 μm diffusion lengths in MAPbI3 single crystals are grown by a solution
growth method under 1 sun (100 mW cm−2 ). Even this could exceed 3 mm under
weak light for both types of carriers. The reason behind this long diffusion length
was ascribed to longer lifetime, higher carrier mobility, and much smaller trap densi-
ties compare to polycrystalline MAPbI3 thin films. Thin film showed an absorption
cutoff at 800 nm whereas the absorption of single crystal extended up to 850 nm.
The shorter wavelength (~770 nm) emission in single crystals than the excitonic
absorption peak position (~790 nm) indicates dissociation of all excitons in free
electron and hole charge carriers in single crystal with a bandgap of 1.61 eV. The
narrower and blue-shifted PL peak of the single crystals suggests the presence of
low trap density. For measuring the optoelectronic properties, a single crystal device
was fabricated by depositing 25 nm thick gold (Au) film on one facet of the crystal
that acts as an anode and for cathode, gallium (Ga) was connected on the opposite
facet. The EQE of a 3 mm thick single crystal-based solar cell is ranged from 12.6 to
15.8% for wavelengths from 520 to 810 nm. The red shift (~50 nm) of the EQE up to
850 nm for the single crystal device compare to polycrystalline thin films increased
the upper limit of the short-circuit current density (J SC ) for single-crystal-based solar
cells from 27.5 to 33 mA/cm2 . The decrease of EQE for the single crystal device at
shorter wavelengths indicates that the metal–single crystal interface contains a large
defect density. The reason for this large defect density was ascribed to the formation
of Pb2+ clusters due to the partial loss of the more soluble methylammonium iodide
during the removal of the single crystal from solution. In a separated work, the same
group has shown theoretically that Pb2+ clusters tend to form charge traps on the
surface of MAPbI3 [30]. A near unity internal quantum efficiency (IQE) (95 ± 7%)
was obtained for 3 mm thick single crystal device.
Diffusion length L D is related to carrier mobility (μ) and carrier lifetime τ by the
following relation
170 M. Dutta and A. B. Mallick

  21
μkB T τ
LD = (2)
e

where k B is Boltzmann’s constant, T is the absolute temperature, and e is electronic

charge. To estimate μ and τ, dark current (J D ) versus voltage characteristics of the
device was studied. Two types of devices were made: one hole-only device with
the structure Au/MSC/Au and other electron only with the structure Ga/phenyl-
C61-butyric acid methyl (PCBM):C60/MSC/PCBM:C60/Ga. Three regions were
indentified. (1) At low bias, the current increases linearly with applied bias (with n
= 1), (2) at higher bias voltage J α V 2 , i.e., trap free space-charge-limited current
(SCLC) regime (with n = 2), (3) an intermediate regime identified (a trap-filled
regime) by the rapid increase of current with bias. In the SCLC regime above 10.7 V,
the J D of the device was well fitted by the Mott–Gurney law

9εε0 μV 2
JD = (3)
8L 3

A large hole mobility ~164 ± 25 cm2 V−1 s−1 was obtained by curve fitting. The
trap-filled limit voltage V TFL defined as the voltage at which all the traps are filled
is directly proportional to the trap density by the relation

en t L 2
VTFL = (4)
2εε0

where L is the thickness of the single crystal, ε (=32) is relative dielectric constant of
MAPbI3 , and ε0 is the vacuum permittivity. The trap density nt was estimated to be
3.6 × 1010 cm−3 which is five orders of magnitude lower than that of polycrystalline
thin films of MAPbI3 . Similarly, the electron mobility and electron trap density for
the electron-only device were measured to be 24.8 ± 4.1 cm2 V−1 s−1 and 4.5 ×
1010 cm−3 .
In a different work, on organolead trihalide MAPbX3 (MA=CH3 NH3 + ; X=Br−
or I− ) perovskites single crystals of volume larger than 100 cc grown by anti-solvent
vapor-assisted crystallization approach, it was found that the trap densities are excep-
tionally low on the order of 109 to 1010 per cc which is comparable to the best quality
Si [31]. The absorption spectra of MAPbX3 single crystals show a clear cutoff at band
edge with no excitonic absorption. This feature arises due to subsequent reduction
in the number of in-gap defect states. However, absorption spectra of polycrystalline
MAPbX3 thin films show excitonic features near band edge [32]. The optical band
gap was determined to be 2.21 and 1.51 eV for MAPbBr3 and MAPbI3 single crys-
tals, respectively. Both types of single crystals show a sharp transition at band edge
that could enhance photon harvesting and photocurrent generation compare to their
thin film counterpart. Similarly, single crystals show narrow PL peak corresponding
to band gap. For determining the carrier diffusion length L D , carrier life time (τ )
and carrier mobility (μ) were separately measured using time of flight technique
[33] and PL decay in addition to transient absorption spectroscopy, respectively. For
Progress in Growth and Development of Perovskite Single … 171

MAPbBr3 single crystal, the transient current for various driving voltages (V ) and the
transit time τ t , (defined as the position of the kink in the time traces) were plotted as
a function of V −1 . Using the transit time τ t , sample thickness d, and applied voltage
V, mobility μ was estimated to be 115 cm2 V−1 s−1 by linear fit of τ t versus V−1
using the equation

d2
μ= (5)
V τt

This estimation of mobility was higher than the value measured from Hall Effect
measurement (20–60 cm2 V−1 S−1 ). The disagreement was attributed to the surface
effects that are negligible for time of flight measurement. Carrier lifetime t was
estimated from transient absorption (TA) and PL spectra. Bi-exponential fits prove
the presence of two types carrier dynamics: the fast (t ≈ 74 ns) and the slow (t ≈
978 ns) carrier dynamics. For MAPbI3 single crystals, mobility was estimated by
measuring the current–voltage characteristics (space-charge-limited current (SCLC)
technique) where a quadratic dependency of the current was observed at 300 K. From
this, dependency μ was obtained as 2.5 cm2 V−1 s−1 .
The time-dependent PL measurements for MAPbBr3 and MAPbI3 single crystals
were carried out for the wavelength of the main PL peak (i.e., λ = 580 nm and λ
= 820 nm for MAPbBr3 and MAPbI3 , respectively). Through bi-exponential fits,
the bromide- and iodide-based perovskite single crystals showed a combination of
fast and slow dynamics (t ≈ 41 and 357 ns for MAPbBr3 , and t ≈ 22 and 1032 ns
for MAPbI3 ). These two very different time scales were assigned to the presence
of a surface component (fast) in addition to a bulk (band to band recombination)
component (slow). By combining the longer (bulk) carrier lifetimes with the higher
measured bulk mobility and shorter carrier lifetime with lower mobility, L D was
estimated [by using Eq. (1)] to be ~17 and ~3 μm in MAPbBr3 single crystals,
respectively. Similarly, for MAPbI3 single crystals L D was found to be ~8 and ~2.
The current–voltage responses of these hybrid perovskite crystals in the SCLC
regime were further investigated in order to find trap density that plays a crucial
role in determining μ, τ , and L D . The I–V curves were divided in three regions:
at low voltages, the I–V response was ohmic (i.e., linear); at intermediate voltages,
non-linear behavior evidenced transition into trap-filled limit (TFL) where injected
carriers filled all trap states (V TFL = 4.6 V for MAPbBr3 and 24.2 V for MAPbI3 );
At high voltages, a quadratic dependence in the Child’s regime was observed. As the
density of trap states is linearly proportional to the onset voltage V TFL , for MAPbBr3
and MAPbI3 single crystals trap densities were found to be 5.8 × 109 cm−3 and 3.3
× 1010 cm−3 , respectively.
In a separate study on FAPbI3 and FAx MA1−x PbI3 crystals formed by hydroiodic
(HI) acid-assisted inverse temperature crystallization method, it was found that
substitution of 15% MA+ on FAPbI3 crystals stabilizes the phase and gives best
charge transport characteristic [34]. Using slower component of time-resolved
photoluminescence (TRPL) curves, the carrier lifetime of FAPbI3 and MAPbI3
single crystals were estimated to be 839.31 ns and 145.5 ns, respectively. All the
172 M. Dutta and A. B. Mallick

Table 2 Lifetimes obtained from the analysis of PL spectra of FA(1−x) MAx PbI3 single crystals
with x = 0, 0.05, 0.1, 0.15, 0.2, 0.8, 0.85, 0.9, 0.95, 1 [34]
FA(1−x) MAx PbI3 x=0 x = 0.05 x = 0.1 x = 0.15 x = 0.2
τ 1 (ns) 91.26 61.43 52.11 27.26 31.58
τ 2 (ns) 839.31 689.92 381.86 579.75 236.74
FA(1−x) MAx PbI3 x=1 x = 0.95 x = 0.9 x = 0.85 x=8
τ 1 (ns) 7 32.45 122 88.05 105.3
τ 1 (ns) 145.65 557.5 1074.78 926.39 956.8

FA(1−x) MAx PbI3 (x = 0.1–0.2) single crystals showed shorter carrier lifetime than
that of FA(1−x) MAx PbI3 (x = 0.8–0.9) single crystals. The carrier lifetime of the single
crystals with different compositions are listed in Table 2. The cut-off absorption wave-
length of FA0.85 MA0.15 PbI3 and FA0.15 MA0.85 PbI3 crystals were found at 872 nm
and 851 nm, respectively, that reflects a bandgap of 1.42 eV and 1.46 eV, respec-
tively, for the crystals. PL emission peak for these two types of crystals were found
to be centered at 827 nm and 807 nm, respectively. Using Indium (In)/perovskite
single crystal/In (electron-only) device and Au/perovskite single crystal/Au (hole-
only) device current–voltage characteristics were studied to estimate both types of
charge carrier mobility. By fitting Eq. (2) and using the values of ε = 46.9 for
FA0.85 MA0.15 PbI3 [24] and 32 for FA0.15 MA0.85 PbI3 single crystal [15], electron and
hole mobility were estimated to be 10.19 cm2 V−1 s−1 and 5.31 cm2 V−1 s−1 , 0.77 cm2
V−1 s−1 and 0.66 cm2 V−1 s−1 , respectively. Interestingly, when the hole mobility
of FA0.15 MA0.85 PbI3 was measured in vacuum, it increased to 17.12 cm2 V−1 s−1
which is much higher the mobility measured in air. This indicates that atmosphere
interacts with the single crystal and could increase the surface defects.

5 Applications

5.1 Photovoltaics

The characteristics features of the inorganic–organic hybrid perovskite single crys-

tals, such as long carrier diffusion length, very low trap density, absence of grain
boundary, etc., if could be transported to perovskite films may overcome the chal-
lenges in the development of perovskite solar cells (PSC). In this regard, transition
from bulk perovskite single crystals to perovskite single crystal films could provide
the potential solution. Up to now, there are few attempts to fabricate bulk single
crystal perovskite solar cells as discussed in Sect. 4. Bakr group [28] has reported
PSC based on monocrystalline perovskite (MAPBr3 ) film grown by CTAC strategy.
One set of solar cells were fabricated by depositing Au electrode on the surface of
monocrystalline films grown on ITO glass. In another set of cells, monocrystalline
film was grown on compact TiO2 -coated FTO glass and Au was deposited on the
Progress in Growth and Development of Perovskite Single … 173

perovskite monocrystalline film to get a comparison with PSC devices that made from
perovskite polycrystalline film of the same device structure. The cell with 1 μm thick
monocrystalline film showed a J SC ~ 7.39 mA/cm2 , V OC ~ 1.25 V, and fill factor (FF)
~0.59 with over all conversion efficiency of 5.49%. However, the cell with 4 μm thick
monocrystalline film showed a little lower performance with J SC ~ 7.42 mA/cm2 ,
V OC ~ 1.24 V, and FF ~ 0.58. The large JSC value of the cells is further confirmed
by calculating the integrated current density from the EQE curve. IQE of the device
is more than 90% over a broad spectral range with maximum 97% at 507 nm and
onset at 550 nm. By considering IQE to be 100% (only loss through the reflec-
tion and absorption by ITO), upper limit of this current density was estimated to be
7.64 mA/cm2 . Using the C–V measurement (Mott–Schottky plot), built-in potential
was estimated to be 1.21 which is close to the experimental value obtained for V OC .
For FTO/TiO2 /MAPbBr3 monocrystalline film (thickness: 1 μm)/Au structure solar
cell, the power conversion efficiency was improved to 6.53% (with V OC of 1.36 V,
a J SC of 6.96 mA cm−2 and an FF of 0.69). The behavior is similar to the ITO/
MAPbBr3 /Au-structured solar cell with a sharp decrease in EQE and IQE beyond
350 nm in UV region due to strong absorption of UV irradiation by FTO/TiO2 .

5.2 Detectors

Low trap density (~109 to 1010 per cc), long carrier diffusion length, narrower
bandgap with high light absorption, and improved photocurrent suggest huge poten-
tial of these hybrid perovskite single crystals to be used as photodetectors [35].
Bakr group has reported a UV detector (rise time: 24 ms; decay time: 62 ms) based
on MAPbCl3 single crystals (thickness 350 μm) whose performance is comparable
to the performance of TiO2 thin films and ZnO nanoparticles-based UV-detectors
[20]. The detector was fabricated by depositing 20 nm thick platinum (Pt) layer of
transparency 20% at 365 nm as a top electrode and 20 nm Ti/100 nm Au layer as
a back electrode. This detector showed a low dark current (4.15 × 10−7 A) and
high photocurrent (4.7 × 10−4 A) at 15 V with an ON–OFF ratio 1.1 × 103 . The
responsivity of photodetector was estimated as 46.9 mA/W by using the formula

Ilight − Idark
R= (6)
Plight × S

where I light is the photocurrent, I dark is the dark current, and Plight is the power of
incident light, and S is effective area. Detectivity of the same detector was estimated
to be 1.2 × 1010 Jones by using the formula

R
D= (7)
(2q Jdark )1/2
174 M. Dutta and A. B. Mallick

Fig. 7 a Schematic diagram of the planar-type photodetector produced on the (100) facet of a
MAPbI3 single crystal. b Durability and stability of the MAPBI3 single crystal photodetector.
Reproduced with permission from Ref. [14]. Copyright 2014, Nature

where q is the elementary charge and J dark is the dark current density. Without any
encapsulation, the MAPbCl3 single crystal photodetector showed photostability up
to 8000 s biased at 15 V under continuous light (365 nm, 1 W/cm2 ) illumination in
ambient condition with humidity 55–60%. The same device shows high photosta-
bility over 12 h under blue light (1 Sun excitation density) which is attributed to the
low trap density.
Figure 7a shows a schematic of MAPBI3 single-crystal-based photodetector
(effective illuminated area 1.19 × 10−7 m2 ) where a pair of interdigitized Au film
electrodes, with bridging gap of about 20 μm were deposited on the (100) facet of
the single crystal [14]. The dark current of this device was found to be very low as 11
nA at 4 V bias. Current–voltage characteristics revealed that a Schottky contact was
formed between Au electrode and the crystal. The incident power density was varied
from 0.11 to 3.22 mW cm−2 by using a 532 nm laser as the light source. Responsivity
(R) was estimated by using formula (6) and external quantum efficiency (EQE) by
using the formula
 
hc
EQE = R × (8)
eλ

where h represents the Planck’s constant, c is the velocity of light, e is the electronic
charge, and λ is the wavelength of incident light. From this, the lowest detectable
irradiance power density of the single crystal device was estimated to be 2.12 nW
cm−2 with R value of 953 A W−1 . For polycrystalline film of MAPBI3 below 120
nW cm−2 , irradiance power could not be detected as it was covered by noise. The
highest R and EQE for the photodetector based on polycrystalline film were estimated
to be 0.28 A W−1 and 64.64%, respectively, at 1 V bias. Again, under a relative strong
light irradiance of 1 mW cm−2 , the single crystal device showed about 100 times
higher R value of 2.55 A W−1 compared with the similar photodetector based on
polycrystalline film (R: 0.0197 A W−1 ). For this single crystal photodetector, a peak
photocurrent of 7.6 μA was achieved at 3 V bias with ON–OFF ratio of 224 (rise
Progress in Growth and Development of Perovskite Single … 175

time: 74 μs and decay time: 58 μs). Figure 7b shows the stability and durability of
this single crystal photo-detector in a time scan of 2000 s for the same device before
and after 40 days storage at room temperature. A 6% decay in photocurrent value
was notice after 40 days storage.
By using the improved photocurrent generation and exciton separation by built-in
electric field in the hybrid perovskite single crystals (achieved either by choosing
proper asymmetric electrode material or fabricating heterojunction), self-powered
photodetectors have been proposed [35]. This self-powered photodetectors even-
tually works as photovoltaic devices. A self-powered photodetector, achieved by
exploiting Pt (thickness: 20 nm, transparency: 20% in visible region)/CH3 NH3 PbBr3
single crystal Schottky junction has shown photodetectivity of 1.4 × 1010 Jones
at zero bias [36]. This device showed stable performance in air ambient for over
45 days with rise time of 70 μs and decay time of 150 μs. In another similar type
of work by using asymmetric electrodes of Au–Al (with channel length of 30 mm
between the electrodes), self-powered photodetector based on CH3 NH3 PbI3 single
crystal has been realized [37]. The photovoltaic effect comes into play in this device
depending on the formation Schottkey contacts between the semiconducting single
crystal surface and metal electrode that creates the built-in electric field to separate
photogenerated electron–hole pairs. This self-powered single crystal photodetector
or rather single crystal photovoltaic device produced short circuit current density
(J sc ) of 6.86 mA cm−2 , open-circuit voltage (V oc ) of 0.7 V, and fill factor (FF) of
16.5% with a overall efficiency of 0.79%. The photocurrent showed by this device
is 2 orders of magnitude higher than its polycrystalline perovskite film-based device
with similar device architecture. The lowest incident power detected by this device
was 1 × 10−8 W cm−2 with responsivity (R) 0.24 A W−1 at zero bias. The rise
and decay times of this device were estimated to be 71 and 112 μs. In another
report, Cao et al. [38] showed that photodetector made of a core–shell heterojunc-
tion based on the MAPbBr3 single crystal renders the feature of self powered due
to the built-in electric field at the junction. The perovskite heterojunction is made of
a single-crystalline MAPbBr3 core and a crystalline MAPbIx Br3−x shell with sharp
frontier and interface between each pure component. The perovskite heterojunction
photodetector was constructed on FTO glass over which Au was deposited as anode.
This device showed peak responsivity up to 11.5 mAW−1 under 450 nm irradiation
at zero bias and a maximum EQE of 3.17% with a rise time of 2.3 s and a fall time of
2.76 s. Both this values are higher than self-powered device based of pure MAPbBr3
single crystal. This self-powered photodetector produced a short-circuit photocurrent
of 0.1961 mA cm−2 , an open-circuit voltage of 0.61 V, and a fill factor of 0.413.
Detection of high energy photons having energy ~50 keV to 10 MeV (like gamma
(γ) ray, X-ray, etc.) emitted from decay of various radioactive isotopes has importance
in several fields of research and also in non-destructive testing of industrial products,
medical diagnostics, and defense [39, 40]. High charge carrier lifetime, mobility, low
density of charge traps, high absorption of hard radiation by heavy metals present
in hybrid perovskite single crystals allow the fabrication of low-cost hard radiation
detectors that are highly sensitive and could be operated at room temperature [41].
Yakunin et al. [42] have demonstrated that semiconducting single crystals (SCs) of
176 M. Dutta and A. B. Mallick

hybrid lead halide perovskites (MAPbI3 , FAPbI3, and I-treated MAPbBr3 ) of size
0.3–1 cm could work as solid state γ ray detecting material due to the high μτ product
of 1.0–1.8 × 10−2 cm2 V−1 , a low charge trap density of 109 to 1010 cm−3 [15, 31],
a low dark carrier density of 109 to 1011 cm−3 [23, 31], and a high absorptivity of
hard radiation by the lead and iodine atoms. Single crystal of MAPbI3 gives rise to
a sensitivity of 0.65 μC mGyair−1 cm−2 for a photon flux of ~5.6 × 107 cm−2 s−1
and a photocurrent of 22 nA. If the full penetration depth ~30 μm is considered,
then the sensitivity goes to ~220 μC mGyair−1 cm−3 that is one order of magnitude
higher than polycrystalline perovskite film detector [43]. Wei et al. [25] reported a
highly sensitive X-ray detector based on MAPbBr3 single crystal with a record-high
mobility–lifetime product of 1.2 × 10−2 cm2 V−1 and surface charge recombination
velocity of 64 cm s−1 . Detectors based on 2–3 mm thick single crystal showed
detection efficiency up to 16.4% at near zero bias under the irradiation of X-ray up
to 50 keV. For this type of detectors can detect X-ray dose rate as low as 0.5 μGyair
s−1 with a sensitivity of 80 μC Gy−1 air cm−2 .

6 Future Aspects

In a very short span, these metal organic halide perovskites have shown unique
properties. Superior semiconducting properties with low-cost deposition techniques
open new paths for the metal hybrid halide perovskite applications. Properties like
long carrier diffusion length and low trap state density make these hybrid single
crystals comparable to best photovoltaic quality Si. This book chapter focuses on
the different growth methods for the hybrid halide perovskite with an outlook for
possible applications.
Around the globe, researchers from all genres are making continuous efforts to
unlock the full potential of these versatile materials. Apart from these, some demerits
like toxicity due to presence of heavy metal (e.g., Pb) is needed to be addressed. One
such option is to go for fully inorganic halide perovskite like CsPbBr3 which can be
grown using solution processes.
Most studied application of single crystal halide perovskite is photodetectors that
have shown brilliant performance. Another application of these could be in solar cells
based on single crystal but to date, the application is not flourished properly. This
is due to unavailability of high quality monocrystalline films along with appropriate
thickness to be used as perovskite solar cells. Though, the deposition of monocrys-
talline perovskite films by CTAC method has shown a path toward this goal [28].
However, a lot has to be remaining to achieve. Other methods should be explored
in this direction so as the fascinating properties of bulk single crystals could be
incorporated in the geometry of thin films [61]. Nevertheless, Liu group [29] has
developed a process for the production of thin and shape controlled large size single
crystal perovskite wafers for mass production based on ITC growth method. Figure 8
shows the similar schematic of the arrangement used for this type of large size thin
single crystal wafer growth. Two slides of glass are kept parallel and aligned with
Progress in Growth and Development of Perovskite Single … 177

Temperature Temperature
Controller Controller

Pump Pump Pump Pump

in out in out

Time
Solution
Crystal
Glass
Spacer
Glass

Hot Plate Hot Plate

Fig. 8 Schematic representation for large size single crystal perovskite wafer growth by ITC method

each other by using two spacers. Thickness of the spacers defines the thinness of the
grown perovskite single crystal wafer. Growth of the single crystal confines within
the gap between the glass slides. Shape of the single crystal wafers is decided by
the design of the channel between the two glass slides. To maintain the flow of fresh
precursor solution during growth inside the channel, peristaltic pump is used.
In the near future, prospects of creating single crystal of high quality with
controlled thickness and orientation would fulfill the requirements of this application.

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Perovskite Oxides as Advanced Energy
Materials for Solid Oxide Fuel Cell
and Supercapacitor Applications

P. Muhammed Shafi

Abstract The present chapter reveals a detailed explanation of ABO3 -type

perovskite oxides with their physiochemical properties. The crystallographic struc-
ture and its impact on stability and properties are well discussed in various sections
of this chapter. Even though the perovskite oxides exhibit a wide range of appli-
cations owing to their unique crystallographic and physiochemical property, here
the electrochemical energy conversion/storage applications are mainly focused. The
importance of electronic and ionic conductivities of ABO3 -type perovskite oxide
materials and their impacts on electrochemical conversion and storage properties
are elucidated with suitable schematic representations and theoretical backgrounds.
Particularly, application toward the supercapacitor as electrode material and toward
all the three components (cathode, anode, and electrolyte) of solid oxide fuel cells
(SOFCs) is addressed. The possibility of anionic as well as cationic storage mecha-
nism in perovskite-based supercapacitors are discussed as well. Moreover, the role of
these perovskite materials for oxygen ion conducting electrolyte as well as the proton-
conducting electrolytes for the SOFCs is schematically illustrated. The chapter also
covers a broad literature survey to understand the current scenario and development
of these materials to the given applications.

Keywords Perovskite oxide · Tolerance factor · Cationic array · Oxygen

vacancy · Mixed ionic electronic conductivity · Fuel cell · Supercapacitor

1 Introduction

Compared to common binary (rutile structure) oxides, the complex or mixed oxides
have attracted great interest in material science owing to their wide range of appli-
cations. Multiple numbers of cations together formed to a single oxide material is
usually referred as mixed oxide. However, an oxide material with one single cation

P. Muhammed Shafi (B)

School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 38541, Republic
of Korea
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 181

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_8
182 P. Muhammed Shafi

of different oxidation states is also often considered as mixed oxide material. But,
in a general perceptive, unlike rutile oxides, a mixed oxide consists of two or more
cations with different oxidation states, ionic sizes and co-ordination numbers [1–3].
The spinel and perovskite are well-known examples for complex oxide structures. In
both the cases, the diversity of ions, oxidation states and sizes offer different prop-
erties depending upon the ions present. Hence, these types of complex oxides are
explored to a variety of applications. There are two types of spinel structures namely:
normal spinel and inverse spinel. The normal spinel has a structure of AB2 O4 where
A cations occupy the 1/8 tetrahedral hole and B cation occupy the 1/2 of the octa-
hedral hole. The inverse spinel has a common formula of B[AB]O4 where B cations
occupy the 1/8 tetrahedral hole and the second B and A cations occupy the cation
occupy the 1/2 of the octahedral hole. Moreover, the rutile oxide (AO2 ) comprises
of only one cation and an oxygen, which are octahedrally coordinated. Unlike these
binary rutile structured oxides and complex spinel structured oxides, the perovskite
oxide structure follows a general formula of ABO3 , where A and B are cations of
different atomic and mass numbers, and O is the oxygen anion in the ratio of 1:1:3
[3–5]. The history of these types of materials start from the discovery of CaTiO3
in 1839 by Gustav Rose, a famous geologist and is named as perovskite after a
renowned Russian mineralogist, Lev Alexevich von Perovski (1792–1856). A site is
usually occupied by lanthanides/alkaline earth elements of larger ionic radius and B
site by transition metal of comparatively smaller radius. The A cation usually has a
12-fold dodecahedral co-ordination and B cation has sixfold co-ordination [5]. The
spatial structure of a perovskite material is given in Fig. 1a. The choice of cations
and anion, oxidation state of cation, and ionic radii of A and B site cations affect the
structure and properties of perovskite material. The diversity of cations and anions
of these structures provide a wide variety of applications including photovoltaic,
ferroelectric, dielectric, pyroelectric, piezoelectric, magnetic, catalytic, and energy
storage/conversion. The synthesis route and controlling morphology of the perovskite
material are very crucial and have a strong impact on their properties.

Fig. 1 a Spatial
arrangement of atoms in
perovskite structure and
b unit cell for an ideal cubic
perovskite
Perovskite Oxides as Advanced Energy Materials for Solid … 183

2 Material Properties

2.1 Structural Stability

The stability of a perovskite structured material is usually defined by tolerance factor,

τ. The first explanation on perovskite tolerance factor was made by Victor Moritz
Goldschmidt, mineralogist, and now the formula of tolerance factor calculation is
often called as Goldschmidt tolerance factor (Eq. 1). Here, rA , rB and rO are radii of
A cation, B cation, and oxygen anion, respectively. The tolerance factor range 0.7 <
τ < 1 is considered as a stable structure.
rA + rO
τ=√ (1)
2(rB + rO )

The perfect crystal structure is considered as cubic (τ = 1) and by further lowering

the τ value, the structure tilts to rhombohedral and then to orthorhombic and so on.
The decrease in rA or increase in rB definitely lowers the τ value and will result in
a decrease in the symmetry. For a τ value greater than unity, the crystal tends to
stabilize with hexagonal structure [1]. Hence, the calculation of τ can be used to
opt cations for A and B sites in order to tailor the property without losing structural
stability. The ideal perovskite structure, that is the cubic phase belongs to the pm3m
(221) space group [2]. Figure 1b shows the pictorial representation of a unit cell of
an ideal cubic structure, where the A cations are occupied at the corners, B cation at
the body center and the oxygen ions are located at the center of each face of the cube.
The packing factor of these perovskites is usually high and is 0.76 for LaMnO3 [3].
Generally, the packing factor for perovskite structure lies around 0.75 [1, 2]. For a
perfect cubic structure, the B–O–B bond forms a linear chain with 180° bond angle.
The reduction in τ value induces deviation from the cubic phase by tilting the BO6
octahedra, resulting in a reduced B–O–B bond angle (<180°). Hence, opting choice
of cations is very crucial in order to maintain the stable phase of perovskite oxide.
Despite considering the oxidation state and radii of A and B site cations as important
factors to decide the material properties, their role in upholding the stable phase also
should be taken care of.

2.2 Electronic and Ionic Conductivity

The electronic and ionic conductivity of the perovskite adapts them to various appli-
cations like superconductivity, electrodes for energy storage, and catalytic applica-
tions. Cu-based perovskite achieved great potential toward superconductivity, where
Cu occupies the B site. There are many examples of superconducting perovskite
oxides with Cu as B cation. YBa2 Cu3 O7 , Bi2 Sr2 Ca2 Cu3 O10 , and HgBa2 Ca2 Cu3 O8+δ
are some examples. Apart from these superconducting materials, there are many
184 P. Muhammed Shafi

perovskite materials that exhibit nearly metallic behavior, and hence they are used
as electrodes for solid oxide fuel cells and metal-air batteries. LaMnO3 and LaCoO3
are commonly used electrode materials. The BO6 octahedra play a major role in
the electronic conductivity of the ABO3 perovskites. The anion polarization induces
to form a covalent bond between B cation and oxygen anion, which facilitates the
electronic conductivity. Electrons of n-type and holes of p-type perovskites are trans-
ported through B–O–B chains. The electronic conductivity of these materials could be
further improved by partial substitution of A or B site cation with different oxidation
states. Furthermore, it is believed that the perovskite oxide has an inherent prop-
erty of having oxygen vacancy. This oxygen vacancy will play as a medium for ionic
mobility and result in an improved ionic conductivity. Hence, these types of materials
are largely used as ion-conducting electrolytes for solid-state fuel cell SOFCs. Similar
to electronic conductivity, the ionic conductivity of the perovskite oxides could effec-
tively improve by cationic substitution. Therefore, the electron/hole conduction along
chains of B–O–B bond and vacancy mediated oxygen ion mobility, having played
a major role in bringing the material as a mixed ionic and electronic conduction
application, is being explored for electrodes as well as ion-conducting electrolytes
of various conversion and storage devices.

3 Tuning Electronic and Ionic Conductivities

in ABO3 -Type Perovskite Materials

The extensive array of cationic selection possibility of perovskite structure over A and
B sites is well known to tailor the specific properties. Though the critical properties of
the perovskite materials are defined by the B site cation, A site cation plays a vital role
in tuning these properties. Furthermore, this class of material allows a wide range of
cationic substitution over A and B sites without affecting the structural stability factor.
This offers intriguing possibilities for further improvement of material properties.
The electronic and ionic conductivities or mixed ionic and electronic conductivity of
these materials are effectively tuned depending upon the application by such cationic
substitutions.
For instance, consider an ABO3 -type perovskite oxide where the electric neutrality
is maintained with charge distribution of A3+ B3+ O3 . Now let us see how the cationic
substitution at A site affects the conductivity of the material.
Let us consider another cation, À of similar ionic radii, (so that it may not affect
the tolerance factor) with an oxidation state of +2 (a divalent acceptor, À2+ ) and is
substituted partially for trivalent A cation (A3+ ).
Now, in order to maintain the electron neutrality, the effective negative charge
induced by À substitution should be compensated either by electronic compensation
or ionic compensation [4].
Perovskite Oxides as Advanced Energy Materials for Solid … 185

3.1 Electronic Compensation

• The extra electron left at the A site lattice by À substitution will be balanced by
converting an equal amount trivalent B transition metal to tetravalent state.
i.e. xÀ + A(1−x) B O3 → À2+ 3+ 4+ 3+
x A(1−x) Bx B(1−x) O3
(substitution of xÀ induces a conversion xB3+ to xB4+ ).
• As a consequence, the divalent cationic substitution at the A site causes to form
an electron hole (hz ) at the tetravalent B site as p-type.
• Hence, the electronic conductivity through the B–O–B chains will be due to the
transportation of holes, i.e., the electronic conduction occurs through the migration
of hole associated with the tetravalent B site cation to the nearest trivalent B site
cation.
• The amount of transition metal B4+ /B3+ couple is proportional to the amount of
divalent acceptor À substitution at trivalent host cation, A.
• Higher the B4+ /B3+ couple, higher the electronic conductivity expected. Theoret-
ically, 50% of mole percentage divalent acceptor substitution is expected to have
a maximum electronic conductivity.
• Electronic conductivity,

C −Ea /kT
σ = e (2)
T
where the pre-exponential constant C includes the carrier concentration along
with other material-dependent parameters, T is the absolute temperature, E a is the
activation energy and k is the Boltzmann constant.
Figure 2 shows the schematic representation of electronic conductivity exerted by
the partial substitution of a divalent acceptor cation.

Fig. 2 Electronic conduction through electron hole migration from B4+ to B3+ state. The B4+ /B3+
couple formed due to the introduction of divalent cation (À) to the A site
186 P. Muhammed Shafi

3.2 Ionic Compensation

• If the B cation is not multivalent, the extra negative charge occurred at the
host lattice by divalent À acceptor cation is balanced by reducing the oxygen
stoichiometry.
• Consequently, charge imbalance due to each 2À substitution is compensated by
forming an oxygen vacancy at anionic sites.

(i.e., two electron holes are eliminated by removal of single oxygen from the
lattice)

δ
2δÀ + A(1−2δ) B O3 → À2δ A(1−2δ) B O 3−δ + O2
2
• The ionic conductivity in ABO3 -type oxides occurs due to the oxygen vacancy
mediated oxygen ion transport. The oxygen vacancy of any vacancy site will be
filled by an adjacent oxygen ion. This diffusive jump of O2− ion from the adjacent
oxygen site by exchanging their position facilitates the ionic conductivity.
• Hence, the ionic conductivity of any ABO3 perovskite oxide is directly propor-
tional to their measure of oxygen vacancies [5].
• Nonetheless, the electronic conductivity is limited due to the decreased amount
of B4+ /B3+ couple, which leads to decreased amount of available hopping sites.
Hence, the modified electronic conductivity is,

 C
σ = Á − 2δ e−Ea /kT (3)
T
The new term included in the pre-exponential factor represents the oxygen vacancy
limited carrier concentration.

Fig. 3 Ionic conduction through diffusive jump of adjacent O2− ion due to the divalent acceptor
cationic substitution induced oxygen vacancy
Perovskite Oxides as Advanced Energy Materials for Solid … 187

Figure 3 shows the schematic representation of ionic conductivity through oxygen

mobility through the perovskite lattice exerted by the partial substitution of a divalent
acceptor cation.
However, the simultaneous presence of transition metal B4+ /B3+ couple and
oxygen vacancies can perform a mixed ionic and electronic conductivity.

4 Perovskite Oxides as Advanced Energy Materials

Since the perovskite oxides are structurally stable even at elevated temperatures
and have the mixed ionic electronic conductivity, these materials are tradition-
ally used for multiple applications. More importantly, these materials have great
potential insight in energy conversion and storage applications. Though there many
energy applications for perovskite oxide materials (photovoltaic, fuel cell, secondary
batteries, and supercapacitor), this chapter mainly focused on solid oxide fuel cell
and supercapacitor applications.

4.1 As Advanced Energy Conversion Materials

For a conversion device like the so-called fuel cell, perovskite oxides have been
studied for all the three components (anode, cathode, and electrolyte). Especially,
in the case of SOFC, perovskite has been used for electrodes (cathode and anode)
as well as for electrolytes. The cathode material should have high electrochemical
activity toward oxygen reduction reaction (ORR), high oxygen ion diffusivity to
transfer the reduced oxygen ion through the bulk cathode material. Hence, perovskite
materials of mixed ionic electronic conductivity along with high ORR activity are
favorable to cathode application. The properties required for anode material are
similar to the cathode material properties except for one additional property of high
catalytic activity toward the hydrogen oxidation reaction. The mixed ionic electronic
conductivity is a must for electrolytes of SOFC so as to transport the reduced oxygen
ion from cathode to anode where the combustion reaction or hydrogen oxidation
takes place.
• Components of SOFC
A solid oxide fuel cell is a solid-state electrochemical device that converts chem-
ical energy to electrical energy and heats by the efficient combustion of fuels or
oxidants. Generally, SOFC is a bipolar conversion device with three basic compo-
nents such as cathode, anode, and electrolyte. Figure 4a represents the scheme for
the basic structure of a SOFS device. The cathode and anodes are made up of porous
ceramics as it should sustain higher temperatures. The porous structure of anode
material enables the easy diffusion of fuel gases to and from the electrode–elec-
trolyte interface. The reduction of oxygen at cathode and oxidation of fuel/oxidant
188 P. Muhammed Shafi

Fig. 4 a Basic structure of a solid oxide fuel cell and b the tubular SOFC design from Siemens–
Westinghouse

at the anode are spatially separated and the electrons are directed to flow through an
external circuit. The movement of oxygen ion from the cathode to anode through the
solid electrolyte is controlled and driven by the oxygen chemical potential gradient
between the cathode and anode. The oxygen partial pressure exerted at the cathode
is very high and at the anode is very low due to the consumption of oxygen ion by the
fuel combustion. The critical component of a SOFC is the gas-tight solid electrolyte,
which separates the cathode and anode safely. A light crack or presence of a pinhole
will lead to diffusion of fuel gas from anode to cathode. Such leakages cause a direct
reaction of fuel with oxygen ions at cathode, and the device then becomes ineffi-
cient. According to the design and spatial arrangement of these components, there
are planar, tubular, and single chamber SOFCs [6]. Figure 4b represents the famous
tubular design of SOFC developed by Westinghouse and taken over by Siemens.
a. Cathode materials
Numerous perovskite oxides have been developed as efficient cathode materials for
SOFC in recent years [7–15]. The cathode material for SOFC should be catalytically
active toward the ORR activity. Besides, it should be conductive electrically as well as
ionically in order to transport the oxygen ion through the bulk. The chemical stability
of cathode material is also a critical parameter for the SOFC to work effectively.
Because, the cathode side will be oxygen ion rich always, the material should be
highly stable even in this oxidizing environment. Moreover, the thermo-mechanical
property of the cathode material should be well-matched with the electrolyte; other-
wise, the possibility of stress development is maximum upon heating and cooling
conditions. The state-of-the-art of cathode material for SOFCs generally comprises
of a highly ORR catalytic with electrically conducting or with mixed ionic electric
conductive material and an ionic conductor (Y2 O3 stabilized ZrO2 , so-called YSZ)
[16]. There are two types of cathode materials based on the conducting nature.
1. Electrically conducting cathode materials:
Here, the electrode acts as electron supplier and the ORR activity will take place
at the triple phase boundary (TPB), where the cathode catalyst, oxygen gas, and
Perovskite Oxides as Advanced Energy Materials for Solid … 189

Table 1 Perovskite oxide materials used as cathode material for SOFCs with their operating
temperature (°C), electronic and ionic conductivities (S cm−1 ) and TEC (K−1 )
Cathode materials Temperature Electronic Ionic TEC [× References
(°C) conductivity conductivity 10−6 K−1 ]
(S cm−1 ) (S cm−1 )
La0.65 Sr0.35 MnO3−δ 800 102 1.7 × 10−4 [7]
(La0.8 Sr0.2 MnO3 ) 700 180 11.8 [8]
La0.7 Sr0.3 MnO3 800 240 11.7 [9, 10]
La0.8 Sr0.2 FeO3 700 90 12.2 [11]
La0.6 Sr0.4 FeO3 800 129 5.6 × 10−3 16.3 [12]
La0.6 Sr0.4 Co0.2 Fe0.8 O3 800 302 8 × 10−3 [7]
Ba0.5 Sr0.5 Co0.8 Fe0.2 O3−δ 15 19.95 [13, 14]
La0.6 Sr0.4 CoO3 800 1600 0.22 20.5 [7, 15]
Pr0.8 Sr0.2 Co0.2 Fe0.8 O3 800 76 1.5 12.8 [7]
Sr0.9 Ce0.1 Fe0.8 Ni0.2 O3 800 87 0.04 18.9 [7]

electrolytes meet. Hence, in this case, the TPB length plays a critical role in the
cathode performances toward high current density and lower overpotential.
2. Mixed ionic and electronic conducting cathode materials:
Here, the cathode material is a mixed ionic electronic conductor, and hence the ORR
activity will take place at the surface of cathode material and it will diffuse through
the bulk. Thus, the surface and bulk pathways coexist in parallel. Mostly, these two
are in competition with each other, the fastest will determine the overall kinetics
of SOFC cathode. Few important perovskite-based cathode materials are listed in
Table 1.
Considering these parameters, the widely used cathode materials are
La1−x Srx MnO3 (LSM) materials and La1−x Srx Co1−y Fey O3 (LSCF). However, the
LSM perovskites are still struggling due to its relatively lower ionic conductivity
and larger activation energy for ORR activity. The ORR activity happening at SOFC
cathode is as follows:
1
O2 + 2e− = O2− (4)
2
b. Anode materials

Anode is an important component of SOFC device since it serves as an electro-

chemical active site for oxidation of fuel gas. Anode also requires higher electronic
conductivity as the electron released after the fuel oxidation should transport to the
connecting component of the fuel cell. Moreover, the anode should support a good
catalytic activity toward the fuel gas oxidation. The oxidation reaction for a hydrogen
fuel SOFC is as follows;
190 P. Muhammed Shafi

H2 + O2− = H2 O + 2e− (5)

In the early stages of anode material development for SOFCs, noble metals such
as platinum, gold, silver, palladium, and rhodium were used. In addition, some tran-
sition metals were also examined such as manganese, copper, nickel, cobalt, and iron
[17]. The nickel in its pure metal form achieved great attraction owing to its high elec-
trochemical activity, redox stability, and low cost. However, the sintering problem,
carbon surface deposition, sulfur poisoning, and the thermal expansion coefficient
mismatch from the usual electrolytes lead to the reduced life span of SOFCs, and thus
it hinders its commercialization [6, 18–21]. In this context, perovskite oxide mate-
rials have gained much attention to develop efficient anode for SOFCs and to replace
the traditional anodes. The mixed ionic electronic conductivity of these materials
can overcome the confinement of electrochemical oxidation activity at the TPB by
extending its solid-gas two-phase boundaries [22]. Besides, some perovskite oxides
provide few additional properties, which are important to the SOFC anode. They are
listed below;
• High thermal stability
• Compatibility with a solid-state electrolyte
• Excellent electronic conductivity (>100 S cm−1 ), preferably n-type conductivity
• Better oxygen surface exchange kinetics
• Highly porous structure to ease the fuel gas transportation
• Inherent property of oxygen vacancy to enhance oxygen ion diffusion
• Tunable ionic conductivity by choosing proper B cation.
Based on the crystalline nature, the perovskite cathode materials are classified as
chromite, titanate, and vanadate. Among the chromite perovskite oxides, Ca doped
LaCrO3 or Sr doped LaCrO3 are widely used owing to their reduced sinterability to
YSZ electrolyte, no carbon formation and excellent thermal expansion coefficient
(TEC) match with YSZ electrolyte. Further to enhance the electrocatalytic activity,
numerous efforts were made by various material scientists by doping the A and B
sites cations [23–27]. S Feir et al. investigated an array of dopant cations for the A
and B site substitution and found Sr and Ni are the best for SOFC anodes to enhance
the electrochemical catalytic activity [28]. LnSrTiMO3 is another class of successful
anode materials, where Ln stands for lanthanides like La, Nd, and Sm elements,
and M stands for Mn and Fe transition metal. It is observed by jeong et al. that the
substitution of Mn or Fe to the B site enhances both the structural stability as well as
catalytic activity [29]. Among the various doped LnSTMO3 , the Nd-doped material
is found to be promising due to its improved conductivity. The Nd substitution at
the A site induces some Ti molecules to exhibit metallic behavior [30]. Some of the
commonly studied materials for SOFC cathode application are tabulated in Table 2
[31–45].
Recently, double perovskite structured (A2 B2 O6 ) materials are also being exam-
ined for anodes of SOFC devices due to their promising electrochemical prop-
erty, rich active sites, excellent defense capability toward carbon deposition and
sulfur poisoning [43, 46–48]. Sr2 Fe1.5 Mo0.5 O6−δ , Sr2 MgMoO6−δ , and layered
Perovskite Oxides as Advanced Energy Materials for Solid … 191

Table 2 Perovskite oxide materials used as anode material for SOFCs with their operating
temperature in °C and conductivity in S cm−1
Anode materials Temperature (°C) Conductivity (S References
cm−1 )
Reducing Oxidizing
La0.7 Mg0.3 CrO3 800 0.17 3.35 [31]
La0.75 Sr0.25 CrO3 800 7.07 59.1 [31]
La0.7 Ca0.3 CrO3 800 1.6 50.1 [31]
La0.75 Sr0.25 Cr0.5 Mn0.5 O3 900 1.5 38 [32]
La0.9 Ca0.1 Fe0.95 Nb0.05 O3−δ 850 42.55 3.52 [33]
La0.75 Sr0.25 Cr0.3 Fe0.2 Mn0.5 O3−δ 750 1.04 15.42 [34]
SrFe0.9 Ti0.1 O3−δ 600 2.53 4.19 [35]
Sr0.9 Ce0.1 Co0.2 Fe0.8 O3−δ 600 22 180 [36]
La0.3 Sr0.7 Ti0.8 Cr0.2 O3 800 53 8 [37]
La0.9 VO3 800 2.9 [38]
La0.8 Sr0.2 VO3 800 45 [38]
La0.7 Sr0.3 VO3 800 120 [38]
Ce1−x Cax VO3 (x = 0.1, 0.2, 0.3, 0.4) 700 2-13 ~10−3 [39]
Sr2 FeNb0.2 Mo0.8 O6−δ 800 5.3 19.5 [19]
Sr2 FeMoO6−δ 800 186.9 [40]
Sr1.8 Sm0.2 Fe1.5 Mo0.5 O6 850 25 [41]
Sr2 Fe1.4 Ni0.1 Mo0.5 O6−δ 800 20.6 [42]
PrBaMn2 O5 800 8.16 91.5 [43]
PrBaMn1.5 Fe0.5 O5+δ 800 7.4 112.5 [44]
(PrBa)0.95 (Fe0.9 Mo0.1 )2 O5+δ 800 59.2 [45]

PrBaMn2 O5+δ are few of the excellent double perovskite anode materials having
superior electrochemical activity and resistance toward sulfur poisoning and carbon
deposition [43, 47, 48]. Both A2 BB O3 and AA B2 O3 type double perovskites were
investigated for the SOFC anode by various people. Few of these materials are listed
in Table 2.
c. Electrolytes
The electrolyte of a SOFC device is another important component, which categorizes
the SOFC depending upon the nature of the electrolyte’s conductivity. The primary
requirement for a SOFC electrolyte is the ionic conductivity rather than electronic
conductivity. The electrolyte with maximum ionic conductivity and minimum elec-
tronic conductivity is believed to be the best choice [6]. Moreover, the electrolyte
should be dense enough to prevent the gas mixing possibility. So far, YSZ is the
most commonly used SOFC electrolyte since the trivalent yttrium doping creates a
large amount of oxygen vacancies and thus ionic conductivity to the zirconia lattice
[6]. However, the substantial growth of its grain size at high-temperature calcination
192 P. Muhammed Shafi

and not being cost-effective to practical use brought researchers to think about alter-
nate options. Ceria-based (CeO2 ) electrolytes are also largely used for SOFCs due
to its much higher ionic conductivity. Gd2 O3 doped ceria (CGO) has exhibited large
oxygen vacancies and thus show a much better ionic conductivity. These results drive
the attention of researchers to the ABO3 -based perovskite materials as it contains
large number of inherent oxygen vacancies, and further the vacancies are tunable by
proper substitutions at A and B sites. Based on the conductivity nature, there are two
types of electrolyte.
(i) Oxygen ion conducting electrolyte
In the case of SOFC with oxygen ion conducting electrolyte, the O2− diffuses to
anode and the fuel combustion takes place at anode. Hence, the oxygen ion mobility
is a must for proper functioning of this type of SOFCs. Since ABO3 -type perovskites
have already drawn much attention by its capability of oxygen ion diffusion through
the lattice, the property is much explored in SOFC electrolyte field. Lanthanum
gallate (LaGaO3 ) is one of the hot materials being examined well in this applica-
tion. The intermediate operating temperature range and excellent ionic conductivity
even higher than stabilized zirconia made LaGaO3 a promising candidate for SOFC
electrolyte application [49]. Furthermore, doped LaGaO3 exhibits exciting advan-
tages over YSZ and other competing electrolytes. Partial substitution for trivalent
La and Ga by divalent acceptor cations drastically improved the oxygen vacancies
and thus oxygen ion conductivity of the material. For example, the divalent Sr and
Mg co-doped La1−x Srx Ga1−y Mgy O3−x/2–y/2 showed significant improvement in ionic
conductivity and stability than CGO-based electrolytes [50]. Thus, this electrolyte
material is explored well in intermediate operating temperature range (600–800 °C)
SOFCs [51]. However, the complexity of preparing this material without impurities
formation and instability under oxidizing and reducing conditions suppressed the
applications [52, 53]. Similarly, perovskite oxides of structure LnBO3 (Ln = La, Dy
and B = Al, In, Sc, Y) were also examined by various people as an ion-conducting
electrolyte. LnAlO3 received considerable interest owing to their high stability, rela-
tively low cost, and moderate thermal expansion [54, 55]. Few oxide ion conducting
perovskite electrolyte materials are listed in Table 3 [56–60].
(ii) Proton-conducting electrolyte
The role of perovskite in SOFC electrolyte became more relevant while focus was
on proton-conducting electrolyte. Here, the SOFC can be used at lower operating
temperature due to the lower activation energy of proton. Again, the possibility of
using high conductive material for proton-conducting electrolyte applications allows
an array of materials to be used for this application. Iwahara et al. [61, 62] analyzed
this ABO3 perovskite material (SrCeO3 ) for proton conduction first, after that the
topic gained popularity for SOFC electrolyte application. Once this material comes
in contact with water molecule, it starts proton conduction. The mechanism can be
explained using Kröger–Vink notation as Eq. 6 [63] where, V•• •
0 , O0 , and OH0 are
x

an oxygen vacancy, a lattice oxygen ion, and a hydroxyl ion. The proton defect
formation happens when water vapor is incorporated with the oxygen vacancy and
Perovskite Oxides as Advanced Energy Materials for Solid … 193

Table 3 Some perovskite-based oxygen ion conducting electrolyte material for SOFCs with their
operating temperature (°C), electronic and ionic conductivities (S cm−1 ) and TEC (K−1 )
Electrolyte materials Temperature Electronic Ionic TEC [× References
(°C) conductivity conductivity 10−6 K−1 ]
(S cm−1 ) (S cm−1 )
La0.9 Sr0.1 Ga0.8 Mg0.2 O2.85 800 0.1 10.7 [56]
LaSc0.9 Mg0.1 O3−δ 800 200 2× 10−4 [57]
La0.9 Sr0.1 AlO3−δ 800 60 2 × 10−3 [58]
La0.9 Sr0.1 Al0.9 Mg0.1 O3−δ 800 70 2 × 10−4 11.2 [59, 60]
La0.9 Sr0.1 ScO3−δ 800 46 7 × 10−3 [58]
La0.9 Sr0.1 InO3−δ 800 23 7 × 10−3 [60]

lattice oxygen ion of the electrolyte material.

H2 O + V•• •
0 + O0 ↔ 2OH0
x
(6)

At the anode side, the hydrogen from fuel will incorporate the electrolyte lattice
oxygen ion as shown in Eq. 7. When the number of protonated oxygen ions is suffi-
ciently high, the proton will migrate to the adjacent oxygen ion in the lattice since it is
not bounded to any particular oxygen and is quasi-free to diffuse. Hence, the protonic
conductivity in these types of electrolytes occurs through this proton migration [64].
Consequently, the protons continuously transport to the cathode side and there the
oxygen gas consumes and leaves electrons and water molecules according to Eq. 8.
The major advantage of the proton-conducting electrolyte SOFC is that it will not
release water at anode like oxygen ion conducting SOFC, which helps to keep the
fuel in pure form.

Hads + O0x → OH•0 + e− (7)

1
2OH•0 + O2 (g) + 2e− → H2 Oads + 2O0x (8)
2
Figure 5 represents the schematic illustration of a SOFC with proton-conducting
electrolyte. The protonic conductivity by the proton defect diffusion through the
electrolyte lattice is balanced by oxygen vacancies as a counterpart to keep the
neutral charge. Hence, oxygen vacancy plays a major role here too, similar to oxygen
ion conducting SOFC. Consequently, perovskite oxides materials, well known by
its inherent and tunable oxygen vacancies, were studied for the proton-conducting
electrolyte applications. BaCeO3 -based materials received much attention in this
field due to its higher protonic conductivity [6]. Further, doping with acceptor cation
at Ce4+ site of BaCeO3 leads to promising improvement in proton defect formation,
where the charge neutrality is maintained by forming oxygen vacancy. It is found
that the trivalent cations (M3+ ) result in more protonic conduction than divalent
194 P. Muhammed Shafi

Fig. 5 Schematic
illustration of a
proton-conducting
electrolyte

Table 4 Some perovskite-based proton-conducting electrolyte material for SOFCs with their
operating temperature (°C), ohmic and polarization resistances ()
Electrolyte materials Operating Ohmic Polarization References
temperature resistance resistance ()
(°C) ()
BaZr0.8 Y0.2 O3−δ (BZY20) 800 1.4 1.3 [65]
BaZr0.7 Pr0.1 Y0.2 O3−δ (BZPY10) – 1.33 1.3 [66]
BaCe0.7 Nb0.1 Sm0.2 O3−δ (BCNS) 1.1 1.2 [67]
BaCa0.9 Nd0.1 O3−δ (BCNO) 700 [68]
BaCe0.7 Ta0.1 Y0.2 O3−δ (BCTY) 1.08 0.95 [69]
BaCe0.9 Sm0.1 O3−δ (BCS) 620 [68]

cation, since it produces protonic defect more effectively. The partial substitution
results to form BaCe1−x Mx O3−δ . Similarly, the B site partial substitution on SrCeO3
(SrCe1−x Mx O3−δ ) also received much interest. Some excellent proton-conducting
electrolytes are listed in Table 4.

4.2 As Advanced Energy Storage Materials

The rapid growth of electronic industries and increased use of fossil fuels requires
urgent implementation of sustainable energy conversion/storage devices. Hence,
there is an increased demand for developed and cost-effective high-performance
storage devices. Batteries and supercapacitors are the two major devices in this
field. There are countless efforts paid by researchers to develop efficient electrodes
for these devices. Perovskite oxides received considerable attention owing to their
unique tenability of composition and thus their functionalities. The array of cation
sites and their possible substitutions, and the multiple oxidation states of B site cation
along with inherent and tunable property of lattice oxygen vacancies brought them to
a special space in the field of electrode material development for batteries and super-
capacitors. Though there are many reports available on perovskite oxide materials
Perovskite Oxides as Advanced Energy Materials for Solid … 195

used for electrodes of different types of batteries, this chapter discusses the appli-
cation toward supercapacitor electrode fabrication. While coming to energy storage
application, ternary metal oxides with two different metal cations are found to be
suitable for advanced electrode materials owing to their multiple oxidation states and
improved electronic conductivity. Similarly, perovskite oxides with ABO3 structure
have achieved tremendous attention in replacing metal oxides as electrode mate-
rial in electrochemical energy storage devices. The availability of A site and B site,
where A site is usually occupied by lanthanides and B site by transition metal which
provides enough sites for cationic intercalation. Further, their properties strongly vary
depending on A and B ion’s nature and oxidation states. In majority of the cases, ion
A (rare-earth) is catalytically inactive and merely provides thermal stability, while
ion B (transition metal) is the active component.

4.2.1 Electrochemical Capacitor/Supercapacitor Application

With the high-power capability and relatively large energy density as compared to
conventional capacitors, electrochemical capacitors offer a promising approach to
meet the increasing power demands of energy storage systems in the twenty-first
century. Thus, supercapacitors have achieved great attention among energy storage
devices due to their ability to bridge the gap between power density and energy
density. High energy batteries (deliver energy consistently for a prolonged period)
and high-power capacitors (quick delivery and charging) are equally important in
energy storage/conversion field. Hence, obtaining high energy density at larger power
density becomes a great challenge to the researchers. Coming to the charge storage
mechanism in a supercapacitor device, there are electric double-layer capacitance and
pseudocapacitors depending up on the materials used as its active electrodes. Figure 6
represents the schematic illustration of the electrode–electrolyte interface for a super-
capacitor at its discharged and charged conditions. A supercapacitor stores energy
using either ion adsorption (electrical double-layer capacitors, EDLCs) or fast and

Fig. 6 Schematic
illustration of charge storage
mechanism in
supercapacitors; a before
charging and b in charged
condition
196 P. Muhammed Shafi

reversible faradaic reactions (pseudocapacitors). These two mechanisms can func-

tion simultaneously depending on the nature of the electrode material. Progress in
supercapacitor technologies can be credited to the continuous development of nanos-
tructured electrode materials. For EDLCs, proper control over the pore size and the
specific surface area of the electrode for an appropriate electrolyte solution is crucial
to ensure good performance of the supercapacitor in terms of both power delivery
rate and energy storage capacity. To further enhance the specific capacitance of the
electrode, the pseudocapacitance, due to the intercalation of foreign electro-active
species on the electrode material, can be coupled with the electrical double-layer
capacitance. The material which is used to fabricate electrode presents its own bene-
fits and challenges as this technology moves toward the next generation of superca-
pacitor devices. Generally, carbons or carbon derivatives belong to EDLCs, which
provide physical charge storage at the interface between electrode and electrolyte.
Activated carbon (AC) is the most popular and well-established EDLC electrode
so far. Pseudocapacitive materials undergo redox reactions to store more than one
charge per reactive surface site and hence usually deliver higher energy density than
EDLCs. The pseudocapacitance is a bulk storage mechanism unlike EDLC, which is
constrained to only the surface of the material. Transition metal oxides or conducting
polymers (CPs) are well known to depict this type of storage mechanism owing to
their switching ability between different oxidation states and the potential to store
charges along reactive groups in their polymer backbones, respectively.
As we already know the electrochemical properties of perovskite oxide, which is
being utilized for the electrodes and electrolytes of SOFCs, the application as pseudo-
capacitor electrode is unquestionable. The availability of multivalent transition metal
(B cation) and inherent property of oxygen vacancy at the perovskite oxide lattice
was first explored by Mefford et al. in 2014 [5], and then the idea of anion intercala-
tion became more relevant in perovskite-based pseudocapacitors. The strategy they
followed was just analogous to Hahn B. P. et al. where the cation vacancy is utilized to
have cationic charge storage [70]. There are numerous reports on perovskite oxides
based on LaMnO3 , LaCoO3 , LaNiO3 , LaFeO3 , etc., being used for pseudocapac-
itor electrode applications [5, 71–84], and few are tabulated in Table 5. However,
the storage mechanism based on anionic intercalation was explored more after the
Mefford et al. [5] findings. They prepared both the oxygen-deficient as well as oxygen
excess LaMnO3 electrodes and investigated the storage mechanisms. Interestingly,
their findings proved that the anionic intercalation is not only confined to oxygen-
deficient perovskite but also to oxygen excess compound though the rate is maximum
for oxygen-deficient structure. Thus, the anion intercalation-based storage mecha-
nism in perovskite oxide led to a new strategy to enhance the energy density and
performances of the pseudocapacitors. The anionic intercalation by the oxygen ion
diffusion through the bulk can be understood more clearly from the schematic repre-
sentation as shown in Fig. 7. Here, the oxygen ion from electrolyte intercalates to the
oxygen vacancy or surface leaving the proton to the electrolyte, where it combines
with hydroxyl ion and forms water. The mechanism can be explained as follows:
Table 5 Some perovskite-based supercapacitor with their specific capcitances, energy and power densities, and life span
Material Specific capacitance Energy density Power density Cycle stability References
La0.7 Sr0.3 NiO3−δ 719.5 F g−1 at 2 A 81.4 W h kg−1 500 W kg−1 90% after 2000 [71]
g−1 cycles at 5 A g−1
1 M Na2 SO4 as
electrolyte
Sr0.8 Ba0.2 MnO3 446.8 F g−1 at 0.5 A 37.3 W h kg−1 400 W kg−1 87% after 5000 [72]
g−1 cycles at 10 A g−1
0.5 M Na2 SO4 as
electrolyte
LaMnO3 609.8 F g−1 at 23.4 Wh kg−1 4214 W kg−1 _ [5]
2 mV s−1
1 M KOH as
electrolyte
SrCo0.9 Nb0.1 O2.418 108.125 mA h g−1 37.6 W h kg−1 433.9 W kg−1 95.7% after 3000 [73]
(778.5 F g−1 ) at 5 A cycles at 5A g−1
g−1
SrCo0.9 Mo0.1 O2.5092 168.88 mA h g−1 at 1 74.8 W h kg−1 734.5 W kg−1 97.6% after 10,000 [75]
A g−1 cycles at 10 A g−1
Perovskite Oxides as Advanced Energy Materials for Solid …

6 M KOH as
electrolyte
La0.85 Sr0.15 MnO2.25 102 F g−1 at 1 A g−1 3.6 W h kg−1 at 120 W kg−1 about 50% after 3000 [76]
1 M KOH as cycles at 2 A g−1
electrolyte
La0.8 Na0.2 Fe0.8 Mn0.2 O3 21.15 mA h g−1 (56.4 1.8 W h kg−1 _ [77]
F g−1 ) at 3 mV s−1
1 M H2 SO4 as
electrolyte
(continued)
197
Table 5 (continued)
198

Material Specific capacitance Energy density Power density Cycle stability References
Reduced LaNiO3 powder 28.75 mA h g−1 (230 3500 cycles at 5A g−1 [78]
F g−1 ) at 1 A g−1
6 M KOH as
electrolyte
LaMnO3 520 F g−1 at 1 A g−1 52.5 W h kg−1 1000 W kg−1 117% after 7500 [79]
0.5 M Na2 SO4 as cycles at 10 A g−1
electrolyte
LaNiO3 139.2 mAh g−1 at 65.8 Wh kg−1 1.8 kW kg−1 92.4% after 10,000 [74]
1.0 A g−1 cycles
6 M KOH
Y2 NiMnO6 77.76 F g−1 at 0.89 W h kg−1 19.27 W kg−1 70.17% after 1800 [80]
30 mA g−1 cycles
BiFeO3 nanowire/reduced graphene oxide 116.05 mA h g−1 18.62 W h kg−1 950 W kg−1 87.51% after 1000 [81]
(928.43 F g−1 ) at 5 A cycles at 5 A g−1
g−1
3 M KOH as
electrolyte
La0.7 Sr0 .3 CoO3−δ /Ag composite 118.59 mA h g−1 21.9 mW h cm−3 90.1 mW cm−3 85.6% after 3000 [82]
(517.5 F g−1 ) at cycles at 50 mA cm−2
1 mA cm−2
1 M KOH as
electrolyte
(continued)
P. Muhammed Shafi
Table 5 (continued)
Material Specific capacitance Energy density Power density Cycle stability References
La0.85 Sr0.15 MnO3 /NiCo2 O4 Core–shell 260.75 mA h g−1 63.5 W h kg−1 900 W kg−1 200% after 10,000 [83]
architecture (1341 F g−1 ) at 0.5 A cycles at 20 A g−1
g−1
6 M KOH as
electrolyte
CaTiO3 /active carbon 270 F g−1 at 1 A g−1 26.3 W h kg−1 375 W kg−1 Constant over 5000 [84]
6 M KOH as cycles at 1 A g−1
electrolyte
LaMnO3 /Mn3 O4 540 F g−1 at 1 A g−1 75 W h kg−1 1000 W kg−1 No change up to [85]
0.5 M Na2 SO4 as 50,000 cycles
electrolyte
Porous LaMnO3 58 F g−1 at 1 A g−1 43 W h kg−1 770 W kg−1 Stable for > 100,000 [86]
0.5 M Na2 SO4 as cycles
electrolyte
Perovskite Oxides as Advanced Energy Materials for Solid …
199
200 P. Muhammed Shafi

Fig. 7 Schematic illustration of oxygen ion intercalation in ABO3 -type perovskite oxides a with
oxygen vacancy and b with oxygen excess material

(a) For the material with oxygen vacancy (ABO3−δ )

• The charge imbalance due to the presence of oxygen vacancy in the ABO3−δ
is neutralized by reduction of 2δ amount of B3+ cations to B2+ state.

A3+ B 3+ O3 → A3+ [B2δ B(1−2δ) ]O3−δ

2+ 3+

• The oxygen ion from electrolyte OH− will intercalate to the oxygen vacancy
by leaving the proton (H+ ) to the electrolyte, where it combines with another
hydroxyl ion to form water and the filling of oxygen site oxidize B2+ to B3+ .

A3+ [B2δ B(1−2δ) ]O3−δ + 2δO H − ↔ A3+ B 3+ O3 + 2δe− + δH2 O

2+ 3+

The mechanism is schematically illustrated in Fig. 7a.

• Then, the diffusion of O2− ion will take place along the octahedral edges and
fill the vacancies with the oxidation of two B2+ to two B3+ per one oxygen
ion.
Perovskite Oxides as Advanced Energy Materials for Solid … 201

(b) For the material without any oxygen anion (ABO3 )

• Here, the perovskite oxide is in perfect form (A3+ B3+ O3 ).
• The excess oxygen is intercalated to the surface through diffusion of B cation
to the surface and oxidizing two B3+ to two B4+ states per one oxygen ion
intercalation.

A3+ B 3+ O3 + 2δO H − ↔ A3+ [B2δ B(1−2δ) ]O3+δ + 2δe− + δH2 O

4+ 3+

The mechanism is schematically illustrated in Fig. 7b.

• Thus, the diffusion of OH− is possible even into oxygen excess perovskite
structure by oxidizing 2δ amount of B3+ cations to B4+ state for a δOH−
concentration.

5 Conclusions

The thermal and electrochemical stability, tunable functionality and cost-effective

availability of perovskite oxides propelled the material to possess numerous appli-
cations. These include applications in all type of battery electrodes, especially of
metal-air batteries, all components of SOFCs, solar cell, photoelectrochemical cell,
and supercapacitor electrode applications. An array of cations can be placed in the
A or B site of the ABO3 -type perovskite oxide with maintaining the tolerance factor,
such that there is no hindrance to structural stability. Further, these cation arrays
can also tune the catalytic activity and control oxygen ion mobility by electrical
polarization, making it a potential candidate for various energy applications. Though
there are many components of different energy devices, which have been fabricated
using perovskite oxides, the direct applications to SOFC’s components and super-
capacitor electrodes are discussed and scientifically demonstrated in detail in this
chapter. This chapter mainly focused on the material science view of applications
rather than device engineering or technological developments. The tunable function-
ality of perovskite oxides by upholding the stability factor (tolerance factor) through
proper cationic substitutions and oxygen vacancy creation and also its role in oxygen
ion mediated ionic conductivity is further scientifically elucidated.

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Phase Change Materials

Rabab Jarrar

Abstract The world’s rapid increase of energy consumption and demand with the
environmental bad effects of fossil and traditional fuels prompted scientists and
researchers to search for methods of storing and reducing energy consumption. Phase
change materials (PCMs) are substances that have the ability to store and release
energy at constant temperature during their change of state and have been widely
investigated and used as thermal energy storage TES and thermal regulator. This
chapter discusses the main types of PCMs with their advantages and disadvantages,
some of the efforts and methods used by scientists to overcome these disadvantages
during the last three decades and to improve their performance and demonstrate their
most common thermal applications.

Keywords Phase change material · Latent heat · Thermal conductivity · Thermal

energy storage (TES) · Supercooling

List of Abbreviations

bcm Billion cubic meters

CNTs Carbon nanotubes
CSP Concentrating solar power systems
DSC Differential scanning calorimetry
DTA Differential thermal analysis
EG Expanded graphite
GO Grapheme oxide
GR Grapheme
HDPE High density polyethyelene
IEA International Energy Agency
LDPE Low density polyethyelene

R. Jarrar (B)
Palestine Technical University—Kadoorie, Tulkarm, Palestine
e-mail: [email protected]

© Springer Nature Switzerland AG 2020 205

S. J. Ikhmayies (ed.), Advances in Energy Materials,
Advances in Material Research and Technology,
https://doi.org/10.1007/978-3-030-50108-2_9
206 R. Jarrar

LHS Latent heat storage

NG Nanographite
PCMs Phase change materials
PEG Polyethylene glycol
PMMA Polymethyl methacrylate
SEM Scanning electron microscopy
SHS Sensible heat storage
TES Thermal energy storage
TWh Tera Watt -hour

1 Introduction

The intensive and exaggerated use of traditional energy, which depends on fossil
fuels as petroleum, its derivatives, coal and natural gas, causes extremely serious
problems to human beings as environmental pollution, global warming and acid
rain. In addition, these resources will vanish sooner or later. These facts led to the
search for sources of clean and renewable energy and methods of decreasing energy
consumption which achieve sustainable development and does not adversely affect
human health and the environment [1].
Figure 1 from International Energy Agency (IEA) shows the increase in word
natural gas production in the period of 1971–2018 as a traditional source of energy,
and at the same time Fig. 2 illustrates the increase of wind and photovoltaic electricity
production as a renewable energy sources from 2005 to 2018, while Fig. 3 shows
the percentage participation of types of traditional and renewable energy sources in
electricity generation for two years 1973 and 2017.

Fig. 1 World natural gas production from 1971 to 2016 by region (billion cubic meters, bcm.).
Source IEA (2018) World Energy Outlook. All rights reserved [2]
Phase Change Materials 207

Fig. 2 World electricity production from 2005 to 2017 by region (TWh): a by wind and b by solar
photovoltaic PV. Source IEA (2018) World Energy Outlook. All rights reserved [2]

Fig. 3 Source shares of electricity generation in (TWh) at the two years 1973 and 2017. Source
IEA (2018) World Energy Outlook. All rights reserved [2]
208 R. Jarrar

These figures and curves which are based on real data emphasize two facts: The
first one is the increase in the world consumption and demand of energy with time,
and the second fact is the attitude and continuous search for alternative and clean
energy sources which is obvious from the increase of the percentage participation of
renewable energy sources in the year 2017 compared with 1973.
Energy storage helps to optimize the use of energy and preserve it from being
lost, to be used when needed. Phase change materials (PCMs) are one of the most
important methods of thermal energy storage (TES), and the last three decades have
shown huge research activity in this field to study, discover and improve the properties
of different types of PCMs that can be used in many thermal applications.

2 Phase Change Material Definition

When heat is added to a solid material below its melting point, the temperature
starts to increase until the melting point is reached and then the temperature will
remain constant until all the solid material is melted. When more heat is added, an
increase in liquid temperature will occur until reaching the boiling point and again
the temperature will not increase by adding heat until all the material evaporates;
then, the temperature will continue in increasing as more heat is added [3]. This
behavior is illustrated in the heating curve of a typical substance as shown in Fig. 4.
The added heat in these portions of constant temperature is used to increase
the potential energy of the atoms or molecules of the material by increasing the
separation distance between them, so in both melting and evaporation, the distance
between molecules or atoms is changing to reduce the attractive forces and affect
the potential energy. This amount of heat absorbed at constant temperature by a
material during melting and boiling is called latent heat of fusion and latent heat of
vaporization, and the same amount of heat is released by cooling; the cooling curve
is the opposite of heating curve shown in Fig. 4.
The process of melting and the process of evaporation are called changes of state
or phase changes of a material, and in general changes of phase or state are:

Fig. 4 Heating curve of a

typical substance
gas
liquid- gas
Temperature

°C liquid

solid- liquid
solid

Heat Added
Phase Change Materials 209

– From solid to liquid and from liquid to solid (solid ↔ liquid)

– From liquid to gaseous state and vice versa (liquid↔ gas)
– From solid to gaseous state directly by a process called sublimation and from
gaseous state to solid by a process called deposition (solid ↔ gas)
Another type of phase change or state change may happen in some solid materials
when heat is used to change the crystal structure of the solid material from one crystal
structure to another (solid ↔ solid).
All these changes of state involve absorbing or releasing energy, and this is the
scientific principle or idea of phase change material.
So phase change materials (PCMs) are substances that absorb or release large
amounts of latent heat when they go through a change in their state or phase at nearly
constant temperature and are considered as thermal energy storage (TES) [4, 5].
To explain more heat is absorbed when the material changes from solid to liquid as
an example without raising temperature, and the same amount of heat is released when
solidified. This regulates and reduces changes in temperature in the environment
surrounding the phase change material [6].
TES is classified into two main types [7]:
– The first one is latent heat storage (LHS) or phase change materials
– The second type is sensible heat storage (SHS).
The two types are well described by Fig. 4. Latent heat is represented by the
horizontal portions and given by the equation:

Q=m×L

where
Q is the amount of heat
m is the mass of the material
L is the latent heat of fusion or evaporation in units of energy per unit mass.
Sensible heat is represented by the linear non-constant portions in which energy
stored in the material depends on the temperature difference, mass and specific heat
capacity of the material and given by the equation

Q = m c T

where
c: is the specific heat of the material in units of energy per unit mass per unit
temperature
T: is change in temperature.
Latent heat energy storage is considered more efficient than sensible heat storage
as the second type needs more amount of material to store the same amount of energy.
210 R. Jarrar

The most commercial applicable PCMs are those involving solid–liquid transi-
tions as liquid ↔ gas, and solid ↔ gas transitions need larger volume for containers
due to big volume changes upon transition of state; solid ↔ solid transitions have
got attention by researchers [8], but in general the heat exchange in this transition is
smaller than that in solid–liquid transition.

3 Properties of Ideal Phase Change Materials (PCMs)

PCMs used in thermal applications should have specified properties to make them
suitable for these applications. These properties are classified as thermal or physical,
kinetic, chemical and economical properties [9, 10].

3.1 Thermal—Physical Properties

– Melting temperature fits or matches the operating temperature range of the appli-
cation. So if PCMs are used in building applications, we choose PCMs of melting
temperature range (20–32 °C) and according to the geographic region of use.
– High latent heat (H) of fusion so as to obtain large quantities of heat with
reasonable volume of PCMs containers.
– Small volume change upon phase transformation (solid ↔ liquid) and small vapor
pressure at operating temperature to reduce the containment problem.
– Thermal stability after many cycles of heating and cooling of the PCM with no
significant changes in melting temperature and latent heat.
– High thermal conductivity of both solid and liquid phases to assist the charging and
discharging energy of the storage system, and this point is one of the challenges in
this field as nearly most PCMs have low thermal conductivity nearly in the range
of (0.13–0.33 W/m K) for organic PCMs and (0.5–0.9 W/m K) for inorganic ones
as reported by Nazir et al. [8] in his review depending on many articles [11–17],
and as a result intensive research efforts and developments are being conducted
to improve thermal conductivity of PCMs.

3.2 Kinetic Properties

– No or very little supercooling, where supercooling is the presence of a material

in liquid state in spite of having a temperature below its freezing point [5, 18], is
expressed by degree of supercooling which is the difference between the melting
and freezing temperature.
– High rate of crystal growth and reproducible crystallization.
Phase Change Materials 211

3.3 Chemical Properties

– Non-degradable or chemical stability after many cycles of heating and cooling.

– Non-corrosiveness.
– Safety issues as non-toxic, non-flammable and non-explosive.

3.4 Economical Properties

– Low cost in production and abundant.

4 Types of PCMs

Phase change materials are classified according to their chemical nature into two
main groups: organic PCMs and inorganic ones, a third and not a main group is
eutectic which is a homogenous mixture of two (binary), three (ternary) or more
from the two main groups. Figure 5 is a schematic representation of groups and
types of PCMs [7, 8, 19].

Fig. 5 Schematic
representation of PCM types
212 R. Jarrar

Each type of PCMs has its own properties with advantages and disadvantages;
none of them has all the physical, chemical and kinetic properties of an ideal PCM
mentioned before, and as a result, researchers are in continuous search to develop and
enhance the desired properties to fit different thermal applications. Table1 summa-
rizes properties, advantages and disadvantages of selected types from different groups
with some examples on each type [7, 8, 10, 13, 19–21].
Commercial paraffin waxes are less expensive than pure paraffins with moderate
latent heat, and they are obtained as by-products from the process of refining oil
and consisting of straight hydrocarbon chains with carbon atoms greater than 15
and contain also volatile compounds as toluene, ketone, formaldehyde which may
cause cancer so care must be taken when they are used in thermal applications. Their
melting temperatures are within the range of 5–67 °C, and they are widely used
because of their low cost and availability [7, 22].
The most important disadvantages of organic PCMs are their low thermal conduc-
tivity and their cost while for inorganic ones as salt hydrates are their thermal insta-
bility and supercooling taking into consideration that both groups suffer from their
low thermal conductivity except metals and metal alloys.
Metals and metal alloys with low melting temperatures are promising type of
PCMs due to their desirable properties mentioned in Table 1 [10].
Eutectic mixtures are widely investigated by researchers and scientists; these
include eutectic mixtures of organic materials alone [23–27], inorganic mixtures
[28] and organic–inorganic eutectic mixtures [29]. A decrease in melting tempera-
ture of binary and ternary mixtures is usually observed in comparison with single
components of the mixture.
Mixing different types of PCMs will produce a new material with modified melting
temperature and smaller in most cases than the single types, and this will provide a
melting temperature that may match with specific thermal application. The mixing
process also may improve or solve some of the problems or limitations in some
types of PCMs [28]. Mixing Na2 HPO4 .12H2 O salt hydrate with Na2 CO3 · 10H2 O
[30] produces novel thermal stable eutectic mixture of salt hydrates with decrease
in phase separation and a decrease in both supercooling and melting temperature in
comparison with mentioned single salt hydrates.
Nazir et al. [8] in their review of energy storage applications gathered information
and data from many research articles about melting temperatures of organic [11–13,
31], inorganic [12, 13, 15–17, 31, 32] and eutectic PCMs [11, 13–17, 32, 33] and
represented them in histograms shown in Figs. 6, 7, 8. Figures 6a–c are for organic
compounds including paraffin, polymers, fatty acids, sugar alcohols and others, while
Figs. 7a–c are for inorganic compounds as salt hydrates, salts and metals with melting
temperatures up to 1000 °C for some salts and Fig. 8 for eutectic PCMs.
Table 1 Properties, advantages/disadvantages and examples of selected types from different groups of PCMs [7, 8, 10, 13, 19–21]
Properties Advantages Disadvantages Examples
Paraffin – Linear alkanes of 8–40 – Stable – Low thermal conductivity Octadecane
carbon atoms of chemical – Non-corrosive around 0.2 W/m K C18 H38
formula Cn H2n+2 – Congruent melting – High cost Eicosane
– May have solid/solid – No or very small – Flammable C20 H42
transition between different supercooling
Phase Change Materials

crystalline structures
- Density around 900 kg/m3
– Obtained from petroleum
Fatty Acids – Derived from vegetable oils – Non-toxic – Moderately corrosive Lauric acid
– Have chemical formula – No supercooling – Expensive with higher cost Capric acid
CH3 (CH2 )n COOH – Stable and good behavior of than paraffin Palmitic
– Melting temperatures melting and solidification – Large change in volume acid
between 30–65 °C upon melting Myristic acid
– Latent heat nearly in the
range of (130–225 J/g)
(continued)
213
Table 1 (continued)
214

Properties Advantages Disadvantages Examples

Salt Hydrates – Chemical formula M.nH2 O – Cheap and abundance – Corrosive KF · 4H2 O
where M is a metal salt -Non-flammable – Low thermal conductivity but CaCl2 · 6H2 O
– Latent heat nearly in the – High energy density (high higher than Paraffin and fatty MgCl2 · 6H2 O
range of (150–250 J/g) latent heat/unit mass) acids Na2 SO4 · 10H2 O
- Wide range of melting – Non-toxic – Unstable after cycles of Na2 CO3 · 10H2 O
temperatures (5 – 130 °C) – Small change in volume melting and solidification Na2 HPO4 · 12H2 O
– Density 1500–2000 kg/m3 upon melting with phase segregation and
incongruent melting.
– They lose some water during
heating cycles and degrade.
– Supercooling
Metals and metal alloys – Some metals have low – High thermal conductivity – Cost Al, Mg, Zn, Ga
melting temperature as – High thermal reliability – Some metals in liquid state Bi44.7 Pb22.6 In19 · 1 Sn8.3 Cd5.3
Gallium Tm = 29.76 °C – Low vapor pressure as gallium is corrosive to
– High density – Small volume changes upon some containers as aluminum
phase transition containers
– High boiling points
– Thermal stability After
millions of cycles of melting
and solidification
Salts – Have high melting – Low cost – Low thermal conductivity Na2 CO3
temperatures up to 1000 °C – High latent heat – Thermal instability
– Used for high temperature – High corrosive to containers
thermal energy storage
applications
R. Jarrar
Phase Change Materials 215

Fig. 6 Melting temperatures Tm of some organic PCMs: a T m < 50 °C, b 50 °C < T m < 80 °C,
c T m > 80 °C. Reprinted from International Journal of Heat and Mass Transfer 129, Nazir et al.
[8]: Recent developments in phase change materials for energy storage applications: A review, 497,
2019, with permission from Elsevier

5 Applications of PCMs

This section demonstrates some of the most common applications of phase change
materials PCMs.

5.1 PCMs in Buildings

Phase change materials as a thermal storage in buildings are the most commonly used
application. PCMs with melting temperature in the range of 20-32 °C are widely used
in both passive (self-absorbing, storing and releasing heat) and active (depends on
pumps and fans in heat transfer) heating and cooling in buildings. PCMs may be
incorporated in building walls, floors, ceilings and may be used as a heat and cold
storage units [9].
The presence of PCMs in building walls or any building component partici-
pate in reducing sharp changes of indoor temperatures which in turn will reduce
energy consumption in heating and cooling. The incorporation of PCMs in buildings
decreases the temperature peaks by 3–5 °C inside the building, and this will decrease
energy consumption by air conditioning systems up to nearly 30% [34].
216 R. Jarrar

Fig. 7 Melting temperatures Tm of some inorganic PCMs: a T m < 50 °C, b 50 °C < T m < 220 °C,
c Tm > 220 °C. Reprinted from International Journal of Heat and Mass Transfer 129, Nazir et al.
[8]: Recent developments in phase change materials for energy storage applications: A review, 498,
2019, with permission from Elsevier

Fig. 8 Melting temperatures Tm of some eutectic PCMs. Reprinted from International Journal of
Heat and Mass Transfer 129, Nazir et al. [8]: Recent developments in phase change materials for
energy storage applications: A review, 497, 2019, with permission from Elsevier
Phase Change Materials 217

Fig. 9 Effect of incorporation of PCM on south and east surface wall temperature. Reprinted from
Build Environ 59, G. Evola et al. [36]: A methodology for investigating the effectiveness of PCM
wallboards for summer thermal comfort in buildings. p. 523, with permission from Elsevier

PCMs may be directly mixed with construction materials as concrete and gypsum
or immersed in brick blocks by capillary phenomenon, but these methods suffer some
drawbacks as the leakage problem and bad effects as corrosion on the construction
materials so macro- or and microencapsulation may be used to prevent leakage and
corrosion, and this is a process which will be explained later in Sect.6 [35]. Another
method used to avoid leakage is by the aid of a supporting material in a process
known as shape stabilization and will be explained later also in Sect. 6.
Organic PCMs as paraffins, fatty acids and inorganic ones as salt hydrates are
widely and commercially used in building applications.
Figure 9 illustrates and represents the effect obtained numerically [36] of inserting
PCM wall board on the inner surface of the building walls; the peak surface temper-
ature of south wall was reduced by1 °C, and the fluctuation of the temperature was
reduced from 7 °C to 4.8 °C for the south wall and reduced from 5.7 °C to 2.9 °C
for the east wall.

5.2 PCMs in Textiles

When PCMs are incorporated in textiles, they will provide comfort to human body
by absorbing excess heat from body and storing this heat as latent heat that will return
back to the body and environment when the temperature decreases and the PCMs
solidify. The change of state from solid to liquid and vice versa is nearly the most
common change of state used in textiles as this type of change occurs with small
volume change and vapor pressure. PCMs may be incorporated as microcapsules in
the synthetic fibers, or these microcapsules will be embedded in a coating compound
218 R. Jarrar

Fig. 10 PCM microcapsules in smart textile [Outlast Technologies Company] [38]

to coat the textiles or included in the structure of a foam which will be added to
the textile in lamination process, and hollow fibers may be used also and filled
with these microcapsules [37]. These capsules must have properties that suit and
fit this application as resistant to heat, chemicals and mechanical failure. Methods
of encapsulation of PCMs will be discussed later in this chapter. Figure 10 from
Outlast Technologies Company [38] illustrates the shape and working principle of
these capsules.
In addition of absorbing excess heat from body, these microcapsules will achieve
thermal insulation by building thermal barrier which will reduce heat transfer from
body to environment, as a result choosing PCMs with melting temperatures ranges
near body temperature will provide the thermal protection and maintain a constant
temperature at a comfortable level. The first incorporation of PCMs in textiles was
in suits for astronauts to protect them from temperature fluctuations in space and
then expands to sports clothing as athletes are exposed to generate lot amount of heat
during exercising and playing and need to get rid of this excess heat to feel comfort.
Nowadays, PCMs are being incorporated in jackets, sleeping bags, curtains, shoes
skiwear and others [38].

5.3 PCMs in Rechargeable Batteries

Phase change materials are used for cooling of rechargeable batteries as lithium-ion
batteries. Their low cost and high energy densities make these batteries widely used
in cell phones, laptops and electric vehicles. But the generation of excess heat during
discharging is one of challenges that need to be treated to prevent them from aging
[39].
Phase Change Materials 219

PCMs with suitable selected melting temperature in contact of the battery pack
will absorb the excess heat during discharging as latent heat of fusion at constant
temperature which controls the temperature of the battery.
As an example, Nasehi et al. [40] located three PCM shells with different thermal
properties (capric acid, eicosane and sodium sulfate decahydrate) around a battery
pack with different arrangements to choose the best arrangement leading to the lowest
battery temperature during discharge. They concluded that the best arrangement was
by locating the PCM with highest thermal conductivity closer to the battery and the
lowest in thermal conductivity as the outer shell by this arrangement they obtained
the smallest battery maximum temperature after 7200 s heat discharge.

5.4 PCMs in Photovoltaic PV Solar Modules

Another interesting application of PCMs is reported by Nazir et al. [8] in his review
in which phase change materials are integrated in PV modules to control and limit
the increase in the temperature of PV module which in turn lead to an improvement
in efficiency of the system [41, 42], and the heat removed from the PV module may
be used for water heating [43].

5.5 PCMs in Concentrating Solar Power Systems (CSP)

Concentrating solar power systems (CSP) concentrate sunlight using mirrors to a

small area to be used later after being converted to heat [44]. Thermal energy storage
of both types of latent heat and sensible heat can be used to store this heat energy
and shift its use to a later time of no solar radiation. PCMs absorb the concentrated
heat and store it as latent heat of fusion or evaporation during their phase transition,
and these amounts of heat can be obtained later or released during the reverse phase
transition.
Due et al. [1] in his review, related to the applications of phase change materials,
classified these applications according to the melting temperature ranges of PCMs
to four categories:
1. Low-temperature range applications [−20–5 °C]
2. Medium-low-temperature range applications [5–40 °C]
3. Medium-temperature range applications [40–80 °C]
4. High-temperature range applications [80–200 °C]
Incorporation of PCMs on the condenser and evaporator sides of refrigerators is
one of the applications in low temperature range which improves the removal and
heat transfer and enhances the coefficient of performance of the refrigerator by nearly
15% leading to a decrease in electrical energy consumption [45, 46].
220 R. Jarrar

Another application in this range is related to storing and transporting of food

and medicine products by refrigerated trucks to protect these sensitive products from
damage due to heat. The incorporation of paraffin as a PCM in the insulating walls
of a refrigerated truck reduced the heat flow by 16.3% per day as reported by Ahmad
et al. [47]. Paraffin, salt hydrates and eutectic mixtures of both types are used in these
applications [48, 49].
Building and textiles mentioned before are commonly used applications in the
range (5–40 °C), while cooling electrical devices is one of the applications in medium
range (40–80 °C). Electricity generation by solar energy is an example of the high
range of melting temperature greater than 80 °C. Sugar alcohol, salt hydrates, binary
and ternary mixtures of salts of alkali and alkaline nitrate metals are used as storage
unit for generating steam [50] in electricity generation at concentrating solar plants
CSP.
Metallic alloys of high melting temperature ranges are also used in concentrating
solar power plants CSP as heat storage units with high energy density and small
storage volumes in comparison with sensible heat storage units.
The role of PCMs in all above applications may be classified into two categories:
the first is thermal regulator and the second is thermal energy storage (TES) [19].
Incorporating PCMs in buildings, textiles, rechargeable batteries, electrical
devices and photovoltaic solar panels are examples of the first role or category as the
presence of PCMs prevents the fluctuating of temperature when choosing suitable
PCMs with melting temperatures in comfort zone for humans in building and textiles
and within the working range of the other applications.
PCMs with high melting temperatures as salts and alloys can be used as heat or
thermal energy storage units (TES) in concentrating solar plants (CSP) and represent
an example of the second category that stores available energy from daily solar
radiation to be used later when it is not available. Also PCMs can be used to store
excess heat or waste heat resulting from industrial and chemical processes to be used
later in heating applications [51].

6 Recent Developments and Improvements on PCMs

As mentioned before, both main groups of PCMs (organic and inorganic) do not
have all the required properties of an ideal PCM.
This section is devoted to discuss the main disadvantages and problems facing
the use of phase change materials and some of the most commonly used techniques
in solving these problems and improving the performance of PCMs.
The most important problems and disadvantages needed to be modified and solved
are:
– Low thermal conductivity
– Supercooling
– Thermal instability
Phase Change Materials 221

– Leakage of molten PCMs

– Volume and pressure variations during the phase change

6.1 Low Thermal Conductivity

The most important problem that restricts using PCMs is their low thermal conduc-
tivity for organic and inorganic ones, although the thermal conductivity of inorganic
PCMs is a little bit better than organic ones; anyhow for both types increasing thermal
conductivity will reduce the heat time of charging and discharging and improve the
performance of PCMs in all applications.
Kant et al. [52] in their review about advancement in phase change materials
for thermal energy storage applications and Kenisarin et al. [5] in their review about
solar energy storage using phase change materials reported most of the improvements
conducted by scientists to address the limitations and to improve the thermo-physical
properties of PCMs.
The methods used to increase the thermal conductivity are [5, 52]:
1. Metallic structures and metallic fins

The attachment of fins in the PCM container will increase the area of heat transfer and
improve the thermal conductivity. Figure 11 shows aluminum fins used by Singhet.al
[53] to improve thermal conductivity of polyethylene glycol (PEG 1000) which is an
organic phase change material with a melting temperature of 37.1 °C. The thermal
conductivity increases from 0.22 W m−1 K−1 for pure PEG to 9.4 W m−1 K−1 by
introducing the aluminum fin stack, i.e., an increase of more than 42 times by using
the fins.
Many researchers investigated the effect of finned structures [54–56]. Other
researchers carried out numerical and simulation studies [57–59] to obtain best fins
configuration and dimensions for best results.
Metallic slags and chips were embedded in paraffin wax PCM to improve its
thermal conductivity [60]. Aluminum, stainless steel metallic structure and coils’
effect on thermal properties of paraffin were studied by Hafner and Schwarzer [61].

Fig. 11 Aluminum fin stack

in R. Singh experimental
setup to improve thermal
conductivity of polyethylene
glycol (PEG) [53]
222 R. Jarrar

One of these structures is shown in Fig. 12 [6]. A six times improvement in thermal
conductivity of this structure with respect to pure paraffin was reported.
2. Carbon Additives to enhance thermal conductivity

Carbon powder, graphite, graphene, carbon fibers and carbon nanotubes (CNTs) as
materials with high thermal conductivity may be added to both organic and inorganic
phase change materials to obtain high thermal conductivity for PCMs. Carbon and
its derivatives (powder, graphite) are non-toxic, cheap, lightweight, non-aggressive
and cause no corrosion to PCMs containers and to construction materials; for these
properties, they have been investigated by many researchers [62, 63].
Li et al. [64] used mechanical agitation and ultrasonic vibrations to prepare
composites of paraffin with expanded graphite EG, graphene GR and graphene oxide
GO with 0.5–2% concentration ranges, and thermal conductivity and heat charge rates
were improved for all the composites with different types of additives and were the
best for graphene as shown in Fig. 13.
3. Metallic and Oxide metallic nanoparticles

Fig. 12 Aluminum filling

structure. Reprinted from
Renewable and Sustainable
Energy Reviews 11(9),
Kenisarin and Mahkamov
[5]: Solar energy storage
using phase change
materials, p. 1939, 2007,
with permission from
Elsevier

Fig. 13 Effective thermal conductivity ratio as a function of the concentration of graphite additives
[64]
Phase Change Materials 223

Nanoparticles have high surface area-to-volume ratio; this aspect increases the
thermal conductivity of PCMs if nanoparticles being incorporated in them [65].
Copper (Cu), gold (Au), silver (Ag) metallic nanoparticles and other nanoparticle
metallic oxides as copper oxide CuO, aluminum oxide Al2 O3 , titanium oxide TiO2
and others are used to enhance thermal conductivity.
One of the problems facing this method of thermal conductivity enhancement is
the dispersion of these nanoparticles in PCMs due to their high density and the weak
chemical/thermal interaction [56]. Some scientists used surfactants during prepara-
tion as Nouani et al. [66] who used sodium stearoyl lactylate in addition to vacuum
pump to get rid of air bubbles and ultrasonic vibrations to ensure a homogeneous
distribution of nanoparticles. An increase of 31% and 13% in thermal conductivity
of solid and liquid state respectively was obtained after the addition of 10 wt% of
nano-Al2 O3 to the paraffin sample.
The addition of nanoparticles to PCMs contributes also to solving the super
cooling problem as reported by Li et al. [67] as these nanoparticles play the role of
additional nucleating agent. They compared the effect of adding 0.5 wt% of different
types of nanoparticles, namely G-Al2 O3 , TiO2 , Cu and SiO2 to calcium chloride
hexahydrate CaCl2 .6H2 0 on supercooling and obtained the best value in decreasing
of supercooling from 5 °C supercooling in CaCl2 .6H2 0 with a normal surfactant to
0.2 °C for CaCl2 .6H2 0/0.5 wt% G-Al2 O3 PCM nanocomposite, after that they studied
the effect of different weight concentration of G-Al2 O3 from 0.5 wt% to 2 wt% in
steps of 0.5. A decrease in supercooling, time of melting and time of solidification
was observed for all concentrations, and an excellent thermal reliability of 1 wt%
concentration upon cycling was registered.
4. Porous metals and metallic foams

Porous metals are metals that have large volume of porosities, and this expression is
more general than metallic foam expression which is porous metals but is produced
by foaming processes. Some of metallic foams are open celled as a sponge and have
very large surface area per unit mass, and some of them are closed cell foams [68].
These cellular structures have large number of porosities nearly 76–95% porosity as
shown in Fig. 14 [69].
Their light weight, huge surface area and their ability to conduct heat and
electricity make them widely used in industrial and thermal applications.
One of these thermal applications is using PCMs incorporated in metallic foams
as passive cooling of electronic devices. The presence of these cellular structure will
decrease the time of melting of the PCM and accelerate the process of cooling of the
electronic device, i.e., enhance heat transfer between PCM and electronic device as
heat is considered a very important cause of electronic devices failure. The decrease
of time of discharging and charging of the PCM is due to enhancement in latent heat
transfer by this metallic structure which has large surface area in contact with PCM.
Chen et al. [70] used paraffin embedded in an aluminum foam and reported the
increase in rate of heat transfer during melting of paraffin due to the presence of the
foam.
224 R. Jarrar

Fig. 14 Open cell structures with various cell sizes (left) SEM image of an open cell stainless steel
foam(right) [from Fraunhofer Institute for Manufacturing Technology and Advanced Materials
IFAM, Branch Lab Dresden] [69]

Numerical and experimental investigations of the effect of copper foam and

porosity on rate of heat transfer for sodium nitrate [71], paraffin wax and other
commercial PCMs [72] were conducted, and all results emphasize the enhancement
behavior of heat transfer by foams.
5. Encapsulation of PCMs.

Encapsulation is the process of surrounding, covering or coating the PCMs by a

suitable shell in which the PCM is being the core. It is most likely as M&M sweat
with PCMs as the chocolate core, and the crispy candy part is the shell or cover.
Encapsulation is classified into three types depending on size of the final product:
1. Macroencapsulation > 1 mm
2. Microencapsulation (0–1000 µm)
3. Nanoencapsulation (0–1000 nm)
This process has many advantages. It prevents leakage of the PCM when being
in liquid state and avoids the interaction of the PCM with surroundings which may
cause corrosion of construction materials in building applications as an example,
safety issues by avoiding contamination of other materials as food and blood by
direct contact with PCM which may have some health hazards in addition to increase
in heat transfer especially when micro- and nanoencapsulation are used due to the
great surface area-to-volume ratio.
In macroencapsulation, the phase change material is filled or stored in packages
of spheres, tubes, pouches and panels to be incorporated in buildings products [73].
Plastic bottles of high and low density polyethylene (HDPE, LDPE), mild steel
and tin plated containers are commercially used. The temperature of the application
determines the type of the container or capsule such that plastic bottles are not used
in high-temperature applications, other required properties of capsules are related to
yield strength, non-flammability and thermal conductivity [74]. Figure 15 displays
some commercially macrocapsules [5].
In micro- and nanoencapsulation, the improvement in heat transfer is more
pronounced due to the increase in surface area-to-volume ratio. Polymers as
Phase Change Materials 225

Fig. 15 Some commercially

macrocapsules from TEAP
and EPS companies.
Reprinted from Renewable
and Sustainable Energy
Reviews 11(9), M. Kenisarin,
K. Mahkamov [5]: Solar
energy storage using phase
change materials, p. 1939,
2007, with permission from
Elsevier

polystyrene [75], polymethyl methacrylate (PMMA) are used as shell materials for
microencapsulation of paraffin, but because of this polymer low thermal conduc-
tivity it will have worse effects when used with PCMs with low thermal conductivity
such as paraffins. Some researchers [76] added nanographite NG to improve thermal
conductivity of the core material. Others used calcium carbonate as a shell [77],
and composites materials are also used for microencapsulation as silicon dioxide—
PS [78]. Gum Arabic is recorded and used as shell material for fatty acids [79]. The
encapsulation of salt hydrates with their corrosion to metals and their chemical insta-
bility is very preferred [80, 81]. Other desired properties must be found in the shell
material in addition to their resistance of corrosion are: flexibility, thermal stability,
low cost, non-flammability, non-toxic especially when used in food and blood cooling
applications and the ability of forming bonds with PCMs as mentioned by Hassan
et al. [43].
Methods of microencapsulation are divided into two main categories:
– Chemical methods
In this method, the shell is built around the core which is the PCM by chemical
reaction as in situ polymerization and interfacial polymerization.
– Physical methods
The core PCM material is being coated by mechanical or physical process as spray
drying and centrifugal methods. Details of both main methods are found in [43, 82].
Nanoencapsulation of PCMs is the most recent area of research in PCMs; nowadays,
nanoencapsulation is also used in drug delivery.
Nanocapsules of PCMs have shown better stable structure than macro- and
microcapsules [83] and better heat transfer due to decreasing capsule size which
will increase surface area-to-volume ratio. Some methods of nanoencapsulation are
similar to microencapsulation mentioned before as spray drying and polymerization,
226 R. Jarrar

but the recent and future development will focus on nanosize multilayer shells as
reported and explained by Shchukina [19]. But still more efforts must be carried out by
researchers to transfer these attempts of manufacturing and preparing nanocapsules
from research work in laboratories to commercial applications.

6.2 Thermal Instability

One of the drawbacks of salt hydrates as mentioned before is their instability after
heating cycles as a result of losing some of their water content. As an example,
heating of Na2 SO4 · 10H2 O salt hydrate above 32.35 °C will cause phase separation
and precipitation of the anhydrous salt Na2 SO4 . The addition of 2.9 wt% of acrylic
acid copolymer as a thickener prevent phase separation of Na2 SO4 · 10H2 O up to
100 cycles of heating and cooling [84]. Some researchers reported that the addition
of other salts up to 10 wt% did not change the melting temperature and latent heat
of the salt hydrate and enhanced thermal stability. The addition of 7wt% manganese
chloride hexahydrate with purity > 98% to magnesium hexahydrate with purity >
99.48% made the mixture stable after 1000 heating cycles with no change in melting
temperature and heat of fusion as reported by Nagano et al. [85].

6.3 Supercooling

As mentioned before, supercooling is one of the problems in some types of phase

change materials in which there will be delay in the beginning of the solidification
process, and additional cooling is needed to initiate it, as a result a delay in obtaining
the stored latent heat will occur which is not preferable in short term applications,
but it is useful in long-term applications. Water is a very common example of this
phenomenon. Pure water can be found in liquid state at very low temperatures below
0 °C (18).
Salt hydrates are the most common type of PCMs that suffer from supercooling.
Some of the methods used to decrease the degree of supercooling are [18]:
1. Addition of nucleating agents with similar crystal structure that will provide
nuclei to initiate crystallization and solidification, and this will decrease the
supercooling degree.
2. Using thickening agents which also contribute in reducing phase separation and
incongruent melting
3. Using rough surfaces of containers and capsules to provide heterogeneous nucle-
ation. It was found that as the roughness increases, the supercooling degree
decreases [86].
Acrylic acid copolymer (3–5 wt%) was used as a thickener agent for different
types of high Na-salt hydrates, while carbon powders, copper and titanium oxide in
Phase Change Materials 227

the micro range were used as nucleating agents. These nucleating agents were found
to decrease the degree of supercooling of a thickened Na2 HPO4 · 12H2 O salt hydrate
with acrylic acid copolymer from 20 °C to (0–1 °C) for carbon and titanium oxide
and to (0.5–1 °C) for copper [87]. The role of the thickener was to prevent phase
separation, and the nucleating agents provide the essential nuclei for crystallization
and solidification.
Mixing PCMs with nanoparticles is also considered a solution to supercooling as
these nanoparticles will play the role of nucleating agents for solidification process in
addition to enhancement of thermal conductivity as mentioned in the subsection 6.1.

6.4 Leakage of Molten PCMs

Encapsulation of PCMs mentioned before is the major method of preventing leakage

when PCMs are in liquid state. Shape stabilization is another process used to solve
this problem [88] in this process a supporting material as high-density polyethylene
HDPE is mixed with the PCM by melting the mixture at a high temperature and
then cooling it below the glass transition temperature of the polymer to become a
solid. PCMs incorporated in porous materials or metallic foams are shape-stabilized
PCMs; the metallic foam or the porous structure play the role of supporting material
that prevent leakage of phase change material if loaded or embedded in the structure
with suitable amount or weight percentage [89, 90]. Expanded graphite EG, single
and multiple carbon nanotubes CNTs with PCMs are all examples of shape-stabilized
PCMs that enhance the thermal conductivity, heat transfer and thermal properties in
addition to preventing leakage of the PCM in liquid state.

6.5 Volume and Pressure Variations During the Phase

Change

Volume and pressure changes during melting and solidification of PCMs are consid-
ered to be one of the problems facing the use of PCMs in thermal applications [91].
Encapsulation process by suitable shell materials with good mechanical properties
and flexibility to be able to withstand stresses resulting from volume changes and
pressure is considered to be a major solution of this problem. Inorganic shells have
good mechanical properties, good thermal properties but poor flexibility, while poly-
meric shells are more flexible with good mechanical properties but unfortunately low
thermal conductivity [78].
The addition of nanoparticles of good thermal conductivity to the polymeric shell
is expected to improve mechanical and thermal properties.
Graphene oxide (GO) nanosheets with poly(melamine-formaldehyde) shell were
prepared by Chen et al. [92] to encapsulate dodecanol PCM by in situ polymerization,
228 R. Jarrar

while a double shell of polystyrene and graphene oxide nanosheets were prepared as
a shell to encapsulate n-hexadecane PCM by Zhang et al. [93]. Both Chen and Zhang
succeeded in complete encapsulation of these PCMs, but thermal conductivity was
not greatly enhanced by Chen and was not reported by Zhang.
Stearic acid as a core PCM material was successfully encapsulated with reduced
graphene oxide multilayer nanosheets by Advincula et al. [94] by using a pickering-
type emulsion technique. The thermal conductivity of encapsulated stearic acid by
this method was enhanced in comparison with stearic acid, but a wider range of
melting and crystallization temperature were reported.

7 Experimental Methods Used to Determine PCMs

Thermal Properties

Thermal properties of PCMs are determined by four principal methods: conventional

calorimetry, differential scanning calorimetry (DSC), differential thermal analysis
(DTA) and T-History method [95]
The most common technique used to determine the latent heat and the melting
temperature is differential scanning calorimetry (DSC). Samples of small amount
(5-10 mg) of the PCM under investigation and a reference sample are used in sealed
aluminum pans. The samples will be heated above the melting point, then cooled and
heated again at constant rate under nitrogen atmosphere. The latent heat is determined
from the area under the melting peak, and the melting temperature is taken to be
the intersection of the steepest line at leading edge of the melting peak with the
temperature horizontal axis.
Differential thermal analysis (DTA) was the earliest thermal measurement tech-
nology used. The temperature difference between the PCM sample and a reference
material is recorded when both were given the same amount of heat this temperature
difference is due to their difference in thermal properties. This method could be used
to measure the specific heat capacity and the phase change latent heat but DSC is more
accurate than DTA as both samples in DSC are kept at the same temperature, and
the difference in heat flow between the PCM sample and the reference is recorded.
Both DSC and DTA use small size samples, and this sometimes lead to differences
compared to results of large sample size of PCMs as a result scientists sometimes use
the T-history method to obtain thermal properties of larger samples. In this method,
the temperature versus time curves of the PCM and a reference are recorded under
natural convection condition and from these curves and using the calculations and
the method proposed by Yinping et al. [96] heat of fusion, specific heat and thermal
conductivity of PCMs may be determined. An explanation and comparison between
most techniques used to obtain thermal properties of PCMs are found in the review
article of Xie et al [97].
Phase Change Materials 229

8 Future Work and Interests

The encapsulation process described above was used to solve more than one problem
or limitations in PCMs such as low thermal conductivity, leakage problem and
volume expansion of the PCM during phase transition. This process enhances the heat
exchange and thermal properties due to large ratio of surface area to volume espe-
cially in nanocapsules. So I think future work should focus on improving methods
of encapsulation and using nanoparticles and nanostructures both in core and shell
to enhance thermal, mechanical properties of capsules and decrease supercooling by
providing nucleating agents which will participate in solving another problem.
Metals and metal alloys are good candidates for both high and low thermal
applications, overcoming the gap between global energy needs and available
resources.
Finally, more efforts in translating research and developments in phase change
technology to more commercial products and applications are definitely needed.

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