B ANGLADESH U NIVERSITY OF E NGINEERING

AND T ECHNOLOGY

Modeling and Simulation of Dye

Sensitized Solar Cell

Supervisor:
D R . M OHAMMAD J AHANGIR A LAM

Author:
Samit Shahnawaz Miftah(1406101)
Kristi Rahman (1406165)

Department of Electrical and Electronic Engineering

April 19, 2019

Declaration of Authorship
This is to certify that the work presented in this thesis titled “Modelling and Sim-
ulation of Dye Sensitized Solar Cell” is the outcome of the study carried out by
us under the supervision of Dr. Mohammad Jahangir Alam. It is also declared
that neither this thesis nor any part of it has been or being submitted elsewhere
for the award of any degree or diploma.

Authors:
Samit Shahnawaz Miftah
Student ID. 1406101

Signed:

Kristi Rahman
Student ID. 1406165

Signed:

Supervisor:
Prof. Dr. Mohammad Jahangir Alam
Department of Electrical and Electronic Engineering,
Bangladesh University of Engineering and Technology,
Dhaka-1205

Signed: .
 Abstract
In this era the demand for energy is highly increasing. To meet the need of the
increasing power consumption researchers are trying to invent new methods of
highly efficient power generation procedure. With this view dye sensitized solar
cell has been a great scope for the researchers to generate power efficiently. New
research about the materials, electrodes, sensitizers which are used in DSSC are
going on to increase the power generation efficiency. TCO plays a great role in de-
termining the power generation by the DSSC. So different types of materials have
been put under the research to find the best material among them to ensure low
absorption of photons. In this thesis we have studied the absorption coefficient
of two inorgananic material, ITO and FTO and one organic material PEDOT:PSS.
A brief discussion of the material best suited as TCO has been given here. Many
organic, inorganic and natural dye sensitizers have been trailed in the past in an
attempt to reduce the cost, improve the performance and make the dye-sensitized
solar cell (DSSC) technology more environment-friendly. Ruthenium-based com-
plexes are by far the most efficient dye sensitizers and have been commercially
used in DSSC technology and achieved approximately 12–14% conversion effi-
ciency. But the problems associated with ruthenium complexes are high cost and
toxicity which drive the researchers to identify new metal-free and environment-
friendly dye sensitizers such as organic and natural sensitizers. In this regard,
natural dye sensitizers due to their low-cost extraction and environment friendly
nature are becoming a new area of research in the field of DSSC technology.
These dye sensitizers are naturally occurring dye pigments, such as chlorophyll,
betanins, carotenoids, anthocyanins and tannins extracted from flowers, leaves,
stems and roots of plants using water, acetone and/or alcohols. At present, the
efficiency of natural dye sensitizers is quite low compared to ruthenium-based
dye due to selective light absorption. Recently, highest recorded efficiency of
2% has been reported using cocktail of natural dyes extracted from flowers. At-
tempts have been made to improve the performance of natural dye sensitizers by
making cocktails and/or by using a variety of solvents for the extraction of dye
molecules. A brief comparison among different types of sensitizers and find out
the best suited sensitizer for a modern day DSSC is also the focus of our study.
 Contents

Declaration of Authorship i

Abstract ii

1 Introduction 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Early and Recent Development of DSSC . . . . . . . . . . . . . . . . 3
1.3 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Thesis Objective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5 Thesis Layout . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2 Photovoltaic Cell 8
2.1 Photovoltaic Cell Basics . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.2 Solar Cell Radiation and Ideal Conversion Efficiency . . . . . . . . . 9
2.3 Characteristic Equation of a Solar Cell . . . . . . . . . . . . . . . . . 11
2.4 Open-circuit voltage and short-circuit current . . . . . . . . . . . . . 12
2.5 Effect of Physical Size . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.6 Series Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.7 Shunt Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.8 Reverse Saturation Current . . . . . . . . . . . . . . . . . . . . . . . 15
2.9 Ideality Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.10 Maximum Power(Pmax ), Current at PMax (IMP ), Voltage at Pmax (VMP ) 17
2.11 Fill Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.12 Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

3 Dye Sensitized Solar Cell 20

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2 DSSC Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2.2 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
TCO Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . 23
TiO2 Nano-Particle . . . . . . . . . . . . . . . . . . . . . . . . 24
Ru-Complex Photosensitizer . . . . . . . . . . . . . . . . . . 24
Redox Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . 25

iii
 Counter-Electrode . . . . . . . . . . . . . . . . . . . . . . . . 26
Sealing Materials . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.3 Transparent Conductive Film . . . . . . . . . . . . . . . . . . . . . . 27
3.3.1 Choosing the Right Materials . . . . . . . . . . . . . . . . . . 27
Indium-Tin Oxide . . . . . . . . . . . . . . . . . . . . . . . . 27
Fluorine-Doped Tin Oxide . . . . . . . . . . . . . . . . . . . . 28
PEDOT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.4 Photo-Sensitizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.4.1 Ru-Complex Sensitizer . . . . . . . . . . . . . . . . . . . . . . 32
3.4.2 Metal-Free Organic Sensitizers . . . . . . . . . . . . . . . . . 34
3.4.3 Natural Dye . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Chlorophyll . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Carotenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Flavonoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Betalain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

4 Modeling of The Proposed DSSC 39

4.1 Modeling a DSSC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2 Modeling the Characteristic Equation . . . . . . . . . . . . . . . . . 40

5 Simulation and Result 43

5.1 Assumptions and Conditions . . . . . . . . . . . . . . . . . . . . . . 43
5.2 Current Density and Power Density Calculations . . . . . . . . . . . 43
5.3 Relation of generated Current and Power with Absorption Coeffi-
cient of TCF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
5.4 Improvement with Dye . . . . . . . . . . . . . . . . . . . . . . . . . . 46

6 Conclusion and Suggestion For Future Work 48

6.1 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.2 Suggestion For Future Work . . . . . . . . . . . . . . . . . . . . . . . 50

Bibliography 51
 List of Figures

1.1 A 3D Model of an DSSC . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.1 Spectral Irradiance vs Wavelength . . . . . . . . . . . . . . . . . . . 10

2.2 Electrical Equivalent Model for an Ideal Solar Cell . . . . . . . . . . 10
2.3 Effect of change in Series Resistance . . . . . . . . . . . . . . . . . . 14
2.4 Effect of Change in Shunt Resistance . . . . . . . . . . . . . . . . . . 15
2.5 Effect of Reverse Saturation Current . . . . . . . . . . . . . . . . . . 16
2.6 Effect of Ideality Factor . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.7 VMP and IMP from the I-V Curve . . . . . . . . . . . . . . . . . . . . 17
2.8 Fill Factor from I-V Graph . . . . . . . . . . . . . . . . . . . . . . . . 18
2.9 I-V curve in absence and presence of light . . . . . . . . . . . . . . . 19

3.1 DSSC simplified Mechanism (a)[20], Schematic structure of nanocrys-

talline dye-sensitized solar cell (DSSC) presenting the mechanism
of electric power generation and scanning electron microscope (SEM)
photograph of a typical nanocrystalline TiO2 electrode[20] . . . . . 22
3.2 Molecular Structures of typical Ru-Complex photosensitizers for
DSSC (a), Absorption spectra of N3 dye and black dye represented
by absorbance and light harvesting efficiency, 1-T (T:transmittance):
(—) N3 dye, (- - -)black dye(b).[20] . . . . . . . . . . . . . . . . . . . 25
3.3 Absorption Coefficient, α (cm-1 ) vs wavelength, λ . . . . . . . . . . . 29
3.4 Electrical and Optical Properties of FTO . . . . . . . . . . . . . . . . 30
3.5 Absorption Coefficient, α, vs incident photon energy . . . . . . . . . 31
3.6 Ru Complexes Developed by Nazeeruddin et al. . . . . . . . . . . . 32
3.7 Molecular structure of T66 and current-potential curves of assem-
bled DSSC (taken from [37]) . . . . . . . . . . . . . . . . . . . . . . . 33
3.8 Molecular structures of Ru(II) sensitizers TFRS-1–3 and absorption
spectra of TFRS, N719 in DMF (taken from [38]) . . . . . . . . . . . 34
3.9 Property Table of some Metal-Free Organic Dyes . . . . . . . . . . . 35
3.10 Absorbance of Chlorophyll . . . . . . . . . . . . . . . . . . . . . . . 37
3.11 Absorbance of Flavonoids . . . . . . . . . . . . . . . . . . . . . . . . 38
3.12 Absorbance of Betalain . . . . . . . . . . . . . . . . . . . . . . . . . . 38

4.1 Designed Model of DSSC . . . . . . . . . . . . . . . . . . . . . . . . 39

v
5.2 I-V and P-V Characteristics of FTO coated DSSC . . . . . . . . . . . 44
5.3 I-V and P-V Characteristics of PEDOT coated DSSC . . . . . . . . . 45
5.4 Effect of Absorption Coefficient on Current and Power of DSSC . . 45
5.5 Characteristic Graph of DSSC with N719 dye . . . . . . . . . . . . . 46
5.6 Characteristic Graph of DSSC with TBA . . . . . . . . . . . . . . . . 46
5.7 Characteristic Graph of DSSC with TER . . . . . . . . . . . . . . . . 47
 List of Tables

3.1 Absorption Coefficient(α) of Materials . . . . . . . . . . . . . . . . . 28

4.1 Layer Thickness used for modeling our DSSC . . . . . . . . . . . . . 40

vii
 List of Abbreviations

DSSC Dye Sensitized Solar Cell

IPCE Incident Photon-to-Electron Conversion Efficiency
TCF Transparent Conducting Film
TCO Transparent Conducting Oxide
MLCT Metal (to) Ligand Charge Transfer
HOMO Highest Occupied Molecular Orbital
LUMO Lowest Unoccupied Molecular Orbital
TBP Tert-Butyl-Pyridine
DMHImI DiMethyl-HexylImidazolium Iodide
PEDOT Poly (3, 4-EthyleneDiOxyThiophene)
PEDOT:PSS Poly (3, 4-EthyleneDiOxyThiophene) PolyStyrene Sulfonate
MPP Maximum Power Point

viii
 Physical Constants

Speed of Light, c0 = 3 × 108 m s−1

Charge of electron, q = 1.6 × 10−19 C
Boltzmann Constant, k = 1.380 648 52 × 10−23 kgm2 s−2 K−1
Planck’s Constant, h = 6.626 070 04 × 10−34 kgm2 s−1
Concentration of electrons n0 = 1 × 1016 cm−3
at equilibrium at Dark,

ix
 List of Symbols

a distance m
P power W (J s−1 )

T Absolute Temperature K

m Ideality Factor

n( x ) The excess concentration of the photogenerated elec- cm-3

trons at position x within the film measured from the
TiO2 /transparent conducting oxide

n0 The concentration of electrons under equilibrium con- cm-3

ditions in dark

τ The Conduction Band Free electron time ms

D The diffusion coefficient of electrons cms-1

Φ0 The illumination intensity cm-2 s-1

α Light Absorption Coefficient of the porous film cm-1

x
 Chapter 1

Introduction

1.1 Introduction
Solar energy is rapidly becoming the most viable, eco-friendly and sustainable
alternate source of renewable energy[1]. There has been an exponential growth
in the production of solar cells over the past two decades[1–3]. One of the most
promising means of solar energy conversion is the use of dye-sensitized solar
cells (DSSC) first developed by Grätzel et al. in 1991 and has attracted much
attention in the last couple of decades leading to a plethora of publications on the
subject[4][5][6]. The Interest in DSSC and more precisely Natural Dye Sensitized
Solar Cell (NDSSC) is mainly due to its low cost of fabrication and environmental
friendly nature[11,12]. A 3D model of an DSSC is shown in Fig. 1.1.

F IGURE 1.1: A 3D Model of an DSSC

1
Currently, DSSC has the potential to convert photons from sunlight to electrical
energy at 13% efficiency[7]. An intensive effort has been directed towards the op-
timization of the various components of DSSC with the goal of fabricating more
efficient and stable cells. The DSSC as displayed in the above figure is composed
of a redox couple electrolyte system, typically iodide and tri-iodide complex,
sandwiched between two glass plates, a photo-anode and a counter electrode.
The redox couple in the electrolyte is used to regenerate the oxidized dye. The
photo-anode consist of glass plate coated with a thin layer of transparent conduc-
tive oxide (Fluorine doped tin-oxide, FTO or Indium doped tin-oxide, ITO) and
a monocrystalline semiconductor (usually titanium dioxide, TiO2 ) which serves
as a scaffold for the dye sensitizer. The counter electrode is also made up FTO
covered glass slide coated usually with a thin film of Platinum or Carbon for the
catalysis of the redox reaction with electrolyte.
The total efficiency of the DSSC is dependent on the nature, optimization and
compatibility of each one of the components of the solar cell and more particu-
larly the photo-anode which plays a vital role in the charge generation and trans-
fer processes. To increase the power conversion efficiency of DSSC, a nanostruc-
tured porous titanium dioxide with a wide band gap and large exciton binding
energy is typically used in constructing the photo-anode. The large surface area
of the nanostructured TiO2 insures the adsorption of sufficiently large number of
dye molecules for efficient harvesting of radiant energy. The dye, typically, with
a wide and intense absorption spectrum is adsorbed on the TiO2 via anchoring
groups such as carboxylic, carbonyl and hydroxyl located on the dye molecule.
A strong adsorption of the dye unto the nanostructured TiO2 is required for the
efficient electron injection into the conduction band of the TiO2 semiconductor.
The dye sensitizer anchored on the surface of titanium dioxide absorbs photons
and gets electronically excited. Energy is produced when the excited electron
moves from the valence band to the conduction band of the semiconductor. The
electrolyte (I- /I3- ) donates electron back to the dye. The sensitizers currently
used in the fabrication of solar cells are transition metal coordination complexes
such as Ruthenium (II) carboxylated polypyridyl complexes, due to their intense
charge-transfer absorption in the whole visible range and highly efficient metal-
ligand charge transfer transition (MLCT)[8][9]. Natural dyes are however more
desirable than these synthetic dyes because they are more economical, easily at-
tainable, and abundant in supply and environmentally friendly[9][10]. In ad-
dition, they turn to have large absorption coefficient owing to allowed π to π*
transitions.

2
1.2 Early and Recent Development of DSSC
In 2003, a group of researchers at the Swiss Federal Institute of Technology has re-
portedly increased the thermostability of DSSC. The stability of the device matches
that of a conventional inorganic silicon-based solar cell. The cell sustained heat-
ing for 1,000 h at 80◦ C. They also increased dye tolerance to water.

In 2006, the first successful solid-hybrid dye-sensitized solar cells were reported.

In 2008, An article published in Nature Materials demonstrated cell efficiency

of 8.2% using a new solvent-free liquid redox electrolyte consisting of a melt of
three salts, as an alternative to using organic solvents as an electrolyte solution.

In 2009, A group of researchers at Georgia Tech made dye-sensitized solar cells

with a higher effective surface area by wrapping the cells around a quartz opti-
cal fiber.[37][38] The researchers removed the cladding from optical fibers, grew
zinc oxide nano-wires along the surface, treated them with dye molecules, sur-
rounded the fibers by an electrolyte and a metal film that carries electrons off the
fiber. The cells are six times more efficient than a zinc oxide cell with the same
surface area.

In 2010, Researchers at the École Polytechnique Fédérale de Lausanne and at the

Université du Québec à Montréal claim to have overcome two of the DSC’s major
issues:

• "New molecules" have been created for the electrolyte, resulting in a liquid
or gel that is transparent and non-corrosive, which can increase the photo-
voltage and improve the cell’s output and stability.

• At the cathode, platinum was replaced by cobalt sulfide, which is far less
expensive, more efficient, more stable and easier to produce in the labora-
tory.

In 2012, Northwestern University researchers announced a solution to a primary

problem of DSSCs, that of difficulties in using and containing the liquid elec-
trolyte and the consequent relatively short useful life of the device. This is achieved
through the use of nanotechnology and the conversion of the liquid electrolyte to
a solid. The current efficiency is about half that of silicon cells, but the cells are
lightweight and potentially of much lower cost to produce.

In 2018, Researchers have investigated the role of surface plasmon resonances

present on gold nano-rods in the performance of dye-sensitized solar cells. They

3
found that with an increase of concentration in the nano-rods, the light absorp-
tion grew linearly; however, charge extraction was also susceptible to the con-
centration. With an optimized concentration, they found that the overall power
conversion efficiency improved from 5.31 to 8.86% for Y123 dye-sensitized solar
cells.

1.3 Motivation
Among sustainable technologies, such as tidal power, solar thermal, hydropower
and biomass , photovoltaic technology is regarded as the most efficient[11]. In
1954, the first practical photovoltaic cell using diffused silicon p-n junctions was
designed at Bell Laboratories, with an efficiency of 6%. The important means
of producing high-efficiency solar cells are reducing reflectance, trapping light
in the cell and increasing light absorption[12]. Silicon solar cells have achieved
electricity conversion efficiencies ranging from 15% to 20%. However, the high
fabrication cost and the usage of toxic chemicals in producing highly purified
silicon during the manufacturing process has motivated the search for an envi-
ronmentally friendly, low-cost solar cell. Dye-sensitized solar cells (DSSCs) have
received considerable attention since O’Regan and Grätzel reported a remarkably
high conversion efficiency of nearly 10%[13] using nanocrystalline mesoporous
TiO2 film. However, these organic solar cells are still limited to low power con-
version efficiencies[12].
DSSCs are photonic devices that convert visible light into electricity and are based
on a porous thin film of a wide-bandgap semiconductor oxide modified by dye
molecules. The manufacturing cost of DSSCs, which are 3 rd -generation solar
cells, is approximately 1/3 to 1/5 times that of silicon solar cells[4]. This type of
film enhances the light absorption due to its sponge-like characteristics and in-
creased surface area.
A typical DSSC consists of a transparent conductive oxide (TCO), semiconduc-
tor oxide, dye sensitizer, electrolyte and counter electrode. TCO substrates must
be highly transparent (transparency > 80%) to allow the maximum passage of
sunlight to the active area [14]. The TCO material characteristics determine the
efficiency of DSSCs [1]due to the efficient charge transfer of electrical conductiv-
ity to minimize energy losses. Fluorine tin oxide (FTO, SnO2:F) and indium tin
oxide (ITO, In2O3:Sn) are typical conductive oxide substrates consisting of soda
lime glass coated with fluorine tin oxide or indium tin oxide, respectively. The
transmittance of ITO films are over 80% in the visible region, with a sheet re-
sistance of approximately 18 Ωcm-2 , whereas FTO films exhibit a transmittance
of approximately 75% with a sheet resistance of 8.5 Ωcm-2 [14]. Sima et al. con-
ducted a study based Int. J. Electrochem. Sci., Vol. 10, 2015 2862 on FTO and
ITO glass substrates sintered at 450 ºC [15]. They found that upon sintering, the

4
sheet resistance of ITO increased from 18 Ω/cm2 to 52 Ω/cm2 , while the sheet
resistance of FTO remained ) of DSSCs based on FTO and ITO are approximately
constant. The overall conversion efficiencies 9.4% and 2.4%, respectively. Thus,
FTO is strongly recommended for use in DSSC fabrication due to its conduction
properties and stable sheet resistance temperature.
The search for new electrodes that are solution processable and able to produce
a comparable or higher performance is one of the main pursuits of organic so-
lar cells studies. The electrode must provide both high optical transparency and
high electrical conductivity concomitantly. In the last few years, several vari-
eties of materials have been used as an electrode in DSSC, including carbon nan-
otubes, Ag nanowires, oxide derivatives and conjugated polymers. One of the
predominant materials that is used is doped polythiophene derivative, poly(3,4-
ethylenedioxythiophene) PEDOT. However, the PEDOT itself exhibits a poor sol-
ubility in any solvent, resulting in a non-optimized morphology. A mixture PE-
DOT:PSS can be dispersed in water, showing a high-quality film[16]. However,
the insulator properties of PSS can increase the resistivity of the film.
This study indicates a progress in DSSCs and a large improvement in the mate-
rials used as TCO in DSSCs in particular. DSSCs were assembled using different
materials for the transparent conductive oxide for comparison among the perfor-
mance of the material. The performance of each material was evaluated based
on photoelectrochemical parameters, including the open circuit voltage (Vcc),
short circuit current (Isc), fill factor (FF) and overall conversion efficiency (η) from
the current-voltage curve. Thisstudy covers several types of materials that have
paved the way for better-performing solar cells and directly influenced the sta-
bility and reliability of DSSCs. The new research trend as well as the previous
research has been highlighted to examine the key challenges faced in developing
the ultimate DSSCs.

1.4 Thesis Objective

The objective of our thesis is to study the construction of a DSSC, its mechanism,
and the effect of change in the properties of the materials. We have simulated
a DSSC model to study them. Sun light is available for free everywhere, but
the guarantee of using this light for solar power is restricted to solar farms and
rooftop panels. Recently, transparent solar cells caught the attention of scientists
due to their variety of possible applications in our daily lives. Transparent solar
cells are already in use for these applications in some countries, while others are
for the far future, once their efficiency is improved. Transparent solar cells can
transform crowded cities from exclusively power consumers into power plants.
Building integrated photovoltaics, also known as BIPV, is the nearest application
for transparent solar cells. If all the buildings with 90% glass on their surface

5
used transparent solar cells printed on the surface of the glass, the solar cells
have the potential to power more than 40% of that building’s energy consump-
tion. Another application of transparent solar cells is in automobile and electronic
devices. If these applications used TSC in their glass surfaces, people could have
cars that do not need fuel or devices that can be self-charged from the sun. Solar-
powered vehicles are a desired application of TSC, with cars, air planes, trains,
and boats potentially being powered with solar energy. TSC has the potential to
power all the electronic devices that we use in our daily lives, from tablets, MP3
players, cell phones, and e-readers, to laptops and other portable devices. Trans-
parent solar materials and semi-transparent materials started to be developed in
the past few years. Some companies have implemented transparent solar cells
with reasonable efficiency but not enough to compete with silicon solar panels.
However, this invention has a high potential of turning every glass surface in the
advanced world into a solar panel. Researchers are now working to improve the
efficiency of TSC without sacrificing transparency; this is expected to be achieved
in the next 5 years. There are approximately nine technologies that apply to the
fabrication of transparent solar cells, and they are a focal point of current research
due to market demand and the potential applications of transparent solar cells
(TSC). The centres of research that report some success with TSC are in Japan,
Germany, the USA, and India. It should be noted that 90% of these technologies
use an FTO or ITO conductor on glass. In this thesis we have discussed how the
emergence of PEDOT:PSS has achieved the best transparency over FTO and ITO.
A detailed analysis of efficiency in power generation using different organic and
inorganic material as transparent conductive film at AM1.5 and AM0 position of
the sun and from that analysis, an optimized and cost efficient dye sensitized so-
lar cell structure has been proposed. Also the problem faced during the thesis
work and the solutions we found to those problems have been discussed in this
thesis briefly.

1.5 Thesis Layout

The thesis includes a total of six chapters. Here is a summary of each chapter:
Chapter 1 is the introduction chapter which includes a brief summary of work
done with dye sensitized solar cell in a commercial level around the world, a
short history of development of DSSC, a brief review on recent developments of
DSSC around the world and our thesis objectives.
Chapter 2 describes the operation principles and basics of photovoltaic cells in
some more details along with some basic theory about PV cell.
Chapter 3 provides a detailed structure of DSSC and describes the various materi-
als of used for producing the cell. Chapter 4 describes the generation mechanism
and theory related to simulation.

6
The simulated results as to generation, absorption, efficiency , power and Fill Fac-
tor have been discussed in chapter 5.
Finally in chapter 6, concluding remarks and scope for future works are pre-
sented.

7
 Chapter 2

Photovoltaic Cell

2.1 Photovoltaic Cell Basics

The photovoltaic effect or the generation of voltage when a device is exposed
to light, was discovered by Becquerel in 1839, in a junction formed between an
electrode and an electrolyte. Since then there had been reports of similar effects
on different solid state devices. The first photovoltaic effect of substantial EMF
voltage was observed by Ohl on a silicon p-n junction in 1940. The photovoltaic
effect on Ge was reported by Benzer in 1946 and by Pantchechnikoff in 1952.
It was not until 1954 that the solar cell received much increased interest, initi-
ated by the works of Chapin et al. on single-crystal silicon cells anf of Reynolds
et al. on Cadmium-Sulfied(CdS) cells. To date, solar cells have been made in
many other semiconductors, using various device configurations, and employ-
ing single-crystal, poly-crystal, and amorphous thin-film structures. A solar cell
is similar to a photodiode. The photodiode can be operated in a photovoltaic
mode, that is, it is unbiased and connected to a load impedance similar to a solar
cell. However, the device designs are fundamentally different. For a photo-diode
only a narrow wavelength range centered at the optical signal wavelength range
is required. Photo-solar cell, wide spectral response over a broad solar wave-
length range is required. Photo-diodes are small to minimize junction capaci-
tance, while solar cells are large area devices. One of the most important figure
of merit for photo-diodes is the quantum efficiency, whereas the main concern
for solar cells is the power conversion efficiency (power delivered to the load per
incident solar energy). The solar cell works in several steps. Photons in sun-
light hit the solar panel and are absorbed by semiconducting materials, such as
silicon. Electrons are excited from their current molecular/atomic orbital. Once
excited an electron can either dissipate the energy as heat and return to its orbital
or travel through the cell until it reaches an electrode. Current flows through
the material to cancel the potential and this electricity is captured. The chemical
bonds of the material are vital for this process to work, and usually silicon is used
in two layers, one layer being bonded with boron, the other phosphorous. These

8
layers have different chemical electric charges and subsequently both drive and
direct the current of electrons.

2.2 Solar Cell Radiation and Ideal Conversion Effi-

ciency
The radiative energy output from the sun derives from a nuclear fusion reaction.
In every second about 6.2 x 1020 Kg of H2 , is converted to He, with a net mass
loss of about 4 x 103 Kg, which is converted through the Einstein relation(E=mc2 )
to 4 x 1020 J. This energy is emitted primarily as electromagnetic radiation in the
ultraviolet to infrared and radio spectral ranges (.2 to 3µm).
The total mass of the sun is now about 2 x 1030 Kg, and a reasonably stable life
with a nearly constant radiative energy output over 10 billion (1010 ) years is pro-
jected. The intensity of solar radiation in free space at the average distance of the
earth from the sun has a value of 1353 W/m2 .
The atmosphere attenuates the sunlight when it reaches the earth’s surface, mainly
due to water-vapor absorption in the infrared, ozone absorption in the ultravio-
let, and scattering by airborne dust and aerosols. The degree to which the atmo-
sphere affects the sunlight received at the earth’s surface is quantified by the air
mass. The secant of the angle between the sun and the zenith (secθ) is defined as
the air mass (AM) number and it measures the atmospheric path length relative
to the minimum path length when the sun is directly overhead. The AM0 thus
represents the solar spectrum outside the earth’s atmosphere. The AM1 spectrum
represents the sunlight at the earth’s surface when the sun is at zenith, and the
incident power is about 925 W/m2 . The AM2 spectrum is about θ=60° and has an
incident power of about 691 W/m2 , and so on. The secant of the angle between
the sun and the zenith (secθ) is defined as the air mass (AM) number and it mea-
sures the atmospheric path length relative to the minimum path length when the
sun is directly overhead. The AM0 thus represents the solar spectrum outside
the earth’s atmosphere. The AM1 spectrum represents the sunlight at the earth’s
surface when the sun is at zenith, and the incident power is about 925 Wm-2 . The
AM2 spectrum is about θ= 60° and has an incident power of about 691 Wm-2 , and
so on. Figure shows the solar spectrum at various AM conditions.
The AM0 spectrum is the relevant one for satellite and space-vehicle applications.
The AM1.5 conditions (with sun at 45° above the horizon) represent a satisfactory
energy-weighted average for terrestrial applications.
For solar-cell energy conversion, each photon produces an electron-hole pair, so
the solar power has to be converted to photon flux. The photon flux density per
unit energy for AM1.5 is shown in the figure together with that for AM0. To

9
 F IGURE 2.1: Spectral Irradiance vs Wavelength

convert wavelength to photon energy, we use the relationship:

c 1.24
λ= = (2.1)
f hυ

The total incident power for AM1.5 is about 1000 W/m2 . The spectral irradiance
at different Atmospheric mass is shown in Fig 2.1

F IGURE 2.2: Electrical Equivalent Model for an Ideal Solar Cell

To understand the electronic behavior of a solar cell, it is useful to create a model

which is electrically equivalent, and is based on discrete ideal electrical compo-
nents whose behavior is well defined. An ideal solar cell may be modelled by

10
a current source in parallel with a diode; in practice no solar cell is ideal, so a
shunt resistance and a series resistance component are added to the model. The
resulting equivalent circuit of a solar cell is shown on Figure 2.2.

2.3 Characteristic Equation of a Solar Cell

From the equivalent circuit, shown in figure 2.2, it is evident that the current
produced by the solar cell is equal to that produced by the current source, minus
that which flows through the diode, minus that which flows through the shunt
resistor which can be expressed as equation 2.2.

I = IL − ID − ISH (2.2)

Where, I = output current

IL = Photogenerated current
ID = Diode Current
ISH = Shunt Current

The current through these elements is governed by the voltage across them,

Vi = V + IRs (2.3)

Where, Vi = voltage across both diode and resistor RSH

V = voltage across the output terminals
I = Output Current
RS = Series Resistance

By the Shockley diode equation, the current diverted through the diode is given
by Eq. 2.4
   
qV
ID = I0 exp −1 (2.4)
nkT

Where, I0 = reverse saturation current

n = diode ideality factor (1 for an ideal diode)
q = elementary charge
k = Boltzmann’s constant
T = Absolute temperature

By Ohm’s law, the current diverted through the shunt resistor is:
Vj
ISH = (2.5)
RSH

11
Where, RSH is the Shunt Resistance.
Substituting the values in Eq. 2.2 We Get:
   
q(V + IRS ) V + IRS
I = IL − I0 exp −1 − (2.6)
nkT RSH
Solving for V using lambert W function, we get

( IL + I0 − I ) RSH
  
I0 RSH
V = ( IL + I0 ) RSH − I ( RS + RSH ) − nVT W exp
nVT nVT
(2.7)
However, when RSH is large it’s better to solve the original equation numerically.
The general form of the solution is a curve with I decreasing as V increases. The
slope at small or negative V (where the W function is near zero) approaches ,
whereas the slope at high V approaches .

2.4 Open-circuit voltage and short-circuit current

When the cell is operated at open circuit, I = 0 and the voltage across the output
terminals is defined as the open-circuit voltage. Assuming the shunt resistance
is high enough to neglect the final term of the characteristic equation, the open-
circuit voltage VOC is,  
nkT IL
VOC ≈ ln +1 (2.8)
q I0
Similarly, when the cell is operated at short circuit, V = 0 and the current I through
the terminals is defined as the short-circuit current. It can be shown that for a
high-quality solar cell (low RS and I0 , and high RSH ) the short-circuit current ISC
is:

ISC = IL (2.9)

It is not possible to extract any power from the device when operating at either
open circuit or short circuit conditions.

2.5 Effect of Physical Size

The values of IL , I0 , RS , and RSH are dependent upon the physical size of the solar
cell. In comparing otherwise identical cells, a cell with twice the junction area of
another will, in principle, have double the IL and I0 because it has twice the area
where photocurrent is generated and across which diode current can flow. By

12
the same argument, it will also have half the RS of the series resistance related to
vertical current flow; however, for large-area silicon solar cells, the scaling of the
series resistance encountered by lateral current flow is not easily predictable since
it will depend crucially on the grid design (it is not clear what "otherwise iden-
tical" means in this respect). Depending on the shunt type, the larger cell may
also have half the RSH because it has twice the area where shunts may occur; on
the other hand, if shunts occur mainly at the perimeter, then RSH will decrease ac-
cording to the change in circumference, not area. Since the changes in the currents
are the dominating ones and are balancing each other, the open-circuit voltage is
practically the same; VOC starts to depend on the cell size only if RSH becomes
too low. To account for the dominance of the currents, the characteristic equation
is frequently written in terms of current density, or current produced per unit cell
area:
   
q(V + JrS ) V + JrS
J = JL − J0 exp −1 − (2.10)
nkT rSH
Where, J = Current Density
JL = Photogenerated Current Density
J0 = Reverse Saturation Current Density
rS = Specific Series Resistance
rSH = Specific Shunt Resistance

This formulation has several advantages. One is that since cell characteristics
are referenced to a common cross-sectional area they may be compared for cells
of different physical dimensions. While this is of limited benefit in a manufactur-
ing setting, where all cells tend to be the same size, it is useful in research and in
comparing cells between manufacturers. Another advantage is that the density
equation naturally scales the parameter values to similar orders of magnitude,
which can make numerical extraction of them simpler and more accurate even
with naive solution methods.
There are practical limitations of this formulation. For instance, certain parasitic
effects grow in importance as cell sizes shrink and can affect the extracted param-
eter values. Recombination and contamination of the junction tend to be greatest
at the perimeter of the cell, so very small cells may exhibit higher values of J0 or
lower values of RSH than larger cells that are otherwise identical. In such cases,
comparisons between cells must be made cautiously and with these effects in
mind.
This approach should only be used for comparing solar cells with comparable
layout. For instance, a comparison between primarily quadratical solar cells like
typical crystalline silicon solar cells and narrow but long solar cells like typical
thin film solar cells can lead to wrong assumptions caused by the different kinds

13
of current paths and therefore the influence of, for instance, a distributed series
resistance contribution to rS . Macro-architecture of the solar cells could result in
different surface areas being placed in any fixed volume - particularly for thin film
solar cells and flexible solar cells which may allow for highly convoluted folded
structures. If volume is the binding constraint, then efficiency density based on
surface area may be of less relevance.

2.6 Series Resistance

As series resistance increases, the voltage drop between the junction voltage and
the terminal voltage becomes greater for the same current. The result is that the
current-controlled portion of the I-V curve begins to sag toward the origin, pro-
ducing a significant decrease in the terminal voltage and a slight reduction in ISC,
the short-circuit current. Very high values of RS will also produce a significant re-
duction in ISC; in these regimes, series resistance dominates and the behavior of
the solar cell resembles that of a resistor. These effects are shown for crystalline
silicon solar cells in the I-V curves displayed in the figure to the right.
Losses caused by series resistance are in a first approximation given by

Ploss = VRs I = I 2 RS (2.11)

and increase quadratically with (photo-)current. Series resistance losses are there-
fore most important at high illumination intensities.
Effect of Series resistance is showed in Fig 2.3.

F IGURE 2.3: Effect of change in Series Resistance

14
2.7 Shunt Resistance
As shunt resistance decreases, the current diverted through the shunt resistor
increases for a given level of junction voltage. The result is that the voltage-
controlled portion of the I-V curve begins to sag far from the origin, producing a
significant decrease in the terminal current I and a slight reduction in VOC . Very
low values of RSH will produce a significant reduction in VOC . Much as in the
case of a high series resistance, a badly shunted solar cell will take on operating
characteristics similar to those of a resistor. These effects are shown for crystalline
silicon solar cells in the I-V curves displayed in the Fig 2.4.

F IGURE 2.4: Effect of Change in Shunt Resistance

2.8 Reverse Saturation Current

If one assumes infinite shunt resistance, the characteristic equation can be solved
for VOC :  
kT ISC
VOC = ln +1 (2.12)
q I0
Thus, an increase in I0 produces a reduction in VOC proportional to the inverse of
the logarithm of the increase. This explains mathematically the reason for the re-
duction in VOC that accompanies increases in temperature described above. The
effect of reverse saturation current on the I-V curve of a crystalline silicon solar
cell are shown in the figure to the right. Physically, reverse saturation current is
a measure of the "leakage" of carriers across the p-n junction in reverse bias. This
leakage is a result of carrier recombination in the neutral regions on either side of
the junction. Effect of reverse saturation current is given in Fig 2.5.

15
 F IGURE 2.5: Effect of Reverse Saturation Current

2.9 Ideality Factor

The ideality factor (also called the emissivity factor) is a fitting parameter that de-
scribes how closely the diode’s behavior matches that predicted by theory, which
assumes the p-n junction of the diode is an infinite plane and no recombination
occurs within the space-charge region. A perfect match to theory is indicated
when n = 1. When recombination in the space-charge region dominate other re-
combination, however, n = 2. The effect of changing ideality factor independently
of all other parameters is shown for a crystalline silicon solar cell in the I-V curves
displayed in Fig 2.6.

F IGURE 2.6: Effect of Ideality Factor

16
2.10 Maximum Power(Pmax), Current at PMax(IMP), Volt-
age at Pmax(VMP)
The power produced by the cell in Watts can be easily calculated along the I-V
sweep by the equation P=IV. At the ISC and VOC points, the power will be zero
and the maximum value for power will occur between the two. The voltage and
current at this maximum power point are denoted as VMP and IMP respectively.
VMP and IMP are shown in Fig 2.7.

F IGURE 2.7: VMP and IMP from the I-V Curve

2.11 Fill Factor

The Fill Factor (FF) is essentially a measure of quality of the solar cell. It is calcu-
lated by comparing the maximum power to the theoretical power (PT ) that would
be output at both the open circuit voltage and short circuit current together. FF
can also be interpreted graphically as the ratio of the rectangular areas depicted
in the following figure.

2.12 Efficiency
Efficiency is the ratio of the electrical power output Pout , compared to the solar
power input, Pin , into the PC cell. Pout can be taken to be PMAX since the solar

17
 F IGURE 2.8: Fill Factor from I-V Graph

cell can be operated up to its power output to get the maximum efficiency.

POUT
η= (2.13)
PI N
PMAX
η MAX = (2.14)
PI N
Pin is taken as the product of the irradiance of the incident light, measured in
W=m2 or in ssuns(1000W=m2), with the surface area of the solar cell (m2). The
maximum efficiency found from a light test is only an indication of the perfor-
mance of the device under test, but, like all of the I-V parameters, can also be
affected by ambient conditions such as temperature and the intensity and spec-
trum of the incident light. For this reason, it is recommended to test and compare
PV cells using similar lighting and temperature conditions.
During operation, the efficiency of solar cells is reduced by the dissipation of
power across internal resistances. These parasitic resistances can be modeled as
parallel shunt resistance and series resistance as depicted in the figure. For an
idea cell, shunt resistance would be infinite and would not provide an alternate
path or current to flow, while series resistance would be zero, resulting in no fur-
ther voltage drop before the load.
Decreasing shunt resistance and increasing series resistance will decrease the FF
and Pmax as shown in the following figure. If shunt resistance is decreased too
much, Voc will drop, while increasing series resistance excessively can cause Isc
to drop instead.
It is possible to approximate the series and shunt resistances from the slopes of
the I-V curve at Voc , however , is at best proportional to the series resistance but
it is larger than the series resistance . Shunt resistance is represented by the slope
at Isc . Typically, the resistance at Isc and Voc will be measured and noted.
If incident light is prevented from exciting the solar cell, the I-V curve shown in

18
the following figure (Fig. 2.9) can be obtained. This I-V curve is simply a reflec-
tion of the “No Light” curve about the V-axis. The slope of the linear region of
the curve in the third quardanr is a continuation of the linear region in the first
quadrant, which is the same linear region used to calculate RsH can be derived
from the I-V plot obtained with or without providing light excitation, even when
power is sourced to the cell. It is important to note, however, that for real cells,
these resistances are often a function of the light level, and can differ in value
between the light and dark tests.

F IGURE 2.9: I-V curve in absence and presence of light

19
 Chapter 3

Dye Sensitized Solar Cell

3.1 Introduction
A dye-sensitized solar cell (DSSC, DSC, DYSC[4] or Grätzel cell) is a low-cost
solar cell belonging to the group of thin film solar cells. It is based on a semi-
conductor formed between a photo-sensitized anode and an electrolyte, a pho-
toelectrochemical system. The modern version of a dye solar cell, also known as
the Grätzel cell, was originally co-invented in 1988 by Brian O’Regan and Michael
Grätzel at UC Berkeley and this work was later developed by the aforementioned
scientists at the École Polytechnique Fédérale de Lausanne until the publication
of the first high efficiency DSSC in 1991. Michael Grätzel has been awarded the
2010 Millennium Technology Prize for this invention.
The DSSC has a number of attractive features; it is simple to make using conven-
tional roll-printing techniques, is semi-flexible and semi-transparent which offers
a variety of uses not applicable to glass-based systems, and most of the materi-
als used are low-cost. In practice it has proven difficult to eliminate a number of
expensive materials, notably platinum and ruthenium, and the liquid electrolyte
presents a serious challenge to making a cell suitable for use in all weather. Al-
though its conversion efficiency is less than the best thin-film cells, in theory its
price/performance ratio should be good enough to allow them to compete with
fossil fuel electrical generation by achieving grid parity. Commercial applica-
tions, which were held up due to chemical stability problems, are forecast in the
European Union Photovoltaic Roadmap to significantly contribute to renewable
electricity generation by 2020.

3.2 DSSC Basics

Electricity generation behavior of illuminated organic dyes were discovered in
the late 1960s[17]. Although electric power generation via the dye sensitization
solar cell (DSSC) principle was demonstrated in 1972[18], instability of the dye
solar cell imposed as a huge challenge[19].

20
A modern DSSC is composed of a porous layer of Titanium Dioxide nanoparti-
cles, covered with a molecular dye that absorbs sunlight like Chlorophyll in green
leaves. The Titanium Dioxide is immersed under an electrolyte solution under a
platinum-based catalyst. As in a conventional alkaline battery, an anode (Tita-
nium Oxide) and a cathode (The Platinum) are placed on either side of a liquid
conductor (the electrolyte).
For a DSSC electrode is a transparent conductor in contact with the anode and
counter electrode is in contact with the cathode, a platinum-based catalyst. Sun-
light passes through the transparent electrode into the dye layer where it excites
the electrons that then flow into the Titanium Dioxide. Electrons flow toward the
transparent electrode where they are collected for powering a load. After flowing
through the external circuit, they are re-introduced into the cell on a metal elec-
trode on the back, flowing into the electrolyte. The electrolyte then transports the
electrons back to the dye molecules.
Dye-sensitized solar cells separate the two functions provided by silicon in a tra-
ditional cell design. Normally the silicon acts as both the source of photoelec-
trons, as well as providing the electric field to separate the charges and create a
current. In the dye-sensitized solar cell, the bulk of the semiconductor is used
solely for charge transport, the photoelectrons are provided from a separate pho-
tosensitive dye. Charge separation occurs at the surfaces between the dye, semi-
conductor and electrolyte.
As the dye molecules are quite small (nanometer sized), in order to capture a
reasonable amount of the incoming light the layer of dye molecules needs to be
much thicker than the molecules themselves. To address this problem, a nano-
material is used as a scaffold to hold large numbers of the dye molecules in a
3-D matrix, increasing the number of molecules for any given surface area of cell.
In existing designs, this scaffolding is provided by the semiconductor material,
which serves double-duty.

3.2.1 Mechanism
The main processes that occur in a DSSC are:

1. The incident photon is absorbed by photosensitizers absorbed on the TiO2

surface.

2. The photosensitizers are excited from the ground state (S) to the excited
state (S*). The excited electrons are injected into the conduction band of the
TiO2 electrode. This results in the oxidation of the photosensitizer (S+ ).

S + hν → S∗ (3.1)

21
 (A)

(B)

F IGURE 3.1: DSSC simplified Mechanism (a)[20], Schematic structure of nanocrystalline dye-
sensitized solar cell (DSSC) presenting the mechanism of electric power generation and scan-
ning electron microscope (SEM) photograph of a typical nanocrystalline TiO2 electrode[20]

TiO
S∗ −−→
2
S+ + e− (3.2)

3. The injected electrons in the conduction band of TiO2 are transported be-
tween TiO2 nanoparticles with diffusion toward the back contact (TCO).
And the electrons finally reach the counter electrode through the circuit.

4. The oxidized photosensitizer (S+ ) accepts electrons from the I− ion redox
mediator leading to regeneration of the ground state (S), and two I− Ions
are oxidized to elementary Iodine which reacts with I− to the oxidized state,
I3 − .
S+ + e− → S (3.3)

5. The oxidized redox mediator, I3− , diffuses toward the counter electrode and
then it is reduced to I− ions.

I3− + 2e− → 3I − (3.4)

22
The efficiency of a DSSC depends on four energy levels of the component: the
excited state (approximately LUMO) and the ground state (HOMO) of the pho-
tosensitizer, the Fermi level of the TiO2 electrode and the redox potential of the
mediator (I− /I3− ) in the electrolyte[20]. The solar energy-to-electric power con-
version efficiency, η ( % ), solar cells, including DSSCs, is defined from the fol-
lowing equation:
J × VOC × FF
η = SC (3.5)
I0

Where, I0 = Photon Flux(CA 100mWcm−2 for AM 1.5G)

JSC = Short Circuit Current Density under irradiation,
VOC = Open Circuit Voltage under irradiation,
FF = Fill Factor

Basically, the VOC value is determined by the energy gap between the Fermi level
of the TiO2 electrode, which is located near the conduction band edge potential
(Ecb ), and the redox potential of the I− /I3− in the electrolyte.

3.2.2 Materials
To construct an efficient DSSC selecting materials is one of the most important
step. There are many factors to consider when deciding what material to use,
when to use and the reason of using. For example, it is very important for the
TCF to be low optical and elecrical power consuming, So that, the TiO2 and Photo
Sensitized layer gets more optical power to convert. Also, the porosity of the
TiO2 is also very important as it determines the surface area in contact with the
photosensitizer and thus affecting the efficiency. A brief description[21] of the
materials that can be used is given below:

TCO Electrode
TCO coated glass is used as the substrate for the TiO2 photoelectrode. For high so-
lar cell performance, TCO must have low sheet resistance and high transparency.
In addition, sheet resistance should be nearly independent of temperature up to
500o C because sintering of the TiO2 is generally carried out at 450-500 o C. Indium-
Tin-Oxide is one of the most famous TCO materials. However, ITO has a low
thermal stability of resistance, but it nevertheless has low resistance at ambient
temperature. Usually, Fluorine-doped SnO2 is used as the substrate for DSSCs. If
TiO2 electrode can be prepared at relatively low temperature below 200 o C, ITO-
coated poly(ethylene terefutarate) (PET) or poly(ethylene naphthalate) (PEN) can
be used as the substrate for plastic DSSCs.

23
TiO2 Nano-Particle
The primary role of porous electrode is to provide sufficient surface area for dye
adsorption, and to convey all injected electrons to TCO. Thus, electrodes should
be transparent for visible and infrared regions. The required surface area and
thickness of the electrode are determined by the absorption coefficients of the
sensitizers, but the thickness is limited by the electron diffusion length of the elec-
trodes. For typical dyes, optimized cells result in 10–20 µm thickness of porous
electrodes consisting of around 20 nm particles. To produce high-performance
DSSCs, colloidal TiO2 prepared by hydrolysis of Ti (IV) alkoxides, such as iso-
propoxide and butoxide, has usually been used. To obtain monodispersed par-
ticles of the desired size, the hydrolysis and condensation kinetics must be con-
trolled. Titanium-alkoxides suitably modified with acetic acid or acetyl acetonate,
yield colloids having a large surface area (>200m2 g−1 ) and smaller particle diam-
eter (5–7 nm). Peptization results in segregation of the agglomerates to primary
particles, after which the large agglomerates are removed by filtration. Autoclav-
ing of the colloidal TiO2 solution leads to growth of the primary particles to 10–25
nm and also to some extent increases the anatase crystallinity present. At higher
autoclaving temperature, more growth of particles and rutile formation occur,
particularly at temperatures above 240 o C. Generally, anatase rather than rutile
TiO2 is more suitable for the electrodes. TiO2 electrodes prepared from small
nanoparticles (10–25 nm) are transparent.

Ru-Complex Photosensitizer
The Ru-complex sensitizer, which contributes the primary steps of photon ab-
sorption and the consequent electron injection, is adsorbed onto the TiO2 surface.
The chemical structure of typical Ru-complex sensitizers developed by Grätzel
and co-workers are shown in the Figure 3.2 (a) while Figure 3.2 (b) shows ab-
sorption properties of the complexes in solution. The Y axis is represented by
absorbance and 1−T. N3 dye, cis-bis (4,40 ; -dicarboxy-2,20 -bipyridine) Dithio-
cyanato Ruthenium (II), can absorb over a wide range of the visible region from
400 to 800 nm. Black dye, Trithiocyanate-o 4,40 4”-Tricarboxy-2,2 0 :6 0 ,2 ”-Terpyridine
Ruthenium (II), absorbs in the near-IR region up to 900 nm. Absorption by these
dyes in the visible and near-IR regions is attributed to the metal-to-ligand charge-
transfer (MLCT) transition. The HOMO and the LUMO are derived from the d-
orbital of Ru metal and the π* orbital of the ligand, respectively. The NCS ligand
shifts the HOMO level negatively, leading to a red shift in the absorption property
of the complex, and also contributes electron acceptance from iodide ions.
These Ru-complex sensitizers are dissolved at a concentration of 0.2–0.3mM in
ethanol or tert-butanol–acetonitrile, 1:1 mixed solution. The TiO2 electrodes are

24
 (B)

(A)

F IGURE 3.2: Molecular Structures of typical Ru-Complex photosensitizers for DSSC (a), Ab-
sorption spectra of N3 dye and black dye represented by absorbance and light harvesting
efficiency, 1-T (T:transmittance): (—) N3 dye, (- - -)black dye(b).[20]

immersed in the dye solution and then kept at 25 o C for more than 12 h to al-
low the dye to adsorb to the TiO2 surface. Ru-complexes have carboxyl groups
to anchor to the TiO2 surface. Anchoring causes a large electronic interaction be-
tween the ligand and the conduction band of TiO2 , resulting in effective electron
injection from the Ru-complex into the TiO2 . The Ru-complex is adsorbed on the
TiO2 surface via carboxylate bidentate coordination or ester bonding as measured
by FT–IR absorption analysis. The coverage of the TiO2 surface with the N3 dye
reaches near 100% as derived from the surface area of TiO2 and the amount of the
dye.

Redox Electrolyte
The electrolyte used in DSSCs contains I− /I−3 redox ions, which mediate elec-
trons between the sensitizers and the counter electrode. Mixtures of iodides such
as LiI, NaI, KI, tetraalkylammonium-iodide (R4 NI), and imidazolium-derivative
iodides with concentrations of 0.1–0.5M (M: molar concentration) and 0.05−0.1M
I2 dissolved in non-protonic organic solvents. Typical organic solvents used for
DSSC are nitrile solvents having relative low viscosity, such as acetonitrile, propi-
onitrile, methoxy-acetonitrile, and 3-methoxy-propionitrile. Viscosity of solvents
directly affects ionic conductivity in the electrolyte, and consequently the solar-
cell performance. To improve solar cell performance, especially Jsc, low-viscosity
solvents are desired for high ionic conductivity. On the other hand, low-viscosity

25
solvents typically have high vapor pressure, making it difficult to seal it for long
term usage. The diffusion coefficient of I−3 in methoxy-acetonitrile is estimated
as 5.4−6.2 × 10−6 cm2 s−1 .
Solar cell performance of DSSCs also depends on counter-cations of iodides such
as Li+ , Na+ , K+ , and R4 N+ due to different ion conductivity in the electrolyte
and adsorption property on the TiO2 surface. The adsorption of cations shifts
the conduction band level of the TiO2 electrode positively. Basic compounds
such as 4-tert-butylpyridine (TBP) have been added to the electrolyte solution,
where TBP shifts the conduction band level of the TiO2 electrode negatively,
improving the open-circuit voltage. Electrolytes also influence the charge re-
combination rate probably by changing the thickness of the double layer and
the free energy difference between the electrons in the electrode and I−3 ions.
A typical electrolyte composition that produces high solar-cell performance for
the Ru-complex sensitizers reported by Grätzel’s group is a mixture of 0.5M 1,2-
dimethyl-3-hexylimidazolium iodide (DMHImI), 0.04M LiI, 0.02M I2 , and 0.5M
TBP in acetonitrile. It has been reported that imidazolium derivatives, such as
DMHImI and 1,2-dimethyl-3-propylimidazolium iodide (DMPImI), decrease the
resistance of the electrolyte solution and improve photovoltaic performance. Br− /Br2
and hydroquinone have also been used as redox electrolyte for DSSC, but the io-
dine redox electrolyte gives the best performance.

Counter-Electrode
Tri-iodide ions, I3− , formed by reduction of dye cations with I− ion, are again
reduced to I− ions at the counter-electrode. To reduce the tri-iodide ions, the
counter-electrode must have high electrocatalytic activity for the reaction. Sput-
tered Pt coated on a TCO substrate (5–10 µg cm−2 or approximately 200 nm thick-
ness) has been usually employed as a counter-electrode. In addition, the electro-
catalytic activity of the Pt-sputtered TCO electrode for reduction of triiodide ions
can be improved by formation of Pt colloids on the surface . Small amounts of an
alcoholic solution of H2 PtCl6 are dropped on the surface of the Pt-sputtered TCO
substrate, followed by drying and heating at 385o C for 10 minutes, resulting in
formation of Pt colloids on the surface. The resistance of the Pt counter-electrode
and electrolyte interface directly affect fill factor of the solar cell. A desirable ex-
change current density corresponding to electrocatalytic activity for the reduction
of tri-iodide ions is 0.01–0.2 A cm−2 . Carbon materials and polymer materials
such as PEDOT can also be used as the counter electrode instead of Pt.

Sealing Materials
A sealing material is needed to prevent leakage of the electrolyte and evapora-
tion of the solvent. Chemical and photochemical stability of the sealing material

26
against the electrolyte component, iodine, and solvent is required. Surlyn (Du
Pont), a co-polymer of ethylene and acrylic acid has been used for the purpose.

3.3 Transparent Conductive Film

Transparent conducting films (TCFs) are thin films made of optically transpar-
ent and electrically conductive material. TCFs for photovoltaic applications have
been fabricated from both inorganic and organic materials. Inorganic films typi-
cally are made up of a layer of transparent conducting oxide (TCO). Some of the
common TCO includes indium tin oxide (ITO), fluorine doped tin oxide (FTO) or
doped zinc oxide. Organic TCF are being developed using carbon nanotube net-
works and graphene. These can be fabricated to be highly transparent to infrared
light, along with networks of polymers such as poly(3,4-ethylenedioxythiophene)
and its derivatives.
Transparent conducting films are typically used as electrodes when a situation
calls for low resistance electrical contacts without blocking light (e.g. LEDs, pho-
tovoltaics). Transparent materials possess wide bandgaps whose energy value
is greater than those of visible light. As such, photons with energies below the
bandgap value are not absorbed by these materials and visible light passes through.
In the case of a solar cell, it is required to have a wider range of transparency be-
yond visible light to make efficient use of the full solar spectrum.

3.3.1 Choosing the Right Materials

To construct an efficient solar cell it is required for the TCF to be highly conductive
and as less light absorbing as possible. From the value of absorption coefficient,
light absorption of a material can be determined. A list of Absorption Coefficient
of some common TCOs for light of 435nm wavelength are given below(table 3.1):
From the table, a basic idea of optical power consumption can be achieved. Fur-
ther analysis of their properties is now described below:

Indium-Tin Oxide
Indium tin oxide (ITO) is a ternary composition of indium, tin and oxygen in
varying proportions. Depending on the oxygen content, it can either be de-
scribed as a ceramic or alloy. Indium tin oxide is typically encountered as an
oxygen-saturated composition with a formulation of 74% In, 18% O2 , and 8% Sn
by weight.It is transparent and colorless in thin layers, while in bulk form it is
yellowish to grey. In the infrared region of the spectrum it acts as a metal-like
mirror[24].
ITO is a heavily doped n-type semiconductor with a large bandgap of around 4

27
 TABLE 3.1: Absorption Coefficient(α) of Materials

Material Absorption Coefficient, α(cm-1 )

ITO(λ < 450nm[22] >5613

ITO( 490nm≤ λ ≤ 650nm[22] <100

ITO( λ ≥ 650nm[22] 100 ≤ α ≤ 1000

FTO (λ < 350nm) 2154

FTO (λ ≥ 350nm) 359

PEDOT (λ < 600nm)[23] ∼140000

PEDOT (λ ≥ 600nm)[23] ∼8000

eV[25]. Because of the band gap, it is mostly transparent in the visible part of
the spectrum and its extinction coefficient, k, in this wavelength range is zero. In
the ultraviolet (UV), it is opaque, so that k is non zero in the UV spectral range,
because of band-to-band absorption (a UV photon can excite an electron from the
valence band to the conduction band). It is also opaque in the near infrared (NIR)
and infrared (IR), because of free carrier absorption (an infrared photon can ex-
cite an electron from near the bottom of the conduction band to higher within the
conduction band). In this wavelength range k is non-zero, and reaches its maxi-
mum value in the IR regime, similar to the behavior of k for metals. Absorption
Coefficient, αof ITO and Glass are given in Figure 3.3.

Fluorine-Doped Tin Oxide

Fluorine-doped tin oxide (FTO) coated glass is electrically conductive and ideal
for use in a wide range of devices, including applications such as opto-electronics,
touch screen displays, thin film photovoltaics, energy-saving windows, RFI/EMI
shielding and other electro-optical and insulating applications. Fluorine doped
tin oxide has been recognized as a very promising material because it is rela-
tively stable under atmospheric conditions, chemically inert, mechanically hard,
high-temperature resistant, has a high tolerance to physical abrasion and is less
expensive than indium tin oxide. Moreover, FTO based materials avoid prob-
lems with indium diffusion into the N-type TiO2 or ZnO nano-structured films.

28
 F IGURE 3.3: Absorption Coefficient, α (cm-1 ) vs wavelength, λ

These FTO glass materials have a wide range of thermal and heated glass perfor-
mance properties, while also increasing light transmittance and optimizing elec-
trical conductivity. Optical and Electrical Properties of FTO is shown in figure
3.4.

PEDOT
Poly(3,4-ethylenedioxythiophene)(PEDOT) is an organic TCF, which has conduc-
tivity of up to around 1,000 Scm-1 [26]. Thin oxidized PEDOT films have approx.
10% or less absorption in the visible spectrum and excellent stability.[27] How-
ever, PEDOT is insoluble in water making processing more difficult and costly.
The bandgap of PEDOT can be varied between 1.4 and 2.5 eV by varying the
degree of π-overlap along the backbone.[27] This can be done by adding sub-
stituents along the chain, which result in steric interactions preventing π-overlap.
Substituents can also be electron-accepting or donating which will modify the
electronic character and thus modify the bandgap. This allows for the formation
of a wide bandgap conductor which is transparent to the visible spectrum.
PEDOT is prepared by mixing EDT monomer with an oxidizing agent such as
FeCl3 . The oxidizing agent acts as an initiator for polymerization. Research has
shown that increasing the ratio of [FeCl3 ]/[monomer] decreases the solubility of
the PEDOT.[27] This is thought to be a result of increased crosslinking in the poly-
mer making it more difficult to dissolve in a solvent.
Doping PEDOT with poly(styrene sulfonate) can improve the properties over the

29
 ( A ) Absorption Coefficient, α vs Wavelength, λ

( B ) Resistivity, Ωcm vs Wavelength, λ

F IGURE 3.4: Electrical and Optical Properties of FTO

unmodified PEDOT. PEDOT:PSS is water-soluble, making processing easier[28].

PEDOT:PSS has a conductivity ranging from 400 to 600 Scm-1 while still transmit-
ting 80% of visible light[29]. Treatment in air at 100o C for over 1000 hours will
result in a minimal change in conductivity[30]. Recently, it was reported that the
conductivity of PEDOT:PSS can be improved to be more than 4600 Scm-1 [31].
PEDOT:PSS is prepared by polymerizing EDT monomer in an aqueous solution
of PSS using Na2S2O8 as the oxidizing agent. This aqueous solution is then spin
coated and dried to make a film[30].
Poly(4,4-dioctyl cyclopentadithiophene) can be doped with iodine or 2,3-dichloro-
5,6-dicyano-1,4-benzoquinone (DDQ) to form a transparent conductor. The doped
polymer has low absorption of the visible spectrum with an absorption band cen-
tered around 1050 nm. When doped with iodine, a conductivity of 0.35 Scm-1 can
be achieved. However, the iodine has a tendency to diffuse out in air, making the
iodine-doped poly(4,4-dioctyl cyclopentadithiophene) unstable[32].

30
DDQ itself has a conductivity of 1.1 Scm-1 . However, DDQ-doped poly(4,4-
dioctyl cyclopentadithiophene) also tends to decrease its conductivity in air. DDQ-
doped polymer has better stability than the iodine-doped polymer, but the stabil-
ity is still below that of PEDOT. In summary, poly(4,4-dioctyl cyclopentadithio-
phene) has inferior properties relative to PEDOT and PEDOT:PSS, which need to
be improved for realistic applications.
Poly(4,4-dioctyl cyclopentadithiophene) is solution polymerized by combining
monomer with iron(III) chloride. Once the polymerization is complete the doping
is done by exposing the polymer to iodine vapor or DDQ solution. Absorption
Co-efficient, α vs Energy of the incident photon is given in the Figure 3.5.

F IGURE 3.5: Absorption Coefficient, α, vs incident photon energy

From figure 3.5, it can be said that for light below 2eV energy or above 1000nm
wavelength PEDOT:PSS is opaque.

3.4 Photo-Sensitizers
The optimal sensitizer for the dye-sensitized solar cell should be panchromatic,
i.e. absorb visible light of all colors. Ideally, all photons below a threshold wave-
length of about 920 nm should be harvested and converted into electric cur-
rent.From the thermodynamic considerations, a limit is derived and it shows
that the conversion efficiency of any single-junction photovoltaic solar converter
peaks at approximately 33 percent near a threshold energy of 1.4 eV [33][34]. This
directionality should be engineered to provide an efficient electron transfer from
the excited dye to the Ti02 conduction band via good electronic coupling between
the lowest unoccupied molecular orbital (LUMO) of the sensitizer and the Ti 3d
orbital. Also, the sensitizer should have suitable interlocking groups for grafting
the dye on the semiconductor surface to ensure intimate electronic coupling be-
tween its excited state wave function and the conduction-band manifold of the
semiconductor [35][36]. At present Ru-based Sensitizers are broadly used. there
are many types of Ru sensitizers. Also Metal free sensitizers are also becoming
very efficient and should be taken in consideration.

31
3.4.1 Ru-Complex Sensitizer
Ruthenium complexes, in particular, have been investigated intensively for DSSC
applications since Regan and Gratzel reported the good device performance[4]
from a Ru complex dye in 1991. Tris(2,2 -bipyridyl)ruthenium(II) and its ho-
mologues have been extensively investigated as redox sensitizers, very little is
known about the excited-state redox properties of the corresponding bis(2,2 -
bipyridyl)ruthenium(II) analogous. Apart from their chemical stability and ease
of interfacial charge exchange with semiconducting solids, the attractive feature
of these complexes is their large visible light-harvesting capacity.

F IGURE 3.6: Ru Complexes Developed by Nazeeruddin et al.

In an effort to fulfill demanding requirements of the sensitizer, Nazeeruddin et

al. [35] have succeeded in developing a panchromatic ruthenium complex sensi-
tizer having carboxylated terpyridyl and three thiocyanate groups as ligands (Fig.
3.6). The purpose of incorporating carboxylate groups in the ligand is threefold:
(i) to increase the molar extinction coefficient of the complex, (ii) to facilitate the
grafting of the dye on the semiconductor surface, and (iii) to ensure intimate elec-
tronic coupling between its excited-state wave function and the conduction band
manifold of the semiconductor. On the basis of photovoltaic performance mea-
sured under full AM 1.5 sunlight, this black dye is superior to all charge-transfer
sensitizers known thus far. At present the certified short circuit current under
standard AM 1.5 sun light is 20.5 mA/cm2 , and the open-circuit voltage is 0.72 V,
yielding an overall conversion efficiency of 10.4%. The discovery that the black
dye exhibiting enhanced light harvesting in the red and near-IR region opens up

32
the way to improve significantly the overall efficiency of nanocrystalline photo-
voltaic devices. The phenyl substitution should increase the molar extinction co-
efficient, permitting a reduction in film thickness which should benefit the open-
circuit potential and overall efficiency of these solar cells.
Ru-based Complexes have come very far through a lot of researches. In order
to engineer new ruthenium-based dyes as strong light absorbents and efficient
dyes for DSSCs, Kisserwan and Ghaddar [37] investigated a new cyclometalated
ruthenium complex T66 (Figure 36) and incorporated it as a sensitizer in a DSSC.
Efficiency of 4.5% has been measured for T66 in a nonvolatile ionic liquid-based
electrolyte.

F IGURE 3.7: Molecular structure of T66 and current-potential curves of assembled DSSC
(taken from [37])

A new series of neutral, thiocyanate-free Ru(II) sensitizers (TFRS-1–3) (Figure 37),

which are assembled using both 4,4 -carboxy-2,2 -bypyridine and 2-pyridyl pyra-
zolate ancillaries, exhibit a light-harvesting capability up to 700 nm and superior
DSSC performance in conversion efficiency[38].
The highest power conversion efficiencies are close to 9.5% for TFRS-2. This re-
sult eliminates the need for proximal contact between the soft sulfur atom of
thiocyanate and electron donor in electrolyte for effective regeneration of dyes.
Further development is versatile and of great perspective.

33
 F IGURE 3.8: Molecular structures of Ru(II) sensitizers TFRS-1–3 and absorption spectra of
TFRS, N719 in DMF (taken from [38])
.

3.4.2 Metal-Free Organic Sensitizers

Significant progress in the use of organic dyes in DSSCs was first made by Hara et
al. and Yanagida and coworkers using oligoenes 1–3 containing dialkylaminophenyl
groups as the donors and cyanoacrylic acid as the acceptor. The use of these dyes
as sensitizers in liquid electrolyte systems yielded overall power conversion effi-
ciencies of up to 6.8%.During the last few decades, p-conjugated oligothiophenes
have played a major role in the development of organic electronic materials be-
cause of their well-known high polarizability as well as their tunable spectro-
scopic and electrochemical properties. They have also been used as core building
blocks in the synthesis of a wide variety of novel p systems that are suitable for
DSSCs. The use of coumarins (4–6) as donor groups and cyanoacrylic acid as the
acceptor linked to an oligoene or oligothiophene core led to efficiencies of up to
8.2%—values comparable to the standard N719 sensitizer. The introduction of
a CC double bond (-CH=CH-) between the cyanoacrylic acid and the coumarin
framework increased the p conjugation of dye 4 and resulted in a wide absorp-
tion in the visible region. DSSCs based on dye 4 produced a short-circuit current
density (JSC) of 14.0 mAcm-2 , with a maximum photon-to-electron conversion ef-
ficiency (h) of 6.0%.

Replacement of the CC double bond by a thienylenevinylene (in 5) or by a

34
 F IGURE 3.9: Property Table of some Metal-Free Organic Dyes

bithiophene (in 6) bridge did not change the absorption spectra in solution. In
contrast, a broadening of the absorption spectrum was observed when dyes 5
and 6 were adsorbed on the TiO2 surface, leading to an increased photocurrent
and overall efficiency. Expansion of the p system in sensitizer 7 by insertion of a

35
CC double bond red-shifted the absorption maximum relative to that of sensitizer
6. DSSCs based on 7 generated an efficiency of 5.0% (JSC = 12.0 mA cm2 , VOC
= 0.59 V, FF = 0.71) without any coadsorbent. The efficiency and photocurrent
were significantly improved to 8.2% and JSC = 15.9 mAcm-2 , respectively, upon
addition of 120 mm DCA to the dye solution before adsorption onto TiO2 .
In the case of dye 9, in which a regioregular hexylsubstituted quaterthiophene
bridges a carbazole and a cyanoacrylic acid unit, the increased efficiency over
the lessalkylated derivative 10 seems to be due to the longer electron lifetime in
the former.[50, 51] This longer electron lifetime was attributed to the high hy-
drophobicity, which improved the packing of the dye on the surface and acted
as a barrier preventing hydrophilic I3 ions from approaching the TiO2 surface,
thereby retarding electron leakage to the redox electrolyte. This effect accounted
for the significant improvement in the VOC value. The efficiency of DSSCs made
from 9 dramatically increased to 8.3% (JSC = 15.22 mAcm-2 , VOC = 0.73 V, FF =
0.75) when the iodine concentration in the electrolyte was increased from 0.05 to
0.2m. This result is reflected by an improved JSC value, which is attributable to
the enhanced electrolyte diffusion and efficient regeneration of the dye. Under
comparable conditions, DSSCs based on the dye N719 gave efficiencies of 8.1%.

3.4.3 Natural Dye

Natural dye pigments have been classified into four broad categories, i.e. (1)
chlorophyll, (2) carotenoids, (3) betalains and/or (4) flavonoids.

Chlorophyll
Chlorophyll is a common green pigment found in plants and algae. It is essen-
tially a chlorine pigment with magnesium ion in the centre of the chlorine ring.
Moreover, chlorophyll a and chlorophyll b are the most used types. The basic
difference is in the composition of side chain (in chlorophyll a, it is –CH3, and
in chlorophyll b it is CHO). Other less common types are chlorophyll d, c1, c2
and f. Figure depicts the UV-VIS spectroscopic analysis of chlorophyll a and b.
Both the types absorb visible portion of solar spectrum from red, blue and violet
wavelengths with a maximum absorption at 670 nm for chlorophyll a and 470
nm for chlorophyll b. Since the first evidence of its use as dye sensitizer in DSSC
by Kay and Gratzel, many improvements and advantages have been reported
by different research studies (Syafinar et al. 2015a, b; Shah et al. 2016). The main
disadvantage of using chlorophyll is its long chain length which causes steric hin-
drance and leads to low-electron transferability. Another issue is its low adsorp-
tion ability on TiO2 semi-conductor. Some derivatives such as methyltrans32-
carboxypyropheophorbide alpha showed high binding ability with semiconduc-
tor surfaces via chelating and monodentate modes (Calogero et al. 2009).

36
 F IGURE 3.10: Absorbance of Chlorophyll

Carotenoids
Carotenoids are organic pigments produced by plants and also found in some
microorganisms. Carotenoids absorb red, orange and yellow wavelength from
solar spectrum. These are broadly classified into two categories, (1) xanthophylls
which contain oxygen and (2) carotenes which are essentially pure hydrocar-
bons containing no oxygen. These pigments have been successfully employed
in DSSCs as sensitizers and show excellent properties. The maximum claimed
conversion efficiency of DSSCs using carotenoids is 2.6%, while the conversion
efficiency of combination of carotenoids and chlorophyll is reported to be 4.2%.

Flavonoids
These are very important pigments present in almost all land plants. Flavonoids
are essentially sugar compounds bonded with polyphenols and are responsible
for colouration of many flowers and fruits. Other roles include attracting insects,
photoprotection, antioxidation activity and enhancement of photosynthesis. The
flavonoids can be classified into anthocyanins, aurones, flavones, chalones and
flavonols. Among them anthocyanins are the most important pigments for DSSC
applications due to their absorption in visible range and ability to transfer elec-
trons efficiently. Anthocyanins are the basis for most orange, pink, red, magenta
and blue colours. The light absorption properties of flavonoids are depicted in
Fig. 15.7 (Stintzing and Carle 2004; Marais et al. 2006). These pigments are
also quick to make bonds with TiO2 due to absorption of cyanine which leads
to development of effective and strong complex via OH- displacement and for-
mation of water molecules. The ability of fast charge transfer using anthocyanin

37
extracted from blackberry has been successfully demonstrated using femtosec-
ond analysis. Despite high electron transfer ability, the conversion efficiency was
low due to possible agglomeration and high recombination reactions (Yamasaki
et al. 1996; Cherepy et al. 1997).

F IGURE 3.11: Absorbance of Flavonoids

Betalain
These pigments are an additional class of natural sensitizers and are present in
flower petals, roots, stems and leaves of caryophyllales plants. They possess high
extinction coefficient in visible range, and their redox properties are dependent
on pH of the solution. They generally absorb red-purple wavelengths in solar
spectrum (Calogero et al. 2009). UV-VIS spectroscopic analysis is presented in
the following figure. Various plants and their selected parts have been utilized
for the extraction of natural dyes.

F IGURE 3.12: Absorbance of Betalain

38
 Chapter 4

Modeling of The Proposed DSSC

4.1 Modeling a DSSC

The Dye Sensitized Solar Cell was modelled using nano rods of TiO2 submerged
in dye. The model is built by placing 3 layers of dye, redox electrolyte and a thin
gold layer sandwitched by TCO.
The two layers of TCF are shorted by copper block to find out the short circuit

F IGURE 4.1: Designed Model of DSSC

current by simulating the model in COMSOL. The model was built in SolidWorks
and then imported to COMSOL for conveniency.The modelled DSSC is shown in
Fig. 4.1. For our design, we have chosen the layer thickness as follows:

39
 TABLE 4.1: Layer Thickness used for modeling our DSSC

Layer Name Layer Thickness(µm)

TCO 10

Dye Sensitizer 45

Redox Electrolyte 15

Gold 3

4.2 Modeling the Characteristic Equation

From the suggestion of Södrgren et al[39], a simple model of DSSC can be as-
sumed which is based on two simple equations. The first one being, the continu-
ity equation of generation, transportation and recombination within the nanoporous
film given in eqn 4.1.

δ2 n ( x ) n ( x ) − n0 δn
D 2
− + φαexp(−αx ) = (4.1)
δx τ δt
Where, n(x)= The excess concentration of the photogenerated electrons at position
x within the film measured from the TiO2 /transparent conducting
oxide
n0 = The concentration of electrons under equilibrium conditions in dark
τ = The conduction band free electrons life time
D = The diffusion coefficient of electrons
Φ0 = The illumination intensity (incident photon flux, cm-2 s-1 )
α = The light absorption coefficient of the porous film

Under a steady-state condition of an irradiated DSSC, Eq. 4.1 becomes

δ2 n ( x ) n ( x ) − n0
D − + φαexp(−αx ) = 0 (4.2)
δx2 τ
Under short-circuit conditions, electrons are easily extracted as photocurrent and
none of the electrons are drawn directly to the counter electrode. Therefore, the
two boundary conditions are:

40
 n (0) = n0 (4.3)
dn
=0 (4.4)
dx x =d

Where, d = porous electrode thickness

The second equation completing the model links the excess concentration of pho-
togenerated electrons at the back contact, ncontact , with the photovoltage, Vph ,
through the following expression[39][40]

kT ncontact
Vph = m ln (4.5)
q n0

Where, k = Boltzmann Constant

T = Absolute Temperature
m= Ideality Factor

Solving, Eq. 4.2 with the boundary conditions in Eq. 4.3 and Eq. 4.4, short
circuit current density, JSC can be achieved.
 
 
qφLα  d Lα exp (−dα) 
JSC = 2 2
− Lα + tanh +   (4.6)
1−L α L cosh d ] L

Where, L is the diffusion length, given by

√
L = Dτ (4.7)

If the DSSC operates under a potential difference V between the Fermi level of
the TiO2 and the redox potential of the electrolyte, the density of the electrons at
the TiO2 /TCO interface (x = 0) increases to n giving a new boundary condition

n (0) = n (4.8)
The second boundary condition at x = d remains unchanged as shown in Eq. (4.4).
Solving Eq. (4.2) and using Eq. (4.5) yields the relation ship between the current
density and V[39][40].
 
kTm  L ( JSC − J )
V= ln   + 1 (4.9)
q qDn tanh d0 L

41
Rearranging Eq. 4.9, we get,
    
qDn0 d qV
J = JSC − tanh exp −1 (4.10)
L L kTm
If J = 0 mAcm-2 , then we get V = VOC . So, The Open Circuit Voltage is given by
Eq 4.11.  
kTm  LJSC
V= ln   + 1 (4.11)
q qDn0 tanh Ld
And at MPP, J = JMP . Therefore From Eq. 4.9, we get.
 
kTm  L ( JSC − J MP )
VMP = ln   + 1 (4.12)
q qDn tanh d 0 L

Again, We Know that,

P = JV (4.13)
 
dP dJ
= Jmp + =0 (4.14)
dV V =Vmp dV

Also, transperancy of TCO with absorption coefficient, α1 is,

T = exp (−α1 Th ) (4.15)

Where, Th is the thickness of the TCO layer.
So, if Φ0 is the incident optical energy density on the DSSC, actual optical energy
received by the photosensitizer layer will be,

φ = φ0 × exp (−α1 Th ) (4.16)

42
 Chapter 5

Simulation and Result

5.1 Assumptions and Conditions

Using Eq. 4.12 and Eq. 4.10, a simulation can be done. Assuming AM1.5 global
spectrum we have an incident optical intensity of 100mWcm-2 . In our model, we
have considered the effective photo sensitized layer has a width of 45µm. Also,
we have used TCF with width of 10µm.
For the materials we have used,
Absorption Coefficient of the porous film, α = 5000 cm-1
Ideality factor, m = 4.5
Intrinsic electron concentration, n0 = 1 × 1016 cm-3 .

5.2 Current Density and Power Density Calculations

For ITO, at 500nm wavelength we have I-V Characteristic Graph and P-V charac-
teristic graph as shown in Figure 5.1.
From Figure 5.1, it can be seen that,
Maximum Power Generated, P ≈ 2.926 mWcm-2
Open Circuit Voltage, VOC ≈ 0.433V
Short Circuit current density, JSC ≈ 13.91 mAcm-2
Fill Factor,FF ≈ 0.487
At the same wavelength, with FTO we get the characteristics of the same DSSC
as shown in Fig. 5.2.
From Figure5.2, it can be seen that,
Maximum Power Generated, P ≈ 1.93 mWcm-2
Open Circuit Voltage, VOC ≈ 0.4V
Short Circuit current density, JSC ≈ 10.29 mAcm-2
Fill Factor,FF ≈ 0.47

43
 F IGURE 5.1: I-V and P-V Characteristics of ITO coated DSSC

F IGURE 5.2: I-V and P-V Characteristics of FTO coated DSSC

Now if we test it with PEDOT:PSS Coated Solar Cell we can get the characteristics
of the same DSSC as shown in Fig 5.3.
From Figure 5.3, it can be seen that,

Maximum Power Generated, P ≈ 3.062 mWcm-2

Open Circuit Voltage, VOC ≈ 0.43V
Short Circuit current density, JSC ≈ 14.37 mAcm-2
Fill Factor,FF ≈ 0.496

44
 F IGURE 5.3: I-V and P-V Characteristics of PEDOT coated DSSC

5.3 Relation of generated Current and Power with Ab-

sorption Coefficient of TCF
Absorption Coefficient, α, of the TCF is very important for the performance of
DSSC. Keeping all the parameters same, if we simulate the data with respect to
absorption coefficient of the TCF we get the result shown if Fig. 5.4.

F IGURE 5.4: Effect of Absorption Coefficient on Current and Power of DSSC

It can be seen that, if the absorption coefficient, α is greater than 1613 cm-1 , then
the solar cell acts as a photo-conductive device which means it consumes power
from the bias source.

45
5.4 Improvement with Dye
Over time, Dyes have come very far. One of the most popular dyes at present is
N-719. As it is very efficient in absorbing solar radiation. Using this dye we have
the characteristic graph shown in Fig 5.5.

F IGURE 5.5: Characteristic Graph of DSSC with N719 dye

From Figure 5.5 we find,

Maximum Power Generated, P ≈ 3.84 mWcm-2
Open Circuit Voltage, VOC ≈ 0.4952V
Short Circuit current density, JSC ≈ 15.1 mAcm-2
Fill Factor,FF ≈ 0.5135
But as time has progressed, so have technology. If we use TBA as dye. we have
slight improvement on MPP in our DSSC but the Fill Factor is decreased. The
Characteristic Graph of DSSC with TBA is shown in Fig 5.6.

F IGURE 5.6: Characteristic Graph of DSSC with TBA

From Figure 5.6 we find,

46
Maximum Power Generated, P ≈ 3.89 mWcm-2
Open Circuit Voltage, VOC ≈ 0.4965V
Short Circuit current density, JSC ≈ 15.26 mAcm-2
Fill Factor,FF ≈ 0.5134
With TER the, the characteristic graph becomes as shown on Fig 5.7.

F IGURE 5.7: Characteristic Graph of DSSC with TER

From Figure 5.7 we find,

Maximum Power Generated, P ≈ 3.92 mWcm-2

Open Circuit Voltage, VOC ≈ 0.4969V
Short Circuit current density, JSC ≈ 15.31 mAcm-2
Fill Factor,FF ≈ 0.5143
Using metal free sensitizers and natural sensitizers also give similar results like
N719. Though natural sensitizers are very cost efficient they lack the longevity of
the other two types of sensitizers.
At present, Ru-based sensitizers are the most efficient sensitizer for DSSC as they
have undergone a huge number of researches. With our simplified model, we
have achieved a fill factor of 51.43%.
If more researches on natural sensitizers are performed, they might give similar
or better performance than Ru-based sensitizers.

47
 Chapter 6

Conclusion and Suggestion For

Future Work

6.1 Conclusion
DSSCs are currently the most efficient third-generation (2005 Basic Research So-
lar Energy Utilization 16) solar technology available. Other thin-film technolo-
gies are typically between 5% and 13%, and traditional low-cost commercial sil-
icon panels operate between 14% and 17%. This makes DSSCs attractive as a
replacement for existing technologies in "low density" applications like rooftop
solar collectors, where the mechanical robustness and light weight of the glass-
less collector is a major advantage. They may not be as attractive for large-scale
deployments where higher-cost higher-efficiency cells are more viable, but even
small increases in the DSSC conversion efficiency might make them suitable for
some of these roles as well.
There is another area where DSSCs are particularly attractive. The process of
injecting an electron directly into the TiO2 is qualitatively different from that oc-
curring in a traditional cell, where the electron is "promoted" within the original
crystal. In theory, given low rates of production, the high-energy electron in the
silicon could re-combine with its own hole, giving off a photon (or other form of
energy) which does not result in current being generated. Although this particu-
lar case may not be common, it is fairly easy for an electron generated by another
atom to combine with a hole left behind in a previous photoexcitation.
In comparison, the injection process used in the DSSC does not introduce a
hole in the TiO2 , only an extra electron. Although it is energetically possible for
the electron to recombine back into the dye, the rate at which this occurs is quite
slow compared to the rate that the dye regains an electron from the surrounding
electrolyte. Recombination directly from the TiO2 to species in the electrolyte is
also possible although, again, for optimized devices this reaction is rather slow.
On the contrary, electron transfer from the platinum coated electrode to species
in the electrolyte is necessarily very fast.

48
 As a result of these favorable "differential kinetics", DSSCs work even in low-
light conditions. DSSCs are therefore able to work under cloudy skies and non-
direct sunlight, whereas traditional designs would suffer a "cutout" at some lower
limit of illumination, when charge carrier mobility is low and recombination be-
comes a major issue. The cutoff is so low they are even being proposed for indoor
use, collecting energy for small devices from the lights in the house.[41]
A practical advantage which DSSCs share with most thin-film technologies,
is that the cell’s mechanical robustness indirectly leads to higher efficiencies at
higher temperatures. In any semiconductor, increasing temperature will pro-
mote some electrons into the conduction band "mechanically". The fragility of
traditional silicon cells requires them to be protected from the elements, typically
by encasing them in a glass box similar to a greenhouse, with a metal backing
for strength. Such systems suffer noticeable decreases in efficiency as the cells
heat up internally. DSSCs are normally built with only a thin layer of conduc-
tive plastic on the front layer, allowing them to radiate away heat much easier,
and therefore operate at lower internal temperatures. An accurate approach to
calculate the internal parameters of a DSSC and material preference for better ef-
ficiency is proposed in this article. This method provides a tool for researchers
to estimate theoretically the internal parameters instead of digging through liter-
ature for their experimental value. This approach is based on the values of the
short circuit current density JSC , open circuit voltage VOC , and the current density
and voltage at the maximum power point i.e. Jmp and V’MP , respectively.
The PEDOT:PSS was considered as an efficient alternative structure for indium
tin oxide (ITO) in organic photovoltaics, due to the elimination of some draw-
backs of ITO, such as high production costs and breakable structure under deflec-
tion. Calculating the absorption co-efficient we have found out that PEDOT:PSS
give more power efficiency than inorganic TCO.
This material can provide superior properties like flexibility, low cost and high
safety.
Industrial development of DSSC has also started. Several Several commercial
providers are promising availability of DSCs in the near future:[42]
Dyesol officially opened its new manufacturing facilities in Queanbeyan Aus-
tralia on 7 October 2008. It has subsequently announced partnerships with Tata
Steel (TATA-Dyesol) and Pilkington Glass (Dyetec-Solar) for the development
and large scale manufacture of DSC BIPV. Dyesol has also entered working re-
lationships with Merck, Umicore, CSIRO, Japanese Ministry of Economy and
Trade, Singapore Aerospace Manufacturing and a joint Venture with TIMO Korea
(Dyesol-TIMO).
Solaronix, a Swiss company specialized in the production of DSC materials since
1993, has extended their premises in 2010 to host a manufacturing pilot line of
DSC modules.

49
SolarPrint was founded in Ireland in 2008 by Dr. Mazhar Bari, Andre Fernon and
Roy Horgan. SolarPrint was the first Ireland-based commercial entity involved
in the manufacturing of PV technology. SolarPrint’s innovation was the solution
to the solvent-based electrolyte which to date has prohibited the mass commer-
cialisation of DSSC. The company went into receivership in 2014 and was wound
up.
G24innovations founded in 2006, based in Cardiff, South Wales, UK. On 17 Oc-
tober 2007, claimed the production of the first commercial grade dye sensitised
thin films.
Sony Corporation has developed dye-sensitized solar cells with an energy con-
version efficiency of 10%, a level seen as necessary for commercial use. Tasnee
Enters Strategic Investment Agreement with Dyesol.
H.Glass was founded 2011 in Switzerland. H.Glass has put enormous efforts to
create industrial process for the DSSC technologie - the first results where shown
at the EXPO 2015 in Milano at the Austrian Pavilion. The milestone for DSSC is
the Science Tower in Austria - it is the largest installation of DSSC in the world -
carried out by SFL technologies.

6.2 Suggestion For Future Work

We have studied the loss due to limited optical passband of the TCF and their op-
tical absorption coefficient. As we have seen that, just by improving the material
for TCF, the Form Factor can be increased by 1% - 2% which is very impressive.
Also, PEDOT:PSS is electrically more conductive than ITO and FTO, which re-
duces the electrical loss of the equivalent circuit.
By using, better engineered materials for the DSSC The efficiency was increased
further. Further study on the engineering over the Sensitizers could increase the
performance even more. Changing Protonation, π-conjugation bridge between
carboxylic acidgroups and the ruthenium chromophore, engineering the alkyl
chains of the sensitizer also affects their IPCE.
Also, the performance of the Solar Cell could be increased by engineering the Re-
dox Materials. Redox Materials passively affects the conversion procedure. So,
based on our research and previous researches, following the same approaches
researching on the Redox Materials can vastly improve the performance and effi-
ciency of DSSC.

50
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