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Conductive Polymer Dye Sensitive Solar Cell (DSSC) for Improving the
Efficiency

Thesis · November 2014

DOI: 10.13140/RG.2.2.14506.47045

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Republic of Iraq
Ministry of Higher Education
And Scientific Research
University of Baghdad
College of Science
Department of physics

Conductive Polymer Dye Sensitive

Solar Cell (DSSC) for Improving the
Efficiency

A Thesis
Submitted to the Committee of the College of Science,
University of Baghdad in Partial Fulfillment of the
Requirements for the Degree of Master
of Science in Physics
(Laser and Optoelectronics Physics)

By
Ahmed Ali Assi
B.Sc. Babylon University 2012

Supervised by

Ass. Prof. Dr. Wasan R. Saleh

2014 A.D 1435 A.H

‫[‬

‫سورة النور‪[35]:‬‬
 Certification of the Supervisors

I certify that this thesis was prepared under my supervision at the Department of
Physics, College of Science, university of Baghdad by Ahmed Ali Assi in partial
fulfillment of the requirements for the Degree of Master of Science in Physics (Laser
and Optoelectronics Physics).

Signature:

Name: Dr. Wasan R. Saleh

Title: Assist. Professor
Address: College of Science,
University of Baghdad
Date: / / 2014

Certification of the Head of the Department

In view of available recommendation, I forward this thesis for debate by the
examination committee.

Signature:

Name: Dr. Raad Abdul Kareem Radhi

Title: Professor
Address: Head of physics department,
Collage of Science,
University of Baghdad
Date: / /2014
 Acknowledgments

First, I am thanks deeply Allah for supporting me to

achieve this work which I hope will serve our
community. I wishe to express my great thanks and the
sincerest gratitude to my supervisors Dr. Wasan R.
Saleh For giving me valuable guidance and useful
suggestions and discussions.

I am indebted to the Physics Department/ College of

Science in Bagdad University, the head of the
department, and specially Electro-optics group, for
their support and encouragement.

A special thanks are extended to Dr. Abdul Kareem

M. Ali from (Chemical Dept.), Dr. Thamir Abdul Ameer
Hassan, Mazin Al-Ansari and Dr.salma M. for their
help during the work.

I am greatly thankful to all my class mates especially

to Mr. Hassan Farhan, Mr. Mohanad Qasim, Mr. Naji
talb, and Fouad Abbas ,) for their inspiration and help
for their support

Finally, I express my deep gratefulness to my Family

for their patience and encouragement throughout this
work. And I have to say thank you for everything.

Ahmed

I
 Abstract
In this research we fabricate Dye Sensitive Solar Cell (DSSC) by using
natural dyes (pomegranate dye and Hibiscus sabdariffa dye). The fabricated
cell used additive materials to improve the parts of DSSC (photo electrode,
electrolyte and counter electrode), and thus enhancement the efficiency of
the fabricated solar cell. Transparent conductive glass were prepared by
using Tin (IV) chloride pentahydrate SnCl4.5H2O and Spray pyrolysis
method are used to form Tin Dioxide (SnO2) film, by investigation of the
best condition, substrata temperature between 620˚- 640˚, average sprinkling
number 12 sprinkling each one contain 0.1 mℓ from SnO2 solution at high
20 cm and angle ˚45 are carried out.
The materials that were used in the fabrication of DSSC, both of the Tin
dioxide (TiO2) nanoparticles, multi-walled carbon nanotubes MWCNT,
carboxyl multi-walled carbon nanotubes (f-MWCNT), and silver dispersion
nanoparticles (Ag) used in photo electrode. The polyethylene Glycol 4000
(PEG 4000), Ethylene Glycol (EG), Potassium Iodide (KI), and Iodine (I2)
used to prepared gel-electrolyte and liquid electrolyte. In the counter
electrodes, aniline polymer was used to prepared polyaniline (PANI), carbon
and poly (3,4-ethylene dioxythiophene): poly (styrene sulfonate)
(PEDOT:PSS) modified by dimethyl sulfoxide (DMSO) and the prepared
deposited on conductive glass. The deposition was on SnO2 and on the
purchased ITO substrate conductive glass.
The green conductive polymer polyaniline was prepared by the
electrochemical polymerization method at room temperature. PEDOT:PSS
polymer gave good result as counter electrode, a little information is
available on the measurement of polymer solar cells based on modified
PEDOT:PSS. Best achieved efficiency was 0.72% using natural dye
pomegranate, polyaniline as counter electrode, liquid electrolyte and photo
electrolyte f-MWCNT/Ag/TiO2.

II
 Successfully coated the SnO2 conductive glass by polyaniline polymer by
electrochemical polymerization for aniline to prepare one type of the counter
electrode for DSSC. Polyaniline polymer was coated on ITO conductive
then used as counter electrode for fabrication of DSSC. The resulted
efficiencies were 0.55% for SnO2 and 0.72% for ITO. SnO2 coated glass
gave adhesion for PANI film larger than that for ITO coated glass and the
cost of preparation SnO2 conductive glass was less than that purchased ITO
conductive glass in ratio of 1:5.
From this work we found that Ag nanoparticle enhance the efficiency of
DSSC when used with TiO2 in photo electrode. Added f-MWCNT gave
good enhancement for the efficiency as well as the stability of DSSC. Mixed
Ag nanoparticles with and f-MWCNT gave result better than adding each
one alone when added to the TiO2 paste. The best rates were 1 mℓ/g of silver
dispersion nanoparticles and 0.5 mg/g of f-MWCNT with TiO2, 0.83 g of
KI and 0.083 g with 10 mℓ Ethylene Glycol for liquid electrolyte. 40% W/V
of polyethylene Glycol was added for the same liquid electrolyte to prepar
gel-electrolyte. In counter electrode, it is foundthat polyaniline polymer
given best efficiency in addition to it is easy prepared and low cost.
Used X-ray diffraction pattern to determine structure and type of some
materials such as the prepared SnO2. Absorption spectrum was taken also
for SnO2, ITO, PANI, and Dye to determine the absorbance regions for solar
spectrum especially the visible part. The energy gap for SnO2 film was
calculated 3.825 eV. SEM and AFM measurement were taken to study
topographic shape for SnO2, ITO and PANI surfaces. The grain size for
SnO2 and ITO were 239 nm and 212 nm respectively while diameter tube
for PANI 73 nm while the average surface roughness were 1.24, 0.934
respectively.

III
 List of Content
No. of Subject Page
Item Numbe
r
Acknowledgments I
Abstract II
List of Content IV
List of Symbols VII
List of abbreviations VIII
Chapter One – Introduction and Literature Survey
1.1 Introduction 1
1.2 Power from the Solar Resource 1
1.3 Brief history of Photovoltaics 3
1.4 Solar cell 5
1.4.1 Types of Solar Cell 6
1.4.2 Development of the Solar Cells 8
1.5 Dye Sensitized Solar Cells (DSSCs) 9
1.5.1 Basic Principles of DSSCs 10
1.5.2 Charge Transfer and Transport Dynamics 11
1.5.2.1 Chemical processes in DSSC 12
1.5.3 Parts of DSSC:
1.5.3.1 The Working Electrode (photo electrode) 12
1.5.3.2 The Sensitizing Dye 13
1.5.3.3 Conducting substrates 14
1.5.3.4 The Regenerative Electrolyte 16
1.5.3.5 Additive material to enhance the efficiency 18
1.5.3.6 Sealing cell 19
1.6 Stability of solar cell 20
1.7 Characterization techniques of DSSCs 21
1.8 Comparison of Solar Cell Materials 23
1.9 Advantage of DSSC 24
1.11 Aim of the work 25
1.12 Literature Review 26
Chapter Two - Experimental Work
2.1 Introduction 32
2.2 Chemical Materials 33
2.3 Measurement Techniques 34
IV
 2.4 Preparation of Conductive Glass 36
2.4.1 Indium Doped tin oxide (ITO) Coated Glass 36
2.4.2 Tin Dioxide (SnO2) Coated Glass 37
2.5 Preparation of TiO2 Past 38
2.6 Preparation of Photo Electrode 39
2.6.1 Deposition and Sintering TiO2 Past 39
2.6.2 Staining in the Dye 40
2.7 Preparation of Electrolyte 41
2.7.1 Solution Electrolyte 41
2.7.2 Gel Electrolyte 41
2.8 Preparation of Counter Electrode 42
2.8.1 Carbon Coated Counted Electrode 42
2.8.2 PEDOT:PSS Coated Counter Electrode 43
2.8.3 Polyaniline Polymer Coated Counter Electrode 43
2.8.3.1 Polymerization Method of PANI 44
2.9 Assembling and Sealing The Dye Sensitive Solar Cells 46
2.10 Characterization of DSSC 47
2.10.1 Structural and Morphological Measurements 47
2.10.2 Optical Measurements 47
2.10.3 Electrical Measurement 48
Chapter Three - Result and Discussions
3.1 Introduction 50
3.2 Optical Measurements 50
3.2.1 Absorption spectrum of SnO2 50
3.2.2 Absorption Spectrum of ITO 52
3.2.3 Absorption Spectrum of TiO2 52
3.2.4 Absorption Spectrum of Pomegranate Dye 53
3.2.5 Absorption Spectrum of PANI 53
3.2.6 Fourier Transform Infra-Red (FTIR) of PANI 54
3.3 Structure Measurements 56
3.3.1 XRD Measurement of PANI 56
3.3.2 XRD Measurement of SnO2 57
3.3.3 XRD Measurement of TiO2 58
3.4 The Surface Morphology Measurements 59
3.4.1 The Surface Morphology of SnO2 and ITO Films using 59
AFM
3.4.2 The Surface Morphology of PANI Film using AFM 60
V
3.4.3 The Surface Morphology of PANI Film using SEM 61
3.5 Electrical Measurements 62
3.5.1 Hall Effect measurements for SnO2 62
3.5.2 Sheet Measurement of SnO2 as a Function of Substrate 64
Temperature (Ts) and Sprinkling Numbers (N)
3.6 Effect of Potassium Iodide (KI) Concentration 65
3.7 Effect of Polyethylene glycol 4000 (PEG 4000) 66
Concentration
3.8 Effects of Dye Type 67
3.9 Effect of Additive Materials on Efficiency 68
3.9.1 Effects of adding additive Multi-Walled Carbon 68
Nanotubes (MWCNT) and carboxyl Multi-Walled
Carbon Nanotubes (f-MWCNT)
3.9.2 Effect of Adding Silver Nanoparticle to TiO2 Powder 70
3.10 Effects of Counter Electrode Type 71
3.11 Characterization of Assembled DSSCs 72
3.12 Conclusion 74
3.13 Suggested future work 75
4 Reference 76

VI
 List of Symbols

Symbol Description
°C Centigrade degree (unit for measuring the
temperature)
µ Mobility (cm2 /Vs)
a, b, c Lattice constant
C Speed of light in vacuum (m/sec)
D Average crystallite size (nm)
dhkl Inter planer distance
E Electron charge
Eg Direct energy band gap (eV)
f.f Filling factor
H Planck’s constant(J.s)
hkℓ Miller indices
hυ Photon energy(eV)
I (λ) Photocurrent at wavelength λ (mA)
Isc Short circuit current (mA)

Pin input optical power(W m-2)

Pin (λ) Input optical power (W m-2) at wavelength λ
R Resistance (Ω)
R Constant
RH Hall coefficient(cm3/C)
Sa Surface roughness average
Sq Root Mean Square roughness
Sz the ten point height
T Temperature

VII
 t Film Thickness (µm)
Symbol Description
VH Hall voltage (V)
Vmax Maximum voltage (Volt)
Voc Photovoltage open-circuit (Volt)

λ Wavelength (nm)
ρ Resistivity(Ω.cm)
σ Conductivity(Ω.cm)-1
γ Frequency (Hz)

List of Abbreviations

Symbol Description
A Admittance

ACN Acetonitrile

AFM Atomic Force Microscope

AM Air Mass

PEDOT:PSS poly (3,4-ethylene dioxythiophene): poly(styrene sulfonate)

CPs Conjugated Polymers

DSSC Dye-Sensitized Solar Cell

EC Ethylene Carbonate

EG Ethylene Glycol

Eg Energy Gap (eV)

f-MWCNT Functionalized Multi-Walled Carbon Nanotubes

FTIR Fourier Transform Infrared Spectroscopy

VIII
 FTO Fluorine-Doped Tin Dioxide

IPCE Incident Photon-to-electron Conversion Efficiency

IR Infra-Red

ITO Indium doped Tin oxide

JCPDS Joint Committee on Powder Diffraction Standards

MWCNT Multi-Walled Carbon Nanotubes

PANI Polyaniline

PEG Polyethylene Glycol

PEO Polyethylene Oxide

PV Photovoltaics

Ru Ruthenium dyes

SEM Scanning Electron. Microscope

TCO Transparent Conducting Oxide

UV-Vis UV-Visible spectroscopy

XRD X-Ray Diffraction

IX
1.1 Introduction
It has become a common sense to everyone that we are now living in a
world, in which traditional fossil energy is being consumed at an
unprecedented rate. A serious problem, namely global warming, has
originated from the use of fossil fuel. As a solution, renewable energy sources
serve as a key ingredient for the development of a global sustainable society.
Among the existing renewable energy sources, solar energy is one of the most
promising.
Given the vast amount of energy which the population has become
accustomed to consuming, there is a need to produce energy in a sustainable
and renewable way which has zero (or close to zero) CO2 emissions, with
little to no environmental risk associated with it. Renewable energy elements
such as wind, hydro and biomass systems all have great potential, however
solar energy has the potential to be the largest of them all [1]. The earth's
surface receives approximately 104PW of power from the sun (assuming a
solar constant of 1366 W/m2) [2], which makes any yearly power-use by
mankind seem quite insignificant. The energy supply is clearly there for the
taking, however, it is now up to mankind to utilize this impressive resource.

1.2 Power from the Solar Resource

The energy gained from the sun is converted for human consumption by
various different technologies. It can be argued that the majority of energy
systems on earth owes its roots in some way to the sun [3]. Wind energy (and
subsequent wave and hydro energy) derives its power in part of the
differential in temperature of the earth's surface, due to the heating nature of
the sun. Trees and plants use energy from the sun for photosynthesis to grow,
and in turn can be used in biomass systems. Finally, solar thermal systems
and photovoltaics (PV) use energy from the sun directly to create useful
power either in the form of heat, or electricity. Whilst energy from the sun is

1
used in many diverse ways, it is important to understand the make-up of the
solar spectrum so that its properties can be fully optimised.

Figure 1.1: Incidence spectrum of sunlight just above the earth's atmosphere (AM0) and
at the earth's surface (AM1.5G), used as a measurement standard[3].

Figure 1.1 shows the spectrum of light which arrives to the earth from the
sun. The energy from the sun has a characteristic spectrum. Since the sun
emits as a black body, with a temperature around 5800K. Whilst travelling
through vacuum from the sun to the earth, the shape of the spectrum is hardly
altered from that of a black body. This is the extra-terrestrial spectrum of
light, i.e. spectrum of light outside the earth's atmosphere. Once the light
enters the earth's atmosphere, the intensity is attenuated by scattering from
molecules, aerosols and dust particles, as well as absorption by gases in the
atmosphere [4]. When the sun is directly overhead, the distance the light has
to travel to reach the earth is the lowest possible. As the sun moves away from
the zenith through the sky, light has to pass through a greater portion of the
atmosphere, and so the intensity of light is reduced as it reaches the earth's
surface. Assuming the sun is at an angle, Ѳ, from the zenith, then the distance
light has to travel through the atmosphere is the Air Mass = 1/cosѲ, θ=48o

2
1.3 Brief History of Photovoltaic
The history of photovoltaics dates back to the discovery of so-called
“photovoltaic effect” by the French physicist Becquerel in 1839 [5], which is
defined as the production or change of electric potential between two
electrodes separated by a suitable electrolyte or other substance upon light
irradiation. Since then, a variety of concepts and devices have been developed
to convert sunlight into electricity for the sake of exploring clean and
renewable energy.
The first large area (30 cm 2) photovoltaic device using Se film was set up
by Fritts in 1883, more than one hundred years ago [6]. A modern application
of photovoltaic device initiated in 1954. The researchers at Bell Labs in the
USA discovered that a voltage was produced from the p-n junction diodes
under room light. In the same year, they produced a Si p-n junction solar cell
with 6% efficiency, which is a milestone of photovoltaic technology [7].
Within a year, a thin-film heterojunction solar cell based on Cu2S/CdS also
achieved 6% efficiency [8]. A year later, a 6% GaAs p-n junction solar cell
was reported by RCA Lab in the US [9]. Within a year, Hoffman Electronics
(USA) offered commercial Si photovoltaic cells with 2% efficient at
$1500/W. The efficiency record was refreshed quickly by this company – 8%
in 1957, 9% in 1958 and 10% in 1959. By 1960, fundamental theories of p-n
junction solar cell were developed to explain the relation between band gap,
incident spectrum, temperature, thermodynamics, and efficiency [10-13]. In
1962, the first commercial telecommunication satellite Telstar powered by a
photovoltaic system was launched. In 1963, Sharp Corporation (Japan)
produces the first commercial Si modules. 1973 was an important year for
photovoltaics: worldwide oil crisis spurred many countries to seek for
renewable energy including photovoltaics. Moreover, a great improvement
was made in the GaAs photovoltaic device, which attained an efficiency of
13.7% [14]. During 1970–1979, many big photovoltaic companies were

3
established, such as Solar Power Corporation (1970), Solarex Corporation
(1973), Solec International (1975) and Solar Technology International (1975).
The first book dedicated to PV science and technology by Hovel (USA) was
also published in 1975. The photovoltaic technology developed very fast in
the 1980s. The first thin-film solar cell with over 10% efficiency was
produced in 1980 based on Cu2S/CdS. ARCO Solar was the first company to
provide photovoltaic modules with over 1 MW per year (1982). In 1985, the
researchers of the University of New South Wales (Australia) fabricated a Si
solar cell with more than 20% efficiency under standard sunlight [15].
Worldwide photovoltaic production reached 100 MW per year in 1997 and
this value increased to 1000 MW per year in 1999. Several important events
during this decade included the emergence of GaInP/GaAs multijunction solar
cell with efficiency over 30% [16], photoelectrochemical dye sensitized solar
cell with 11% efficiency [17] and Cu (InGa) Se2 thin-film solar cell with 19%
efficiency [18].

Figure 1.2: Historical trends of cost per watt of solar cells

and volume of production [19].

4
 Although photovoltaics can provide clean and renewable energy, the high
cost of production and installation excludes their widespread application.
Hence, the usage of solar energy is still considered as an alternative to
traditional energy resources (petroleum, coal and natural gas). However, as
the volume production increases, the cost drops remarkably (shown in Figure
1.2), which makes it in the economic reach of wider markets.
It is reasonable to believe that the photovoltaic industry has the potential to
become one of the major electricity suppliers in this century and to improve
people’s life quality in terms of alleviating environmental damage.

1.4 Solar Cells

A solar cell device converts the sunlight directly into electricity through the
photovoltaic. In principle, it depends on two parameters. The generation of
current by absorbing incident illumination and the loss of charge carriers via
so-called recombination mechanisms [20]. Conventional semiconductor, solar
cells are based on p-n junctions. In a p-n junction, two semiconductors with
different majority charge carriers and doping concentrations n-doped and p-
doped material is in close contact, as shown in figure 1.3 [21].

Fig 1.3: p-n junction of solar cell [21].

5
1.4.1 Types of Solar Cell
There are mainly three types of solar cells, according to the materials they
employ: inorganic, organic and hybrid, as shown in figure 1.4. Inorganic solar
cells, such as silicon-based and III-V compounds based, are dominating the
solar cell market with the typical power conversion efficiency of up to 20 %
[22, 23]. A typical inorganic solar cell is composed of two metal electrodes,
p-n semiconductor junction and an optional anti-reflection coating, as shown
in figure 1.5.

Figure 1.4: Types of solar cells [24].

Figure 1.5: The structure of inorganic solar cells [24].

6
 Although inorganic solar cells govern the solar cell market, the
manufacturing processes often involve costly, high vacuum, and numerous
lithographic steps, resulting in a high production cost and high energy
consumption [25, 26].
Still in their infancy, organic solar cells are divided into two categories,
polymer based and small molecule based. Polymer based organic solar cells
are flexible and easy to fabricate, while small molecule based organic solar
cells are intrinsically stable [27]. Organic solar cells have a relatively low
power conversion efficiency [23] and have not yet entered into the
commercial market.
The third type of solar cell is hybrid solar cell. One representative is Dye-
Sensitized Solar Cell (DSSC). This is the focus of the present thesis. There
are two categories of DSSCs, with liquid electrolyte or solid hole conductors
[28, 29] as redox mediator. The power conversion efficiency of DSSCs with
liquid electrolyte is higher than that of DSSCs with solid-state hole
conductors, the latter is comparable to the power conversion efficiency of
organic solar cells (~ 4 % [23, 29]). Currently, the highest power conversion
efficiency of DSSCs with liquid electrolyte is 12.3 % [30]. The typical dye-
sensitized solar cell has sandwich configuration, as shown in figure 1.6. It
includes working electrode, dye, redox mediator and the counter electrode.

Figure 1.6: The structure of dye-sensitized solar cells (DSSCs) [23].

7
 Light comes into the device from the left side, passing through a piece of
conducting glass which is used to collect electrons, a compact layer of TiO 2
preventing short circuit current, and finally reaching the nanoporous working
electrode of TiO2. There is a monolayer of dye molecules attached to the
surface of the TiO2 nanoporous working electrode, which is employed to
convert solar energy into electricity. On the right side, there is a counter
electrode, consisting of a thin layer of catalyst and another piece of
conducting glass. An electrolyte lies between the two electrodes, which
shuttles the electrons between the working electrode and counter electrode,
and thus completes the circuit.

1.4.2 Development of the Solar Cell

The progress in solar cells can be divided into four generations:

a. First generation

First generation solar cells are the dominant technology in the commercial
production of solar cells. These cells are made using a crystalline silicon
wafer; they consist of large areas, single layer p-n junction devices. They are
characterized by broad spectral absorption range and high carrier mobilities,
but they require expensive manufacturing technologies [31].

b. Second generation

The second generation of thin-film solar cell devices are based on low
energy preparation techniques such as vapor deposition and electroplating
[31]. Thin-film solar cells are cheaper but less efficient [32].

c. Third generation

Third generation photovoltaic refers to cell concepts that overcome the

31% theoretical upper limit of a single junction solar cell as defined by
8
Shockley and Queisser [33]. Third generation PV technologies may overcome
the fundamental limitations of photon to electron conversion in single-
junction devices and, thus, improve both their efficiency and cost [34]. The
third generation photovoltaics are very different from semiconductor devices.
These new devices include photo- electrochemical cells, polymer solar cells,
and nano-crystal solar cells [35].

d. Fourth generation
In the fourth generation composite photovoltaic technology with the use of
polymers with nanoparticles can be mixed together to make a single multi-
spectrum layer. Then the thin multi-spectrum layers can be stacked to make
multi-spectrum solar cells more efficient and cheaper based on polymer solar
cell and multi-junction technology [35].

1.5 Dye Sensitized Solar Cells (DSSCs)

It is an urgent task to develop much cheaper photovoltaic devices with
reasonable efficiency for widespread application of photovoltaic technology.
A new type of photovoltaic devices called “dye sensitized solar cells”
(DSSCs) based on nanocrystalline TiO2 was developed by O’Regan and
Grätzel in 1991 [36]. This type of solar cells is featured by their relatively
high efficiency (exceeding 11% of full sunlight) and low fabrication cost
(1/10–1/5 of silicon solar cells) [37]. Since the birth of DSSCs, great efforts
have been devoted to making these devices more efficient and stable. Long-
term stability tests show good prospects of DSSCs for domestic devices and
decorative applications in this century [38,39].

9
1.5.1 Basic Principles of DSSCs
Figure 1.7 depicts the typical structure and operation principle of a DSSC.
Generally, a DSSC consists of four elements: a photoelectrode with a thin
layer of nanostructured wide band-gap semiconductor (usually TiO2, ZnO,
SnO2 or Nb2O5) attached to the conducting substrate (fluorine-doped tin
dioxide, FTO), a monolayer of dye adsorbed on the surface of the
semiconductor, electrolyte containing a redox couple (typically I -/I3-) and a
counter electrode (platinized FTO).

Figure 1.7: Typical structure and operation principle of a DSSC [40].

Photo-excitation of the dye results in the injection of electrons into the

conduction band of the semiconductor. The dye is regenerated by I - in
electrolyte. The I- is regenerated in turn at the counter electrode by the
reduction of I3-with electrons which have passed through the external circuit.
The voltage generated under illumination corresponds to the difference
between the quasi-Fermi level of the electron in the semiconductor and the
redox potential of the electrolyte. The net outcome is the conversion from
light to electricity without any permanent chemical transformation. DSSC is
thus a regenerative-type photo electrochemical cell [41].

11
1.5.2 Charge Transfer and Transport Dynamics
To describe the charge transit and transport dynamics, figure 1.8 shows the
major charge transfer and transport processes in a DSSC [42]. Upon light
absorption by the adsorped dye molecules (route 1), the ultrafast electron
injection into the conduction band of semiconductor photoelectrode (route 2)
takes place on a picosecond timescale. There are two important back-
reactions in a DSSC. One is the recombination of conduction band electrons
with the oxidized dye molecules (route 3), which occurs on a microsecond
timescale.

Counter electrode

Figure 1.8: Major charge transfer and transport processes of a DSSC[42].

It is noted that the reduction rate of the oxidized dye (S +) by I- (route 7) is

also very fast, occurring on a nanosecond timescale, which can compete
efficiently with the back-reaction (route 3) to ensure the collection of
photoelectrons by back-contact. The other is the recombination of conduction
band electrons with I3- in the electrolyte (route 4). The electron transport in the
semiconductor to the back-contact (route 5) occurs on a millisecond to second
time scale. The I- is regenerated in turn at the counter electrode (route 6) by
the reduction of I3- with electrons which have passed through the external
circuit.

11
1.5.2.1 Chemical Processes in DSSC
The photoelectric chemical process in DSSC can be expressed as equations
(1.1) –(1.6). The photo excited electron injects into the conduction band of
TiO2 in subpicosecond time scales [43]. The dark reaction equations 1.5 and
1.6 also occur during the light-to-electricity conversion, but do not play a
remarkable negative effect on the photovoltaic performance of DSSCs owing
to their slow reaction speed compared with that of equation 1.2 [44].

TiO2|S + hv → TiO2|S* Excitation (1-1)

TiO2|S* → TiO2|S+ + e–(CB) Injection (1-2)
TiO2|2S+ + 3I– → TiO2|2S + Regeneration (1-3)
+ 2e–(PT) → 3 Reduction (1-4)
+ 2e–(CB) → 3I– Reception (dark reaction) (1-5)
TiO2|S+ + e–(CB) → TiO2|S Recombination (dark reaction) (1-6)

It can be seen that DSSCs are a kind of complex system for light-to-electricity
conversion. As a basic component, the electrolyte plays an important role in
the process of light-to-electricity conversion in DSSCs. The electrolytes
employed in DSSCs can be classified as liquid, solid-state, or quasi-solidstate.

1.5.3 Parts of DSSC

In general, Dye Sensitized Solar Cell consist of the following parts:

1.5.3.1 The Working Electrode (anode)

Upon excitation in the sensitiser, the electron is injected into the TiO2
working electrode. The deposition of the TiO2 nano-particles are usually done
by a screen printing or a doctor building method, which requires the nano-
particles to be incorporated into a paste, usually made of a solvent, typically
terpineol, and an organic binding material such as ethyl cellulose [45]. The

12
incorporation of the ethyl cellulose is important, since the amount of binder in
the paste very much determines the porosity of the final TiO2 layer, which is
usually around 60%. After deposition of a sufficiently thick layer (around
10µm), the deposited film is annealed, usually in air at 450. To burn off the
supporting ethyl cellulose structure and sinter the individual particles
together, forming a porous, interconnected network of TiO2 nano-particles.
In the case of a conventional DSSC, the Nano size and porous structure of
the TiO2 network gives rise to a very high junction area, since the liquid
electrolyte used can penetrate the entire network.
Finally, a porous network of NiO has emerged as a potential material to be
used in p-type DSSCs, where holes are injected from a dye into the valence
band of the supporting oxide, in contrast to the conventional process [46, 47].

1.5.3.2 The Sensitizing Dye

The sensitising dye drives the electron generation in the DSSC. Without it,
the wide band-gap semi-conductor would only be able to contribute electrons
from high energy photons arriving from the UV, resulting in very low photo-
currents. Grafting the dye to the oxide surface pushes the absorption window
through into the visible, making the whole system useful for PV conversion.
The dye needs to satisfy many requirements for it to be successful in a DSSC
1- It needs to be able to absorb a wide spectrum of light, ideally up to 900
nm.
2- It needs to easily (and permanently) attach to the oxide surface.
3- Its excited state needs to be more negative than the conduction band of the
TiO2 to ensure fast charge injection. Conversely, the oxidized state of the
dye, S+, needs to be more positive than the redox potential, E F redox, of the
electrolyte so it is efficiently reduced back to its ground state.
4- It should be chemically robust and suffer little to no change over the
course of its operation [48].

13
 The dye standard" in the DSSC community is a ruthenium centered
polypyridyl complex, cis-bis(isothiocyanato) bis(2,2'-bipyridyl-4,4'-
dicarboxylato) ruthenium (II), named the N3 dye [48], which was followed by
the tetrabutylammonium adduct of the N3 dye called N719 [49]. Ruthenium
centered complexes like these have shown the best promise over the course of
the development of the DSSC since its initial breakthrough in 1991, to today.
Whilst many of these complexes has been synthesized over the years by
different groups to increase the performance of the DSSC, the basic make-up
of each molecule is essentially the same.

1.5.3.3 Conducting Substrates

New dyes are constantly being synthesized, new oxide architectures are
being explored, and a new hole conducting mediums is being investigated.
Another element of the device, though which is sometimes not appreciated is
the role of the transparent conducting oxide(TCO), which is vital to the
operation of not only DSSCs, but all thin film solar cells. The TCO is a
degenerately doped oxide thin film deposited on a substrate which has both
high transmission in the visible wavelength range, allowing a high amount of
photons through to the absorber, and is of high enough conductivity to collect
electrons efficiently without suffering from significant ohmic losses. The
TCO sandwiches the components of the DSSC together, forming a pathway
for generating electrons to be removed from the device. Probably the most
well-known of the materials is tin doped indium oxide (ITO), which displays
very high transmission in the visible, and high conductivity, mainly due to
possessing a very high carrier concentration.
The Fluorine-Doped Tin Dioxide (FTO) has a lower carrier concentration
than ITO, and so the conductivity is usually lower, and FTO tends to absorb
slightly in the visible and have a noticeable haze, due to incorporation of
undesirable phases in the film from the (atmospheric chemical) deposition

14
process. Table 1-1 shows an outline of some of the TCOs which have been
explored.

Table 1.1: Different oxides and their dopants used in TCO research taken from [50].

Figure 1.9: Transmission, Reflection and absorption spectra of a typical TCO [51].

15
 The transmission properties of TCOs are very well defined, and only vary
slightly between each TCO depending on their individual material properties.
It is characterized by three parts [50]:
1- Strongly absorbing region in the short wavelength range due to band-
gap excitation of the oxide.
2- Transparent region in the visible.
3- Reacting region due to free carriers past a characteristic wavelength in
the infra-red (IR).
All these features are highlighted in figure 1.9. The transmission in the visible
may be attenuated slightly by absorption of un-reacted species in the oxide, or
reaction by scattering at rough surfaces, however it is usually above 80%. For
smooth films, there is a characteristic periodic increase and decrease in
transmission.

(4) Counter Electrode

The counter electrode plays the role of returning electrons that are
generated at the photo-electrode and delivered through the external circuit,
back to the electrolyte. Since the electrolyte is corrosive, the counter electrode
requires high corrosion resistance as well as a high reaction rate when
reducing iodine in the electrolyte to an iodide ion. Considering the balance
between these factors, a conductive glass electrode coated with platinum (Pt)
has been used heretofore. Carbon electrodes and conductive polymers have
been examined as an alternative to expensive Pt, whereas such materials do
not come up to Pt in terms of the reduction rate.

1.5.3.4 The Regenerative Electrolyte

Whilst the working electrode provides a pathway for electrons to travel to
the front, negative contact, the remaining hole must be transferred in some
manner to the back, positive electrode. As is the case in classical photo-

16
electrochemical solar cells, this transfer are mediated through an electrolyte,
and in the case of the DSSC, the most successful is based on a ⁄ redox
couple in a non-aqueous solvent. In the DSSC, the regeneration of the
oxidised sensitiser is performed by diffusion of I - ions to the dye, which is
then formed to which in turn is then catalytically changed back to I - again
after diffusion to the counter electrode. The electrolyte is typically made from
a small concentration of iodine, around 0.05M, and a higher concentration of
an iodide salt, usually around 0.6M, in a low viscosity solvent. The salt can
either be a standard inorganic salt, with cations from group I elements such as
lithium, sodium or potassium, or more commonly an organic cation, such as
quaternary alkyl ammonium [52] or, in high efficiency devices, an
imidazolium anion [53]. As a consequence, lithium iodide (in small
quantities) is usually added to the electrolyte along with the imidazolium salt
to lower the energy of the conduction band of the TiO2, promoting the
electron injection from the sensitiser to the TiO2 [54]. Conversely, other
additives such as 4-tert-butylpyridine are also added to the electrolyte, which
has been shown to also adsorb onto the TiO 2 surface. Here, an increase in the
band energy position of the TiO2 is seen, as well as reducing the
recombination of electrons from the TiO2 with I-3, which manifests itself as a
significant improvement in voltage [55]. It is clear that the multi-component
nature of the electrolyte plays a key role in the performance of the DSSC,
with each additive having to work in synergy to improve the device.
Electrolytes formed from low viscosity organic solvents have so far
produced the highest efficiency devices, due to the high diffusion coefficient
of the I- and in these solvents. Ionic liquids are a feasible alternative to
conventional electrolytes employing a series of components dissolved in an
organic solvent. The problem associated with sealing a liquid element of the
device though still remains, even though in most cases the ionic liquid is more
easy to handle due to the high viscosity of the liquid. Solidification of the

17
electrolyte, either with polymers or gels [56], represents one method to
improve the handling of the device, whilst still benefiting from the well-
established processes associated with using a I-/ couple.

1.5.3.5 Additive Material to Enhance the Efficiency

For the entry of DSSCs into real market, both long-term stability and
efficiency should be further improved. In this regard, ionic liquid [57,58] and
gel-electrolytes [59,62] are widely employed to overcome the leakage and
sealing problems of conventional liquid electrolytes. New dye sensitizers are
developed to increase the energy conversion efficiency of DSSCs. The most
widely used dyes are ruthenium complexes, which involve a rare metal with a
low annual yield. Great efforts have been devoted to replacing ruthenium
complexes with small organic dye molecules [63,64]. The advantages of
sufficiently large absorption coefficient, tunable energy levels and easy
deposition on various substrates make conjugated polymers (CPs) promising
candidates as organic sensitizers in DSSCs.
The application of conjugated polymers as dye sensitizers in DSSCs has
been reported recently [65-71]. Poly(3-thiophenylene acetic acid) was used as
the dye sensitizer for DSSCs with efficiencies varying from 0.4% to 2.4%
[67-69]. The combination of carboxylated poly(p-phenylene ethynylene) and

polythiophene as the dye sensitizer yielded DSSCs with a power conversion

efficiency of 0.89% [70].

Recently, was developed anionic benzothiadiazole-containing

polyfluorenes with dual absorption peaks and demonstrated their applications

in DSSCs with an efficiency of 1.39% [70]. Up to now, the efficiencies of

polymer dye based DSSCs remain low, and great opportunities arise to
improve the device performance through polymer design and device
fabrication.
18
 Efficient photo-induced charge transfer and well matched energy levels
among the polymer and other components in DSSCs are essential
requirements to produce efficient energy conversion efficiencies [67].
A conjugated polymer (CP) sensitizer containing an electron donating
backbone (triphenylamine) and an electron accepting side chain (cyanoacetic
acid) with conjugated thiophene units as the linkers. DSSC with an energy
conversion efficiency of 3.39% is obtained using such novel CP sensitizer,
which represents the highest efficiency for polymer dye sensitized DSSC.

Carbon nanotubes (CNTs) have been widely used in solar cell research
[72], for example, CNTs have been integrated in organic photovoltaic
devices, both as an electron acceptor material and as a transparent electrode
[73]. This is because the high conductivity along the tube axis of CNTs helps
carriers separation and collection. In 2005, GE Global Research observed a
photovoltaic effect in a pristine nanotube diode device consisting of two
CNTs with different electrical properties [74].
The use of silver nanoparticles helps the polymer capture a wider range of
wavelengths of sunlight than would normally be possible. Practically, silver
particles are encased in an ultra‐thin polymer layer (different than the light‐
absorbing polymer), which is deposited below the light‐absorbing layer [123].
Using silver nanoparticles to enhance absorption. The silver nanoparticles can
scatter visible light very efficiently and create a trapped mode for the incident
light.

1.5.3.6 Sealing The Cell

Sealing the DSSCs has long been a difficult question because of the
corrosive and volatile liquid iodide electrolyte used in the cells. Being directly
related to the long term stability of the cells it seems to be one of the main

19
technological challenges of the DSSC technology [75]. A suitable sealing
material should at least:

1. Be leakproof to the electrolyte components and impermeable to both

ambient oxygen and water vapor.

2. Be chemically inert towards the electrolyte and other cell components.

3. Adhere well to the glass substrate and TCO coating.

Several sealing materials have been used, such as epoxy glue [76], water
glass (sodium silicate) [77], an ionomer resin Surlyn® (grade 1702) from Du
Pont [76,78], aluminum foil laminated with polymer foil [77-79], a vacuum
sealant Torr Seal® [80], or a combination of these. Especially for research
purposes sealing techniques based on O-rings [81, 82] and glass soldering
[81] have been developed. Interestingly, despite the fact that the often used
sealant, the Surlyn® ionomer resin from Du Pont, has been classified by the
manufacturer as not resistant towards iodine (in KI solution) in long term
exposure21, stable long term operation has been demonstrated for DSSCs
utilizing Surlyn® sealing with iodide [76]. At the moment a new sealing
technique for low-power indoor DSSC applications is being patented and
waiting to be published [75].

1.6 Stability of Solar Cell

The stability of the dye cells may be affected by the following issues [83].
1- Chemical stability of the sensitizer dye attached to the TiO2 electrode and
in interaction with the surrounding electrolyte.
2- Chemical stability of the electrolyte.
3- Stability of the graphite or platinum -coating of the counter-electrode in the
electrolyte environment.

21
4- Quality of the sealing of the cell against oxygen and water from the
ambient air, and against loss of electrolyte solvent evaporation from the
cell.

1.7 Characterization Techniques of DSSCs

The basic characterization techniques of DSSCs are described as follows.

(1) Photocurrent-photovoltage (I-V) measurement

The overall conversion efficiency of the dye-sensitized solar cell is

determined by the photocurrent density measured at short circuit current (I sc),

the photovoltage open-circuit (Voc), the filling factor of the cell (FF) and the

input optical power (Pin ).

(1-1)

Where Pin is the input optical power, and I sc, Vocare determined from the

photocurrent-photovoltage curve of the cell.

Figure 1.10 Characteristic I-V curve of a DSSC.

The fill factor was calculated from the following equation:

21
 Where; (1.2)

Where I, V were determined from the point of the curve the product of I and
V have maximum values [29]. A typical I-V curve is shown in figure 1.10.
During the I-V measurement, four parameters mentioned above (Voc, Jsc, FF

and η) will be determined.

(2) Incident photon-to-electron conversion efficiency (IPCE)

measurement.
The sensitivity of a DSSC varies with the wavelength of the incident light.
IPCE measures the ratio of the number of electrons generated by the solar cell
to the number of incident photons on the active surface under monochromatic
light irradiation:

……… (1-3)

Where I (λ) is the photocurrent (μA. Cm-2) given by the cell under
monochromatic illumination at wavelength λ (nm), P in (λ) is the input optical
power (W m-2) at wavelength λ, e is the elementary charge, h is the plank
coninstant, ν is frequency of light, C is the speed of light in vacuum. If not
specified differently, the IPCE is measured under short circuit conditions and
displayed graphically versus the corresponding wavelength in a photovoltaic
action spectrum. This measurement is also useful for indirect determination of
the short circuit photocurrent of a DSSC.

22
1.8 Comparison of Solar Cell Materials
Table 1.2 shows the types and characteristics of solar cell materials for
comparison. In terms of energy conversion efficiency and long-term
reliability, the mainstream solar cells at present are silicon-based. For the sake
of promoting the extent to which photovoltaic

Table 1.2: Types and Characteristics of Solar Cell Materials (Comparison of Single-
Junction Cells, as of May 2009). Prepared by the STFC

Generation is used in the future, the challenge is to reduce the material and
process costs significantly from the current 46 yen/KWh. Crystalline silicon
solar cells are used in large quantities, but have an unstable cost factor,
namely price fluctuations due to material supply. The problem with
amorphous silicon solar cells is low energy conversion efficiency. Non-silicon
compound semiconductors are under development, whereas such materials

23
have essential problems, including resource depletion and toxicity in the long
term.

1.9 Advantage of DSSC

Unlike the foregoing cells, dye-sensitized solar cells have the following
advantages:

1) Capable of production in a simple way

No vacuum process is required for manufacturing. The solar cells and
panels can be produced in a simple way in the open air. This means a
significant cost reduction of 1/5 to 1/10 as compared to silicon solar cells.

2) Colorable, transparent
The use of dye and its wide selection allow colored cells and transparent
cells.

3) Flexible thin structure

Using aggregates of fine particles of photoelectric conversion materials, the
solar cells can be formed as flexible thin films.

4) Generation characteristics insusceptible to the incident angle and

intensity of the sunlight
Generation characteristics can be maintained even in a weak light
condition, such as under faint light in the morning and evening and when
indoors.

5) Lighter weight
Plastic substrates can be used to reduce the weight of solar cells and panels.
With these advantages, dye-sensitized solar cells can be installed in locations

24
where appearance is important and other solar cells are hardly applicable,
such as the glass panes and inner and outer walls of a building, the sunroof
and outer panels of an automobile, and the enclosure of a cellular phone. This
allows the creation of new markets with expanded demand. Figure 1.11 shows
examples of prototype models for dye-sensitized solar cell panels. Such
panels can be installed on the colored arched roof of a garage, taking
advantage of the excellent design and drainage performance. The panels can
be variously freely decorated for room walls, windows, and interior use.

Figure 1-11: Prototype Models of Dye-Sensitized Solar Cell Panels.

1.10 Aim of the Work

The aim of this study is fabricated dye sentcsized solar cell with simple
techniques, low cost and improved it's efficiency.

The main aim motive of this work is how can arrive to the benefit from the
large solar energy in our country as an alternative to other source of energy
which is considered expensive, pollution source, as well as may vanish in the
future. Solar power is a free energy can any one use it without effect on the
others .

25
 This work deals with dye solar cells implementation and examination using
natural dyes, carbon nanotubes CNTs and silver nanoparticles. The effect of
addition, chemical substances such as polyaniline polymer was investigated in
order to enhance the value of both voltage and current and consequently solar
cell efficiency.

1.11 Literature Review

Researches on wide band gap oxide semiconductors sensitized with dyes
began in the 19th century, when photography was invented. The work of
Vogel in Berlin after 1873 can be considered the first study of dye-
sensitization of semiconductors, where silver halide were sensitized by dyes
to produce black and white photographic films [84].

In 1991, Brian O'regan and Michael Grӓtzel [85], Here we describe a

photovoltaic cell, created from low-to medium-purity materials through low-
cost processors, which exhibits a commercially realistic energy-conversion
efficiency. The device is based on a 10-µm-thick, optically transparent film of
titanium dioxide particles a few nanometers in size, coated with a monolayer
of a charge-transfer dye to sensitize the film for light harvesting. The overall
light-to-electric energy conversion yield is 7.1-7.9% in simulated solar light
and 12% in diffuse daylight.

In 1993, M. K. Nazeeruddin and et al. [86], cis-X2Bis(2,2’-bipyridyl-4,4’-

dicarboxylate)ruthenium(II) were prepared and characterized with respct to
their absorption, luminescence, and redox behavior. Prepared by sintering of
15-30-nm colloidal Titania particles on a conducting glass be outstanding and
is unmatched by any other known sensitizer. These films were incorporated
into a thin-layer regenerative solar cell equipped with a light-reflecting
counter electrode. A solar-to-electric energy conversion efficiency of 10%
was attained with this system.

26
In 1998, Greg P. Smestad [87], presented simplified solar cell fabrication
procedure is presented that uses natural anthocyanin chlorophyll dyes
extracted from plants. The resulting device, made in under 3 h, can be used as
a light detector or power generator that produces 0.4-0.5 V at open circuit,
and 1-2 mA/cm2 under solar illumination.

In 2003, Michael Grätzel [88], presented the current state of the field and
discussed new concepts of the dye-sensitized nanocrystalline solar cell (DSC)
including heterojunction variants and analyzed the perspectives for the future
development of the technology.

In 2004, Gavin E.T. [89], described the background cell technology and
the modular designs considered for the first production DSSC modules and
explains the reasons for selection of the preferred design for outdoor
applications.

In 2006, Supachai.N and et.al [90], studied The effects of indium tin oxide
(ITO) and ITO/SnO2 conducting substrates on photovoltaic properties of dye-
sensitized solar cells (DSCs) using nanocrystalline TiO 2. The decrease in fill
factor of the DSCs was correlated to the increase in resistance of conducting
substrate. The heat stability of ITO conducting glass was improved by
depositing SnO2 on ITO layer. The efficiency of the cells using double
layered ITO/SnO2 substrate remarkably increased compared with that of the
cells using ITO substrates.

In 2008, Jihuai.W and et.al [91], reviewed recent progress in the field of
liquid, solid-state, and quasi-solid-state electrolytes for DSSCs. It is believed
that quasi-solid-state electrolytes, especially those utilizing thermosetting

27
gels, are particularly applicable for fabricating high photoelectric performance
and long-term stability of DSSCs in practical applications.

In 2008, S. Hasiah and et.al [92], studied the electrical conductivity to the
combination of Polythiophene (PT) thin film and Chlorophyll (CHLO) thin
film by layering on Indium Tin Oxide (ITO) substrate as p-n heterojunction
solar cell.

In 2008, M.S. Roy and et.al [93], used Rose Bengal dye (RB) for
sensitization of nanocrystalline TiO2 to fabricate Dye-sensitized solar cell and
that imparts extension in spectral response towards the visible region by
modifying the semiconductor surface. The photoresponse of the cell was
evaluated by analyzing its J–V and impedance characteristics under
illumination with metal halide light source of 400W with an incident light of
73mW/cm2. Various photovoltaic parameters like Jsc, Voc, FF were evaluated
and found to be 3.22mA, 890mV, 0.53, respectively, resulting conversion
efficiency of 2.09%.

In 2009, Niyom Hongsith and Supab Choopun [94], prepared ZnO

nanobelts layer of the dye-sensitized solar cell by RF sputtered ZnO target
onto a copper substrate and characterized by FE-SEM. The structures of solar
cells based on ZnO as a photoelectrode, Eosin-Y as a dye sensitizer,
iodine/iodide solution as an electrolyte and Pt/TCO as a counter electrode.
The photoelectrochemical characteristics of ZnO DSSCs were tested under
simulated sunlight AM 1.5 came from a solar simulator with the radiant
power of 100 mW/cm2.

In 2009, Jae-.K. and et al [95], Highly ordered mesoporous Al2O3/TiO2 by

sol−gel reaction and evaporation-induced self-assembly (EISA) for use in

28
dye-sensitized solar cells. The average pore size of mesoporous
Al2O3/TiO2 remained uniform and in the range of 6.33−6.58 nm while the
Brunauer−Emmett−Teller (BET) surface area varied from 181 to 212 m2/g
with increasing the content of Al2O3. Mesoporous Al2O3/TiO2 (1 mol %
Al2O3) exhibited enhanced power conversion efficiency (Voc = 0.74 V, Jsc =
15.31 mA/cm2, fill factor = 57%, efficiency = 6.50%).

In 2010, Eva M. B. and et.al [96], discussed using two new

Phthalocyanines (Pcs) sensitizers, differing only in their Zn or metal-free
center in dye solar cells. The behaviour of the Pc dyes as sensitizers in DSC,
and their influence on the solar cell performance, in comparison with standard
N719 dye, at identical electrolyte conditions was discussed also.

In 2011, Voranuch S. et al. [97], presented the influence of ethanol and

water as additives in the composite electrolyte on conductivity and
photoelectric performance of quasi-solid-state dye-sensitized solar cells. It
was found that DSSC composed of the composite PEO electrolyte in 20% v/v
ethanol in acetonitrile solution gave the best overall energy conversion
efficiency of 6.33%. The long-term storage at room temperature demonstrated
that the energy conversion efficiencies of DSSCs gradually decreased to 1%
after 2,000 hours.

In 2012, Karki I.B and et al. [98], studied the pomegranate (Bedana) as a
natural sensitizer of a wide band gap semiconductor ZnO based on Dye-
sensitized solar cells (DSSC). It is one of the most promising devices for the
solar energy conversion due to their low production cost and environmentally
friendly. ZnO nanorods were fabricated using sol-gel spin coating technique.

29
 In the same year, Seok C.C. and et al. [99], studied the effect of light
scattering TiO2 particles surface-modified by Al2O3 coating on the
characteristics of a dye-sensitized solar cell (DSSC). The surface of the light
scattering TiO2 particles was coated with Al2O3 by a modified sol–gel method
as a function of the pH and the concentration of colloidal Al 2O3. It was
revealed that the uniform distribution of Al 2O3 nanoparticles leads to an
increase in short-circuit photocurrent of the DSSC device, resulting in an
increase in energy conversion efficiency.

In 2013, Kuei-Fu Chen and et al. [100], used Polyvinyl butyral (PVB)
incorporated into dye-sensitized solar cells (DSSCs) as a quasi-solid
polymeric electrolyte (SPE) thin film. SPE thin films soaked with different
amounts of liquid electrolyte were prepared. The optimal ionic conductivity
was measured to be approximately 1.1x10-3 S/cm, which is approximately six
orders of magnitude higher than that of the original PVB thin film.

In the same year, Souad A. M. Al-Bat’hi and et al. [101]. constructed dye-
sensitized solar cells (DSSCs) by using the Lawsonia inermis leaves,
Sumac/Rhus fruits, and Curcuma longa roots as natural sensitizers of anatase-
based nanostructure TiO2 thin film Paint-coated on ITO conducting glass. The
orange-red Lawsone, red purple anthocyanin and yellow Curcumin are the
main components in the natural dyes obtained from these natural products. A
blend of 50 weight% Chitosan and 50 weight% polyethylene oxide (PEO)
was used as a solid state thin film electrolyte. The polymer blend was
complexed with ammonium iodide (NH4I) and some iodine crystals were
added to the polymer–NH4I solution to provide I-/I3- redox couple.

Also in 2013. Keisuke Kawata and et al. [102], applied novel Polyaniline
(PAni) /TiO2 nanocomposites were applied on fluoride-doped tin oxide (FTO)

31
glass to act as an efficient counter electrode in dyesensitized solar cell
(DSSC) application. PAni/TiO2 nanocomposites were synthesized via a
chemical oxidation process using di-2-ethylhexylsulfosuccinate sodium salt
(NaDEHS) as dopant. In the application of PAni as the counter electrode in
the solar cell, the film showed poor adhesion on the FTO glass. Palm oil
based alkyd was introduced into the nanocomposite mixture to improve the
adhesion of the film. The findings in the work show that strong adhesion of
PAni on FTO glasses has led to higher incident photon to current conversion
efficiency (IPCE) in solar cell.

In 2014, W. Mekprasart and et al.[103], utilized nanocomposite films of

N-doped TiO2 nanofibers (NFs) and commercial-grade TiO2 nanoparticles
Degussa (P25) were utilized as working electrode of typical dye-sensitized
solar cells (DSSCs) The result shows that as calcination temperature
increases, the anatase-to-rutile phase transformation and the fiber size
reduction of NFs were observed.

In 2014, ZhiPeng Shao and et al.[104], developed a novel polymer based

photocathode with a secondary porous structure was developed for tandem
dye-sensitized solar cells (pn-DSCs). Adopted a narrow band gap polymer
PCPDTBT was adopted as the light absorber in the photocathode.
Complementary absorption was realized in pn-DSCs by sandwiching the
photocathode with a typical TiO2 photoanode. The resulting tandem devices
achieved a panchromatic absorption and a power conversion efficiency of
1.30%, which demonstrates the great potential of the polymer based
photocathode for pn-DSCs.

31
2.1 Introduction

A Dye-Sensitized Solar Cell (DSSC) is a low-cost solar cell belong to

the group of thin film solar cells. It is based on a semicondu-ctor formed
between a photo-sensitized anode and an electrolyte, a photo
electrochemical system. A DSSC has three part; photo electrode,
electrolyte and counter electrode.

In this chapter we are going to review the synthesis methods of DSSCs

and the used materials which added to the photo electrode, electrolyte
and counter electrode to enhancement both the efficiency and the cost of
fabrication DSSC.

The dye has important role in principal work of DSSC. In this work
natural dyes such as pomegranate dye and Hibiscus sabdariffa were
used. Figure 2.1 describe the simple structure of DSSC.

Figure 2.1: Schematic of a dye solar cell [1].

There are three key features to a dye solar cell [105]:

1. Photoelectrochemical: Charge separation occurs at the interface
between the titania, a wide band gap semiconductor, and the
distinctly different material, the electrolyte.
2. Nanoparticulate: The surface area of the titania film is about 1000
times its apparent area. The device comprises essentially

23
 transparent crystalline nanoparticles in a ‘light sponge’ with
nanopores.
3. Dye-sensitized: The dye absorbed as a monolayer to Titanium
dioxide is the primary absorber of light the capture of the photons.
Because the Titanium dioxide is inherently transparent, there is an
increased chance of photon capture by the dye as the angle of the
light moves away from normal.

2.2 Chemical Materials

Table 2.2 shows the list of materials used in processing the DSSC. In
this table the chemical name with its formula, some of their
characteristics and the suppliers of the material are listed.

Table 2.1 Employed chemicals and their suppliers

Substance Formula Specifications Origin Function

Tecnología
Titanium dioxide For fabrication
TiO2 Assay 99.9% Navarra de
nano powder Nanoproductos S. photo electrode
L., Español
Multi-walled Assay 95%
carbon nanotubes ,Length:10-30um, NANOCYL S.A., For fabrication
C
(MWCNT) OD:10-20 nm, ID:5- Belgium photo electrode
10 nm
95%
Carboxyl multi-
Length, 50um, OD:8-
walled carbon NANOCYL S.A., For fabrication
C-COOH 15 nm, ID:3-5 nm, -
nanotubes Belgium photo electrode
COOH Content:
(f-MWCNT)
2.56wt %
Assay; 99.7%; For fabrication
Titanium foil Ti China
thickness 0.25mm polyaniline
For fabrication
Indium doped tin 10 Ω/sq surface
ITO China photo and counter
oxide coated glass resistance
electrode
BDH Chemicals ultrasonic cleaning
Methanol CH3OH assay;95%
Catalog For glass

22
 Substance Formula Specifications Origin Function
high-conductivity
Poly(3,4-
grade, 3.0-4.0%
ethylenedioxythiop For fabrication
PEDOT:PSS in H2O, 150 S/cm Aldrich
hene) Polystyrene counter electrode
sulfonate
(18 μm film
thickness)
Methanol BDH Chemicals To prepare SnCl4
CH3OH assay;99.9%
(Absolute) Catalog solution.
BDH Chemicals To prepare TiO2
Nitric acid HNO3 95%
Catalog paste
To prepare
Sulfuric acid H2SO4 assay; 98% (GCC) U.K
polyaniline
CH2OHCH2O To prepare
Ethylene Glycol assay;99% J.T.Baker, U.S.A.
H electrolyte
To prepare gel
polyethylene Glycol H(OCH2)nO4 M.W 4000 HIMEDIA
electrolyte
BDH Chemicals To prepare
Aniline C6H5NH2 assay; 99.8%
Catalog polyaniline
BDH Chemicals To prepare
Potassium Iodide KI assay;99%
Catalog electrolyte
College of science To prepare
Iodine I2
for women electrolyte
Spacer (two sides
30 µm scotch USA For DSSC sealing
tape)
service Lap in
Deionized distilled Conductivity 10
H2O phy. Dept college To clean
water µm/cm
of science
10 nm particle size
(TEM), 0.02 mg/mL
silver dispersion To prepare photo
Ag in aqueous buffer, Aldrich
nanoparticles electrode
contains sodium
citrate as stabilizer

2.3 Measurement Techniques

Different types of instruments and apparatus were used in this work .

they are listed in table 2.2

23
 Table 2.2: Employed origin and model of devices

Instrument Name Specifications Origin Function

Bank Elelkronik
Potentiostat Mlab200 with software For electropolymerization
,Germany,2008
Ultrasonic cleaner with
Bransonic 3510
Ultrasonic digital Timer Heater To clean glass
R-DTH USA
capacity 5L
Heat gun HAAKE Germany To dry
urnace with digital For annealing process
Furnace thermostat heat to U.K and fabrication SnO2
1200 c conductive glass
Measurement of (voltage,
Avometer mV and µA digits Taiwan
current, resistance )
Voltage maximum
Power supply Metcix Voltage source
30V, 2.5A, AX 503
Digital Electrometer 616 Keithley measures V, I, R,
220V,50Hz,415Watt
Magnetic stirrer stirrer and heater Germany Agitation
Digital timer/heater
The absorption and
UV-Vissible UV-Vis 160V,
Shimadzu, Japan transmission spectra for
spectrometer (200-1100) nm
the prepared electrodes
FT-IR
8400 maximum Shimadzu, Japan To characterize the PANI
spectrophotometer
Angstrom Imaging of insulated
Atomic force
AA3000 Advanced Inc. USA surface structure at
microscope (AFM)
atomic resolution

Hitachi FE-SEM
Scanning electron 0.5 - 20 kV Microscopic imaging of
model S-4160,
microscope (SEM) the surface structure
Japan
20 kV, 30 Ma,
Analysis and
Philips pw 1050 with
XRD Germany characterization The
Cu-Kα (1.5406 A)
used material

Jacketed Glass cell 1000 ml, pyrex glass Germany As container with pot.stat
As container for
Teflon cell 75 ml
anodizing process

24
Figure 2.2 shows the main steps for fabrication and characterization of
the DSSC, the arrangement of review experiments will be as a sequence
as stripes in figure 2.2.

Preparation of Preparation TiO2

deposition of TiO2 Sintering TiO2
Conductive glass past

Preparation and Preparation of

Staining dye DSSC cell assembly
added electrolyte counter electrode

Structural Optical Electrical

Sealing cell measuremants measurements measurement, I-V,
XRD, AFM, SEM UV-Vis, FTIR F.F and efficiency

Figure 2.2: The fabrication and characterization steps of the DSSC.

2.4 Preparation of Conductive Glass

Two types of conductive glass were used in this study:
2.4.1 Indium Doped Tin Oxide (ITO) Coated Glass

This type was purchased from Electronic Materials for Laboratory

Use Company, China. Indium tin oxide (ITO, or tin-doped indium oxide)
is a solid solution of indium (III) oxide (In2O3) and tin (IV) oxide (SnO2),
typically 90% In2O3, 10% SnO2 by weight. It is transparent and colorless
in thin layers while in bulk form it is yellowish to gray. In the infrared
region of the spectrum, it acts as a metal-like mirror.

Indium tin oxide is one of the most widely used transparent conducting
oxides because of its two main properties, the electrical
conductivity and optical transparency, as well as the ease with which it
can be deposited as a thin film. As with all transparent conducting films,

25
a compromise must be made between conductivity and transparency.
Increasing the thickness and increasing the concentration of charge
carriers will increase the material's conductivity, but decrease its
transparency. Thin films of indium tin oxide are most commonly
deposited on surfaces by physical vapor deposition. Often used is
electron beam evaporation, or a range of sputter deposition techniques.

2.4.2 Tin Dioxide (SnO2) Coated Glass

This type of conductive glass was prepared in the laboratory. Tin oxide
(SnO2) is one of the n-type II-VI semiconductor oxides with a wide band
gap (Eg = 3.7 eV) [115]. SnO2 has good optoelectrical properties and the
ability to induce a high degree of charge compensation. It is widely used
as a functional material for optoelectronic devices [107].
All thin film was grown on glass substrates by spray pyrolysis. The
SnO2 film was prepared by using SnCl4.5H2O dissolve in methanol by a
concentration of 1 mg/ml. The prepared Solution for each compound is
translucent and contains ionized atoms in predetermined proportions.
Spraying the solution by using Fragrance Atomizer on a glass substrate at
substrate temperature, TS, between 580-660˚C (substrate temperature Ts).
The product will oxidize by the chemical equation 2-1 due to the
temperature of the surface and induce generally the vaporization of the
solvent and undesirable compounds.
SnCl4 + 2H2O ----------› SnO2 + 4HCl 2-1

When this temperature exceeds 450 °C, the metal ions such as tin or
zinc will be oxidized at the heated surface. The different types of ions in
thermal motion will be attracted or repelled under the action of electrical
forces [106]. The more stable chemical composition will be crystallized

26
on the substrate. A growth of a thin layer neutral and well crystallized is
then observed. The nozzle of fragrance atomize is fixed at a height 20 cm
away from the heated sample as shown in figure 2.3.

Controlled heated plat

Figure 2.3: The Spray Pyrolysis system.

2.5 Preparation of TiO2 Past

In this section, the photo electrodes that used in our work will be
described. A suspension of TiO2 was prepared by adding 9 ml of nitric
acid solution of PH 3-4 (1 ml increment) to 6 g of colloidal TiO2 powder,
A drop of transparent surfactant was added in 1 ml of distilled water to
ensure coating uniformity and adhesion to the transparent conducting
glass electrode.

Figure 2.4: TiO2 paste.

27
 Some materials were added in the TiO2 past to enhance the efficiency.
These materials are:
1- TiO2 powder were doped with Ag nano particles. The doping
achieved by taking three ratios from Ag suspension 0.5, 1, 1.5
ml/GM.

2- TiO2 powder were doped with MWCNT and f-MWCNTs by direct

mixing. The additing of MWCNT was occured in two ways:

a- The TiO2 mixed with MWCNT and then mixes with f-MWCNT by
the ratio 1:0.00025 w/w as in [108]. After that the efficiency of
them was measured and choosing the best result.
b- Take different ratios 0.25, 0.5, 1, 1.5 mg/g. From the CNTS
(MWCNTS OR f-MWCNTS) which gave the best result in the
previous paragraph (a) and mixed with TiO2. After that the
comparisum among the effect of these ratios on the efficiency was
taken in consideration.

2.6 Preparation of Photo Electrode

To prepare the photo electrode for DSSC, two steps must be taken into
consideration:
2.6.1 Deposition and Sintering TiO2 Past
TiO2 paste deposited on a cleaned transparence conductive oxide
(TCO) coated glass by putting sticking tape on the conductive glass to
delimitation area and thickness film as show in figure (2.5). The film will
take the thickness of the tape which about 30 µm, and this method called
Doctor blade method, it was employed in deposition of TiO2 paste.
Latter, the sticking tap was removed and sintered in 450°C for 30
minutes to form a porous, large surface area TiO2 film. The film must be

28
allowed to cool down slowly to room temperature. This is a necessary
condition to remove the thermal stresses and avoid cracking of the glass
or peeling off the TiO2 film.

Figure 2.5: the steps of deposition TIO2 paste film.

2.6.2 Staining in the Dye

The TiO2 film immerse in naturally anthocynin dye, after sintered for
30 minutes. The anthocynin dye was prepared by extracting the juice
from the pomegranate and hibiscus sabdariffa fruit by hand job without
any additives. Figure 2.6 show Staining photo electrode in dye.

Figure 2.6: Staining the TiO2 film in dye.

34
2.7 Preparation of Electrolyte

The electrolyte in a dye-sensitized solar cell has a redox potential that

determines the potential of the cell's positive electrode. The electrolyte is
indispensable for the sake of electron transfer in the electrolyte, based on
the physical diffusion of redox pairs.
Commonly used solvents include acetonitrile (ACN), polyvinyl
carbonate (PC), ethylene carbonate (EC), and ethylene glycol (EG).
Whereas the commonly used iodides are sodium iodide (NaI), lithium
iodide (LiI), potassium iodide (KI), and iodide (I 2) as liquid electrolyte
[109]. Although liquid-type electrolytes can acquire higher conversion
efficiency, they have several shortcomings, including the electrolyte
leaks out easily. It is easy for the organic solvent to be volatilized. In this
work two types electrolyte were used liquid and gel electrolyte. The
prepared method for them are as the following:

2.7.1 Solution Electrolyte

By used potassium iodide (KI), iodide (I 2) and ethylene glycol(EG),

liquid electrolyte was prepared. Five ratios for KI of (1.3, 1, 0.8, 0.6, 0.5)
g were mixed separately with 0.083g from I2 and dissolve in 10 mℓ from
EG. The best result was chosen by comparing between them according to
their efficiencies. This is the same method as mensioned on other work
[110].

2.7.2 Gel Electrolyte

This electrolyte content Polyethylene glycol (PEG4000) as the high-
molecular additive with different concentration (20, 40, 60, 80) w%.
these concentrate were added to solution electrolyte that prepared
previously in section (2.7.1). The best result was chosen reterring to by

34
comparisons among them by their efficiencies. This method was
considered as in previous work [111,112].

2.8 Preparation of Counter Electrode

The counter electrode plays the role of returning electrons that are
generated at the photo-electrode, and delivered through the external
circuit, back to the electrolyte. Since the electrolyte is corrosive, the
counter electrode requires high corrosion resistance as well as a high
reaction rate when reducing iodine in the electrolyte to an iodide ion.
Considering the balance between these factors, a conductive glass
electrode coated with platinum (Pt) has been used heretofore. Carbon
electrodes and conductive polymers have been examined as an
alternative to expensive Pt, whereas such materials do not come up to Pt
in terms of the reduction rate. Three types of counter electrode have been
used as the following:

2.8.1 Carbon Coated Counter Electrode

Using carbon electrode by taking the clean conductive glass and
coating with carbon resulted from burning a candle or a pencil as
showing in figure 2.7.

Figure 2.7: (a) pencil carbon and (b) candle carbon, on conductive glass to
prepared counter electrode.

33
2.8.2 PEDOT:PSS Coated Counter Electrode

This coated solution is prepared by adding 5% from DMSO to the

PEDOT: PSS solution. A thin layer from PEDOT: PSS is coated on the
ITO conductive glass by a spin coating method for 3minutes with 3000
RPM as in [113]. The adhesion of PEDOT:PSS with surfaces ITO is very
weak, so that the conductive glass coated with ITO will coated with a
thin layer of TiO2 paste before coating with PEDOT:PSS to create
counter electrode for DSSC.

2.8.3 Polyaniline Polymer Coated Counter Electrode

Ameen et al. Developed a simple interface polymerization method for

the synthesis of PANI nanofibers (NFs), its doping with sulfuric acid
(SFA) to increase the conductivity [113]. These undoped and SFA doped
PANI NFs were applied as new counter electrodes materials for the
fabrication of the highly efficient DSSCs. The selection of SFA was
based on its exclusively important properties such as high solubility, easy
handling, nonvolatile stable solid acid, and low corrosiveness [114]. The
proposed doping mechanism for PANI with SFA is shown in figure 2.8.

Figure 2.8: Proposed mechanism of sulfamic doping into PANI NFs [114].

32
2.8.3.1. Polymerization Method of PANI

The SnO2 conductive glass was mounted in the working electrode

holder which was prepared previously as mentioned in reterence [115].
Nanostructure polyaniline films have been successfully grown on SnO 2
coated glass substrates using the cyclic Voltammetry (CV) method or
electrochemical polymerization method at room temperature. An aqueous
solution containing 0.3M/L aniline and 1.0M H2So4 was prepared.

Figure 2.9: The complete system setup of cyclic polymerization process.

The SnO2 coated glass working as the an electrode in the three-

electrode system. The others two are Pt auxiliary electrode and Ag/AgCl
reference electrode. The working electrode was immersed in the previous
aqueous solution. Cyclic Voltammetry was carried out using a
Potentiostat and the cell system to deposit PANI onto the SnO2 coated
glass. PANI films were fabricated by potential controlling from -50 mV
to 1500 mV at scan rate of 30 mV/sec for 6 cycles and duration 1:30
minutes. The polyaniline nanofibers /SnO2 electrode was fabricated by
electro polymerization of aniline monomer in sulfuric acid using
computer controlled three electrode potentiostat. The voltage scan range

33
was -100mv to 1500mv and repetition cycles was 5. Figure 2.10
represents the CV of preparing Polyaniline/ITO counter electrode.
J(mA/cm2)

Potential(mV)
Figure 2.10: Cyclic voltagram of preparation polyaniline/ ITO counter
electrode.

After determining the optimum voltage for polymerization of aniline by

using a potentiostat from figure 2.10, Simple electric circuit for
deposition PANI was fabricated. The SnO2 conductive glass and sheet
platinum (Pt) were taken by same area and immersion in anilin solution
(0.1M aniline with 0.3 M H2SO4) as shown in figure 2.11. The
application of 1.3 volt DC for 6 min will form a thin layer from
polyaniline.
The polymer films obtained by H2SO4 in concentration of 0.3M. The
fast rate of deposition current density (J) at H2SO4 of concentration 0.3 M
could be ascribed to higher proton concentration and hence the higher
protonation rate of the film [115]. The sulfate ion (SO4–) from the
electrolyte enters the polymer film in the oxidative polymerization and
remains in the polymer chain as dopant. It contributes to

34
oxidation/reduction by accepting/contributing one electron, which makes
the polymer conducting[116]. Figure 2.11 shows a finale electrode of
DSSC after finish coated.

Deposition system Power supply

Timer Ammeter

b c

Figure 2.11: Simple device for polymerization of aniline (a)complete system (b)
two electrodes (c)final green PANI electrode[117].

2.9 Assembling and Sealing The Dye Sensitive solar Cells

The cell assembly was performed by adding a few drops of (I¯/ I₃¯)
electrolyte on the photoanode and fix both electrodes (photo and
counter). The both electrodes facing each other using a clip binder. The
space between two electrodes was obtained by using two sides scotch
tape as a spacer. this is important to be taken into consideration. The shift
between the two electrodes is needed for the electrical contact. The cell
has to be sealed, otherwise the electrolyte would evaporate. The dye solar

35
cells were isolated using glue around the masked area, as shown in figure
2.12. Two clamps were used to press the two electrodes together until the
sealant became dry.

Figure 2.12: Dye solar cell assembly.

2.10 Characterization of DSSC:

2.10.1 Structural and Morphological Measurements

The Measurements include studying the structure and the surface

morphological for the prepared films and the used materials by using
XRD, AFM, and SEM.

2.10.2 Optical Measurements

The Measurements will study UV-Vis absorption and Fourier

transform infrared spectroscopy (FTIR) of the prepared films.

36
 2.10.3 Electrical Measurement

The photo - response of the pomegranate pigment solar cells was

evaluated by recording voltage V and current I, as shown in figure 2.13.
The illuminatin of the solar cell was carried out 60 mW/cm2 tungsten
halogen lamp. The current–voltage characteristics of the cell in
illumination permit an evaluation of most of its photovoltaic performances
as well as its electrical behavior. The short circuit current I sc is the one
which crosses the cell at zero applied voltage and is a function of
illumination.

0 - 600 Ω

Fig 2.13: Device for measuring the voltage and the electric current .

Charges travel under an internal potential difference typically equal

to open circuit voltage Voc.

The Voc is measured when current in the cell is zero, corresponding

to almost flat valence and conduction bands: the values of Imax and Vmax
are defined in order to maximize the power |Imax ×Vmax|. This is the
maximum power Pmax delivered by the cell. The fill factor (f.f) is the ratio
of the maximum power to the product of short circuit current and open
circuit voltage. To calculate the efficiency, the following steps are
followed:

37
1- Key S1 switched on and key S2 was off to record open circuit voltage
(Voc), keeping the current equal zero.
2- S1 switched off and S2 was on to record Isc, keeping the voltage and
resistance equal zero.
3- S1 and S2 were switched on, the resistance was increased slowly every
time, then the voltage and the current value were recorded. At highest
value of resistance, the voltage is maximum Vmax, filling factor (f.f)
and the efficiency was calculated by using the equations (1-1) and
(1-2).

38
3.1 Introduction

This chapter includes the results and discussion of the experimental

measurements of the components of DSSC; conductive glass, a counter
electrode, electrolyte and photo electrode. The structural morphological,
optical, and electrical properties of the synthesized films were
characterized by X-Ray Diffractmeter (XRD). The Atomic Force
Microscope (AFM), Scanning Electron. Microscope (SEM), UV-Visible
spectrometer (UV-Vis), FT-IR spectrophotometer were used. The
performance and efficiencies of different assembled dye sensitive solar
cell will be presented and discussed.

3.2 Optical Measurements:

The optical measurements concerned the UV-Vis absorption for SnO2,

ITO, TiO2, pomegranate juice, and polyaniline polymer films. Fourier
Trans-Infra-Red(FTIR) form for the PANI was studied.

3.2.1 Absorption spectrum of SnO2

The absorption spectrum for SnO2 coated glass prepared by spray

pyrolysis method at room temperature is plotted as a function of
wavelength in the rang (280-1080) nm is shown in figure 3.1. The figure
shows that SnO2 has two absorption peaks, high peak at 300 nm and
lower peak at 400 nm. The lower absorption occurs at 600 nm which
induct that this material is transmitted in visible range. The dependence of
the absorption coefficient α on the incident photon energy follows the
Tauc equation:

(3-1)
where A is constant, h is plank's constant, is the incident photon
frequency, Eg is optical energy gap, and r is an exponent equal to 2 and

05
1/2 for allowed direct and indirect transition, while it is equal to 3/2 and 3
for forbidden direct and indirect transitions.
0.06

0.05

0.04

0.03
Abs. (A.U.)

0.02

0.01

0
280 480 680 880 1080
wavelength (nm)
Figure 3.1: Absorbance spectrum of SnO2 coated glass.

The optical energy gap was determined by plotting (αhν) 2 versus the
photo energy and extrapolating the linear portion of (αhν) 2 and (αhν)3/2,
taking into account the zero value at αhν=0. The value gives the optical
energy gap for direct transitions.

1.6E+09
1.4E+09
1.2E+09
(αhv)^2 (ev/cm)2

1.0E+09 Eg= 3.825 eV

8.0E+08
6.0E+08
4.0E+08
2.0E+08
0.0E+00
-2.0E+08 2 2.5 3 3.5 4 4.5
hv (ev)

Figure 3.2: Allowed direct transition for SnO2 film.

The energy gap values depend in general on the film crystal structure,
the arrangement and distribution of atoms in the crystal. For SnO 2 film
prepared by spray pyrolysis method, the energy gaps for direct allowed
transition is 3.825eV. Figure 3.2 shows the transition for the prepared
film.

05
3.2.2 Absorption Spectrum of ITO
The absorption spectrum of ITO coated glass is shown in figure 3.3. It is
clear that it has absorption peaks at 300 nm and low absorption above 300
nm, which indicates that it has high transmission in this region.

Figure 3.3: Absorbance spectrum of ITO coated glass.

3.2.3 Absorption Spectrum of TiO2

The absorbance spectrum of TiO2 is ploted in figure 3.4. The figure

shows that TiO2 has an absorbance band at 300 - 400 nm. It is also
obvious that TiO2 has a low absorbance in the visible region.

Figure 3.4: Absorbance spectrum of TiO2 as a function of wavelength.

05
 3.2.4 Absorption Spectrum of Pomegranate Dye

The pomegranate juice dye has an intense absorption band at 280 and
325 nm. Both of them are in the UV portion of the solar spectrum. The
interested absorption peak of the natural dye is that at 510 nm because of its
big matching with the solar spectrum. Figure 3.5 shows these three peaks.

280
1
0.9
0.8
0.7 325
Abs.(A.U)

0.6
0.5
0.4
0.3
0.2 510
0.1
0
250 350 450 550 650 750
Wavelength (nm)

Fig 3.5: Absorbance spectrum of pomegranate pigment as function of wavelength.

3.2.5 Absorption Spectrum of PANI

Figure 3.6 shows the absorption spectra of PANI coated on ITO and
SnO2 conducting glass. The band observed at 300-355 nm for the PANI
samples corresponds to n-p* transitions of aniline. The broad bands at
600-620 nm is due to n-p* transitions of quinine-imine groups and these
in agreement with [118]. The absorption peak intensity also increases due
to the regular arrangement of monomer units in electrochemical
polymerization.

05
 1.10
PAni on ITO

0.90 PAni on
SnO2

0.70
Abs. (A.U)

0.50

0.30

0.10

-0.10 300 350 400 450 500 550 600 650 700 750 800 850 900
Wave length (nm)

Figure 3.6: Absorbance spectrum of PANI coated on ITO and SnO2 conductive
glasses.

3.2.6 Fourier Transform Infra-Red (FTIR) of PANI

The FTIR studies for the preparation and the standard PANI were
carried out by FTIR spectrophotometer (8400 maximum resolution 0.5
cm-1 Shimadzu Japan). Figure 3.7a shows the FTIR spectrum of the
prepared PANI at room temperature in distilled water. To compared with
FTIR spectrum of the prepared PANI taken figure 3.7b shows the FTIR
spectrum of the stander PANI [119], whereas the percentage of
transmittance is plotted as a function of wave number (cm-1).
The characteristic of FTIR can distinguish between benzene rings and
quinoid rings in the (1300-1600) cm-1 region of the spectrum. This region
of the spectrum is also most useful for distinguishing between oxidation
state in the undoped polymer, and doped polymer. Table 3.1 Shows the
observed peak for the prepared polyaniline. The 1139 cm-1 band is
vibrational mode of (B-NH=Q) and (B=NH-Q) which is formed in
doping reaction. this band is very intense which may be attributed to an
existence of positive charges [120].

05
 a

b
Figure 3.7: Infrared spectra of electropolymerized PANI (a) FTIR for PANI
prepared PANI (b)stander PANI [119].

Table 3.1: A list of the observed peak in the prepared polyaniline film
in (KBr) matrix.

Peak (cm-1) Assignment

586-800 C-Cl Aromatics out of plain bend
1139 C═N Imines bending
1292 C-N stretch of benzenoid ring
1488 C═C benzenoid ring stretch(N-B-N)
1558-1566 C═C stretch of quinoid ring (N═Q═N)

00
The absorption peaks at 1564 cm-1 assigned to the quinoid structure, that
concludes that the polymers were prepared using di and tri basic acids. It
has been reported that H2SO4 may interact with PANI by donating either
hydrogen sulfate, (HSO4)- or sulfate, (SO4)-2 anions as dopant anions as
shown in figure 3.6. Many authors agreed that (HSO4) - dopant anions are
present in PANI/H2SO4 [121].

3.3 Structural Measurements

3.3.1 XRD Measurement of PANI

The crystal structure of the deposited PANI was examined by x-ray

diffraction (XRD). Figure 3.8 shows broad scattering peak for PANI
around 2θ of 25.51º which may correspond to the (110) plane of PANI.
This result identify with result mention by [122,123].

(110)

23

18
Inten.

13

3
20 25 30 35 40 45 50 55 60
2ϴ

Figure 3.8: X–ray diffraction of the polyaniline film.

05
3.3.2 XRD Measurement of SnO2
Figure 3.9 shows the XRD patterns of SnO2 synthesized by the spray
pyrolysis method at room temperature. The X-ray diffraction pattern
consists of characteristic diffraction peaks at 2θ= 26.4o, 33.71o, 37.74o
and 51.5o. The peaks were assigned to (110), (101), (200) and (211),
respectively. These results compared with the standard SnO2 of the
JCPDS lines [124]. All peaks can be readily indexed to tetragonal SnO 2
nanoparticales NPs. Other peaks such as Sn or any other Sn based oxide
were not observed, which indicates the high purity of the preparation
SnO2. The diffraction peaks are markedly broadened, which indicates that
the crystalline sizes of the samples are very small. The average grain size
was calculated through the Scherer formula [125, 126]:
D = Kλ/β cosθ (3-2)
Where D is the average crystallite size, K is a constant with a value of
0.9, λ is the X-ray wavelength, β is the angular line width at half
maximum of intensity, and ϴ is the Braggs diffraction angle.

Figure 3.9: XRD of SnO2 thin film (SnO2 coated glass).

The crystallite size of SnO2 NPs was calculated from the peakes in XRD
measurement of SnO2 film and the average crystallite sizes of SnO2 NPs

05
are found to be about 21 nm. It is clear that the films are polycrystalline
structure. The polycrystalline film with preferred growth direction along
(110) is seen from the graph. Other peaks corresponding to the directions
(101), (200), (211) are also seen at 2ϴ 33.65, 37.6 and 51.45 respectively.

3.3.3 XRD Measurement of TiO2

Figure 3.9 shows the XRD of TiO2 paste sample deposited on ITO
conductive glass after annealed at temperature 450 0C. It is clear that the
X-ray diffraction pattern consists of characteristic diffraction peaks at
2θ= 25.24˚, 37.71˚, 48˚, 53.85˚ and 55˚. Which were assigned to (101),
(004), (200), (105) and (211) respectively [127]. These peaks can be
readily indexed to tetragonal TiO2 NPs.

Figure 3.10: XRD of TiO2-NPS TiO2 paste after deposited on ITO glass and
annealed at 450 0C.

These results also compared with the standard TiO2 of the JCPDS lines
[124]. Other peaks (222) at 30˚, (004) at 35˚and (044) at 51˚ are belong to
ITO coated glass substrate as given in the figure 3.7. These miller indices
coincide with the results mentioned by other warkes [128]. The broad

05
peaks indict that the formation structure are of nano dimensions. The
diffraction peaks are markedly broadened, which revealed that the titania
is a poly-crystalline and the crystalline sizes of samples are very small.
According to Scherer's formula, the average crystallite sizes of TiO2 NPs
are about 15 nm for peak related to (101) Miller indices.

3.4 The Surface Morphology Measurements

3.4.1 The surface morphology of SnO2 and ITO film using AFM

Figure 3.11 (a, b) and figure 3.12 (a, b) show two and three
dimensional AFM image of the surface topography of SnO2 and ITO
film respectively. While figure 3.11c and Figure 3.12c represent the
granularity accumulation distribution chart for both of them. The image
shows that the surface roughness average (Sa) is very small which
indicate all films have smooth surface and displayed the granular
structure. Other surface topography parameters such as root mean square
roughness (Sq), ten point height (Sz) and average particle size, which
estimated from the granularity accumulation distribution are summarized
in table (3.2).

Table (3.2): surface topography parameters obtained from AFM analysis for SnO2
and ITO surfaces.
Sample Sa (nm) Sq (nm) Sz (nm) Ave. G.S. (nm)
SnO2 1.24 1.67 7.84 239
ITO 0.934 1.42 6.23 212

05
 a b

c
Figure 3.11: AFM measurement of surface SnO2 coated glass(a) 2D (b)3D
(c)Granularity accumulation distribution report of surface SnO2.

a b

c
Figure 3.12: AFM measurement of surface ITO coated glass (a) 2D (b) 3D (c)
Granularity accumulation distribution report of surface ITO.

3.4.2.The Surface Morphology of PANI film using AFM

Figure 3.13(a,b) shows two and three dimensional AFM image of the
surface to the photograph of PANI film. The image show that the surface

55
roughness average (Sa) is 2.96 nm, the a film of nanofibers with
diameters around 72.23 nm. Root mean square roughness (sq) is about
3.66 nm, and the ten point height (sz) is about 17.5 nm. Figure 3.13 (c)
represents the granularity accumulation distribution chart.

a b

c
Figure 3.13: AFM measurement of surface PANI coated glass (a) two
diminution (b) three dimensions (c) Granularity accumulation distribution report
of surface PANI film.

3.4.3 The Surface Morphology of PANI Film using SEM

The SEM image in figure 3.14 of the prepared PANI shows a

nanofibers formed by star shapes. This structure offers a large area to
help in receiving the electron which injected by the dye to the titania
layer, then return back to the dye again via the oxidation-reduction
reactions of the I-/I3- electrolyte.

55
 Figure 3.14: SEM image of the prepared polyaniline electrode.

3.5 Electrical Measurements

The electrical properties of a material are determined by the
arrangement of atoms in the solid. The existence of a defect give rise to
the electron states in the energy gap which effected on the electrical
properties of the material [129]. The conductivity of semiconductor
depends on the ambient; temperature, pressure, illumination, external
field and irradiation by nuclear partials and also depends on the structure,
i.e crystallinity, defects, and impurities [130].

3.5.1 Hall Effect Measurements for SnO2

It is necessary to determine whether a material is n-type or p-type.
Measurement of the conductivity of a specimen will not give this
information, since it cannot distinguish between positive hole and
electron conduction, but Hall Effect can be utilized to distinguish
between the two types of carriers [131]. Hall measurements are widely
used in the initial characterization of semiconductors, it allows the

55
density of the charge carriers to be determined, as well as carrier
mobility, and the type of the conductivity of the charge carriers. Hall
effect has been known for nearly 100 years, and has been used typey
semiconductor .
From Hall effect measurement revealed that SnO2 film is a
semiconductor and has n-type conductivity. This indicates that the charge
carriers are electrons. Hall coefficient (RH) and the charge carriers nH
have been calculated using the relations [132]:

(3.3)

(3.4)

Where VH is Hall voltage. I is the current of the applied electric field, it

is the thickness, and e is the electron charge. It is found that the values -
2.303X10-2 m2/c and -3.79X1015 cm-2 for Hall coefficient and sheet
concentration respectively. It is fired to have the values -2.303X10-2 m2/c
and -3.79X1015 cm-2 for Hall coefficient and sheet concentration
respectively.
The resistivity and the conductivity of the film were calculated using
the equations [132]:

(3.5)

(3.6)
Where R, A and L are the resistance, area, and distance between the
electrodes of the film respectively. Hall effect measurement showed that
SnO2 film had a low resistivity of approximately 1.8×10 -3 Ω.cm and
conductivity 5.479×10-2 Ω-1.cm-1, while the mobility was 1.262×10 -1 cm-
2
/Vs, for film thickness of about 140 nm.

55
3.5.2 Sheet Resistance Measurement of SnO2 as a Function of
Substrate Temperature (Ts) and Sprinkling Numbers (N)
Table 3.3 displays the experimental result of the resistance of SnO2
films prepared at different substrate temperature and sprinkling numbers.
It is observed from the results of this table that the resistance decreased
with increasing of temperature and sprinkling numbers. The stable case
of these samples was at N=10 and temperature between 620 and 640˚C,
as well as sprinkling number 10 and 14.

Table 3.3 Effect of substrate temperatures (Ts) and sprinkling number (N) on the
sheet resistance (R(KΩ)) of SnO2 film prepared at room temperature.

Ts 550 600 620 640 660

N (˚C) Sheet resistance KΩ
4 80 45 40 - -
6 1.2 0.7 0.30 0.25 0.25
10 1 0.6 0.25 0.20 0.20
14 1.1 0.7 0.20 0.20 0.20

These results were chosen as condition to prepare SnO2 films which,

gives low resistivity of about 1.8×10-3 Ω.cm. This resistivity is much
lower than that for other researchers [124,125].

Figure 3.15:Photographic image for (1) Normal glass (2) SnO2 coated glass.

55
 These conditions can give better results in the fabrication process of
dye sensitive solar cells by wingless quantity from SnCl4. Increasing the
temperature of glass substrate above 660˚C will lead to bend the glass,
and have a concave shape because it melt at this temperature. A
comparison between normal and coated glass was given by figure 3.15.

3.6 Effect of Potassium Iodide (KI) Concentration

KI is a white hygroscopic compound, low and high concentration of KI

reduce the solar cell efficiency. Thus a moderated amount of KI must be
selected to be (0.83 gm/ mℓ) as shown in fig (3.16). This red-ox has good
solubility and provides rapid dye regeneration. At high iodine
concentration reductive quenching might deactivate the excited state
representing losses in the channel, and the rate of back reaction is much
smaller. Another recombination process is the reduction of tri-iodide in
an electrolyte by conduction band electrons.

Figure 3.16 shows the relation between the efficiency and the
concentration of KI in electrolyte solution.

0.38
0.37
0.36
0.35
effi. %

0.34
0.33
0.32
0.31
0.3
0.29
0.053 0.063 0.073 0.083 0.093 0.103
con. (gm/mℓ)

Figure 3.16: the efficiency as a function of KI concentration.

50
It is clear that higher efficiency occurs at 0.083 gm/mℓ while before and
after this concentration the efficiency is less.

3.7 Effect of Polyethylene glycol 4000 (PEG 4000) Concentration on

Efficiency

PEG 4000 is a polyether compound with many applications from

industrial manufacturing to medicine. The structure of PEG is (note the
repeated element in parentheses): H-(O-CH2-CH2)n-OH

PEG is also known as polyethylene oxide (PEO) or polyoxyethylene

(POE), depending on its molecular weight. Figure (3-17) explain the
experimental result for added different ratios of PEG to the electrolyte
solution at best ratio which was 40% W/V (e.g. 40gm+60ml). This is
because PEG has low conductivity or isolator so that increasing its ratio
in the electrolyte will cause increasing in resistivity of electrolyte and
hinder movement of charge. Figure 3.17 shows the behavior of increasing
the ratio of PEG on the values of efficiency.

0.37
0.365
0.36
0.355
0.35
effi. %

0.345
0.34
0.335
0.33
0.325
0.32
0.315
20 30 40 50 60 70 80 90
percent W%

Figure 3.17: The efficiency as a function of PEG ratio in the electrolyte.

55
 PEG, which is almost identical to PEO in its chemical structure, has
been used as a plasticizer because PEGs gives a decrease in crystallinity
and increase in mobility of the salt in the electrolyte, miscibility with the
amorphous PEO-salt complex, and low volatility [133].

3.8 Effects of Dye Type

Two natural dyes were used; Hibiscus sabdariffa, Pomegranate and

mixing of them. Table 3.4 tabulated the filling factor and efficiency result
by using the two types of dyes.

Table 3.4: Effects of dye type on f.f and efficiency of DSSC.

Types of the dye f.f. Efficiency %

Pomegranate 0.32 0.38

Hibiscus sabdariffa 0.36 0.25

mixed of them 0.275 0.28

3 Hibiscus sabdariffa

2.5 mixing
pomegranate
2
I (mA)

1.5

0.5

0Figure (3-18): I-V relation of DSSC by different dyes.

0 0.1 0.2 0.3 0.4 0.5
V(Volt)

Figure 3.18: I-V characteristic for DSSC fabricated by used the dyes of
Pomegranate, Hibiscus sabariff and mixed of them.

55
Returning to the the table and figure 3.18 one can conclude that the
Pomegranate is best dye comparing to their efficiency with other.

3.9 Effect of Materials on Efficiency

The additive material plays an important role to enhance the

photovoltaic parameters in photo electrode-based DSSC. The position of
the conduction band (CB) in the TiO2 depends strongly on the surface
charges and adsorbed molecules. These additives are expected to be
adsorbed onto the TiO2 surface, thus affecting the CB in the TiO2 strongly
associated with the photocurrent and photovoltage. Three types of
additive material were used in this work, multi walled carbon nanotubes
(MWCNTs), functionalized multi walled carbon nanotubes (f-MWCNTs)
and silver nanoparticles Ag.

3.9.1 The Effects of Adding Multi-Walled Carbon Nanotubes

(MWCNT) and Carboxyl Multi-Walled Carbon Nanotubes (f-
MWCNT)

In order to study the effects of added carbon nanotubes to the TiO2

Nano powder. Wight of 0.25mg from MWCNT was added to 1gm of
TiO2. A suspension of TiO2 was prepared by adding 9 mL of nitric acid
solution of PH 3-4 (1 mL increment) to 6 g of TiO2 powder. The I-V
characteristic, F.F. and efficiency were studied by using the same amount
from f-MWCNT and repeat the same steps of mixing and calculation in
order to compare between the effect of them. From figure 3.19 one can
find that f-MWCNT gave 0.13% efficiency higher than that for MWCNT
because the presence of carboxyl grope that attached with MWCNT. To
find the optimized ratio from f-MWCNT which generate highest

55
efficiency, different amount from f-MWCNT (0.25, 0.5,1and 1.5) mg
were taken and mixed with 1gm of TiO2 nanopowder.

1.8
f.MWCNT
1.6
b MWCNT
1.4
1.2
a
I(mA)

1
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5
V(Volt)
Figure 3.19: I-V characteristics of DSSC after adding (a) MWCNT and (b) f-
MWCNT to the TiO2 Nano powder by ratio 0.25mg/g.

Table 3.5 shows the relation between the efficiency and the
concentration of f-MWCNT. From this table it is appeared that the best
value of efficiency occurs at concentrations of 0.5 mg/g from f-MWCNT.

Table 3.5: Effects of f-MWCNT concentration on efficiency of DSSC.

Concentration mg/g f.f Efficiency %

0.25 0.443 0.48
0.5 0.423 0.51
1 0.4 0.35
1.5 0.416 0.34
The enhancement for the efficiency returned to the enhancement of the
Jsc. This enhancement can also be explained by the increase in
interconnection among the TiO2 particles in the TiO2 films prepared with
added of f-MWCNTs. Addition of f-MWCNT induced clusters, enables

55
an increase in interconnection among the TiO2 particles in the film [133],
in comparison with TiO2 films without f-MWCNTs. The increased
interconnectivity in turn lead to increases the electrical conductivity of
the film in the presence of f-MWCNTs. In addition to improve the
interconnectivity among TiO2 particles in the films in the presence of
f-MWCNTs, the anchoring of TiO2 particles to nanotubes can promote
charge separation, owing to the fact that carboxylic acid groups are also
able to attach themselves to TiO2 particles [134]. A single CWCNT itself
can generate electron-hole pairs when shining by the light, that may be
the cause of increasing of efficiency [21].
To study the effect of time on the efficiency of DSSC with f-MWCNTs
as additive, the measurements were repeated after 3 days. It is obvious
from the table (3.6) that the efficiencies were decreased in both cases, but
the stability is more in the case of DSSC with f-MWCNTs.

Table 3.6: Efficiencies with time for DSSC with and without f-MWCNT.

Samples Efficiency of DSSC without Efficiency of DSSC with

f-MWCNT % f-MWCNT %

At fabrication time 0.37 0.52

After 3 days 0.1 0.33

3.9.2 Effect of Adding Silver Nanoparticle to TiO2 Powder

Added Ag nanoparticles with TiO2 powder in the photo electrode

enhance the efficiency according to the enhancement in both current and
voltage. This is due to the increase in the electron transfer speed, where
the addition of silver nanoparticles will increasing the mobility of
electrons. To optimized the suitable Ag concentration which give best

55
efficiency, different ratios of Ag nanoparticles of 10 nm in size was used.
Table (3.8) explain this effect. It is observed that the Ag concentration
which improve the efficiency occur at 1 mℓ/g that gave the highest
efficiency.
More that this concentration will lead to decreasing the efficiency
because this may make a high conductivity in the photo electrode lead in
turn to state like a short circuit which cause decreasing the voltage and
current.

Table 3.8: Effect of added Ag nanoparticles in different concentration on the

efficiency of DSSC. .

Conc. mℓ/g Isc Voc f.f. Efficiency%

0.1 2 240 0.33 0.46
0.2 2.2 350 0.44 0.72
0.3 1.6 430 0.51 0.59

3.10 Effects of Counter Electrode Type

In this study three types of counter electrode were used, carbon,
BEDOT:PSS, and polyaniline. The effect of these types on the filling
factor and the efficiency of DSSC were studied and listed in table (3.6).
The table shows that the polyaniline counter electrode give the highest
efficiency.
Table 3.7: Test result of counter electrode.
Type counter Isc(mA) Voc(Volt) f.f Efficiency%
electrode
Carbon 2 0.42 0.333 0.47

BEDOT:PSS/TiO2 2.214 0.44 0.41 0.67

Polyaniline 3.36 0.42 0.30 0.72

55
 3.11 Characterization of Assembled DSSCs

All types of the assembled DSSCs from a mixed combination of

different counter electrodes and different active anodes were subjected to
I-V characterization, in order to evaluate all parameters of them; current
of short circuit, voltage of open circuit, maximum cell power, the filling
factor, and conversion efficiency (ƞ).

The cell parameters; Isc, Voc, Imax, and Vmax were estimated from the I-V
curves, while the full factor (ff) and the cell efficiency were calculated
from equation (1-1) and (1-2). Table 3.9 reviewed the characterization of
assembled DSSCs at different preparation condition for anode, cathode
and electrolyte.

Table (3-9) Characterization of assembled DSSCs at different conditions with

standard TiO2 NP’s and pomegranate dye.
DSSC parts P input V max I max
F.F E%
C.E. P.E. electrolyte mW/cm2 V mA/cm2

Carbon/ITO TiO2 on ITO Liquid 60 0.2 1.15 0.3 0.37

Ag/f-MWCNT/TiO2
PANI/SnO2 Liquid 60 0.073 0.24 0.146 0.03
on SnO2
Ag/f-MWCNT/TiO2
PANI/ITO Liquid 60 0.6 0.2 0.355 0.07
on SnO2
Ag/f-MWCNT/TiO2
Carbon/ITO Gel 60 0.2 0.92 0.25 0.31
on ITO

PANI/SnO2 Ag/f-MWCNT/TiO2 Liquid 60 0.2 1.644 0.71 0.55

on ITO
Ag/f-MWCNT/TiO2
Carbon/ITO Liquid 60 0.21 1.58 0.33 0.56
on ITO

PANI/ITO Ag/f-MWCNT/TiO2 Liquid 60 0.2 2.16 0.304 0.72

on ITO
PEDOT:PSS/ Ag/f-MWCNT/TiO2
Liquid 60 0.231 1.74 0.41 0.67
TiO2/SnO2 on ITO

55
From the table, it is clear that the efficiency increasing gradually after
each addition. At each time, the best result for certain additive was taken
and applied for the next step in order to reach to the best results which
achive the possible high efficiency for the DSSC.
The best efficiencies were 0.72% and 0.67% which achieved using
PANI/ITO and PEDOT:PSS/TiO2/SnO2 as anode respectively, and Ag/f-
MWCNT/TiO2 as cathode on ITO, and liquid electrolyte. Figures 3.20
and 3.21 show the schematic of assembled for these DSSC.

Figure 3.20: Schematic of Ag/f-MWCNT with TiO2 deposited on ITO coated glass
as cathode electrode, using liquid electrolyte and PANI deposit on ITO coated glass.

as anode electrode.

Figure 3.21: Schematic of Ag/f-MWCNT with TiO2 deposited on ITO coated glass
as cathode electrode, using liquid electrolyte and PEDOT:PSS deposit on thin film
TIO2/SnO2 coated glass as anode electrode.

55
3.12 Conclusions
1. The type of the anode material plays the major role in making the
DSSC, A wide differences in the values of the cell efficiencies was
noticed, while the variation of the catalyst of the counter electrode
plays a less important role. Electropolymerization of aniline can be
conducted easily on ITO glass and the examinations revealed the
nanofiber structure with a diameter around 73 nm.
Gel electrolyte gives stability for DSSC more than liquid electrolyte.
The electrolyte important part after photo electrode where plays a
significant role in the stability of DSSC with time (its lifetime).
2. Added Ag nanoparticles with TiO2 enhance the efficiency, but they
did not give stability with time. Added f-MWCNT with TiO2 enhance
the efficiency and give stability with time. Mixed Ag NPs and f-
MWCNTs with TiO2 given result better than adding each one alone
with TiO2 in photo electrode.
3. Can be made very cheap (not expensive) conductive glass with
suitable resistance by using SnCl4.5H2O and spray Pyrolysis method
and deposited a thin layer of SnO2 on surface glass in special
circumstances or environment. It may use as substrate to counter or
photo electrode. The adhesion of polyaniline when prepared on the
surface of SnO2 coated glass was stronger than that on the surface of
ITO coated glass. Highest efficiencies were 0.72% and 0.67% which
achieved using PANI/ITO and PEDOT:PSS/TiO2/SnO2 as counter
electrode respectively, Ag/f-MWCNT/TiO2 as cathode on ITO, and
liquid electrolyte.

55
3.13 Suggested Futures Works

1- Studying the efficiency by using different dyes for DSSCs as well

as the effect of distance between the anode and the cathode to
improve the performance of cells.
2- Study the effect of using different types of polymer under different
condition of preparation, in order to enhance the efficiency of
DSSCs.
3- Study the effect of improving the electrolyte solution, such as
viscosity, evaporation speed, conductivity. Also study the
possibility of making self-cleaning by using it.
4- Study the effect of adding MWCNT to the electrolyte solution or to
the photo electrode to improve the performance of DSSCs.
5- Study the effect of deposition very thin layer from TiO 2 paste by
controlling the deposition method.
6- Study mechanical element and its effect with time.

50
References

1. H. Graß, J. Kokott, M. Kulessa, J. Luther, F. Nuscheler, R. Sauerborn, H.J.

Schellnhuber, R. Schubert, and E.D. Schulze, "World in Transition", First
published by Earthscan in the UK and USA, German Advisory Council on
Global Change (WBGU), 2004.
2. Richard C. Willson and Alexander V. Mordvinov, "Secular total solar irradiance
trend during solar cycles 21–23", Geophysical Research Letters, Vol. 30, P.
1199, 2003.
3. Zekâi Sen, "Solar irradiation fundamentals", Solar energy conversion and
photoenergy system, vol. 2, 2009.
4. P. Würfel," Physics of Solar Cells: From Principles to New Concepts", Ch.4,
Wiley-WCH, Weinheim, 2005.
5. A.E. Becquerel, "Memoire sure les effects electriques products sous influence
des rayon's salaries". Comt. Rend. Acad. Sci., Vol. 9, P. 561-567 (1839).
6. C. Fritts, "On a New Form of Selenium Photocell", Procedures American
Association for the Advancement of Science, Vol. 33, P. 97, 1883.
7. D. Chapin, C. Fuller, and G. Pearson, "A New Silicon p-n Junction Photocell for
Converting Solar Radiation into Electrical Power", Journal of Applied
Physics, Vol. 25, P. 676–77, 1954.
8. D. C. Reynolds, G. Leies, L. L. Antes, and R. E. Marburger, "Photovoltaic Effect
in Cadmium Sulfide", Phys. Rev., Vol. 96, P. 533, 1954.
9. D. A. Jenny, J. J. Loferski, and P. Rappaport, "Photovoltaic Effect in
GaAs p-n Junctions and Solar Energy Conversion", Phys. Rev., Vol. 101,
p.1208, 1956.
10.M.B. Prince, ―Silicon solar energy converters‖, J. Appl. Phys., Vol. 26, P. 534-
540, 1955.
11.J. Loferski, "Theoretical Considerations Governing the Choice of the Optimum
Semiconductor for Photovoltaic Solar Energy Conversion", J. Appl. Phys.,
Vol. 27, P.777-784, 1956.

67
12.J. Wysocki, P. Rappaport, ―Effect of temperature on photovoltaic solar energy
Conversion‖, J. Appl. Phys., Vol. 31, P. 571-578, 1960.
13.W. Shockley and H. J. Queisser, ―Detailed balance limit of efficiency of p-n
junction solar cells,‖ J. Appl. Phys. Vol. 32, P. 510–519, 1961.
14.J. Lindmayer and J. Allison, Proc. 9th IEEE Photovoltaic Specialists Conf.,
1972, p. 83 (unpublished); Comsat Tech. Rev., Vol.3, P.1, 1973.
15.M.A. Green, A.W. Blakers, S.R. Wenham, S. Narayanan, M.R.Willison, M.
Taouk, T. Szpitalak, ―Improvements in silicon solar cellefficiency‖, Proc. 18th
IEEE Photovoltaic Specialists Conf., Las Vegas(CA), p. 39, 1985.
16.D. J. Friedman, S. R. Kurtz, K. A. Bertness, A. E. Kibbler, C. Kramer, J. M.
Olson, D. L. King, B. R. Hansen, J. K. Snyder, Prog. Photovolt. 1995, 3, 47.
IEEE Photovoltaic Specialist Conf. 1985, 39.
17.M. Grätzel,"Perspectives for dye-sensitized nanocrystalline solar cells", Vol.8, P.
171–185, 2000.
18.M.A. Contreras, B. Egaas, K. Ramanathan, J.Hiltner, A. Swartzlander, F.
Hasoon, and R. Noufi, "Progress toward 20% efficiency in
Cu(In,Ga)Se2polycrystalline thin-film solar cells", Progress in Photovoltaics
Research and Applications, Vol.7, P. 311–316, 1999.
19.A. Luque, S. Hegedus," Handbook of Photovoltaic Science and Engineering ",
ch.1, P.16, 2003.
20.K. Mangersnes, " Back- contacted back-junction silicon solar cells", Doctoral
Thesis, Department of Physics, University of Oslo, 2010.
21.S. Wenger, ‟ Strategies to Optimizing Dye-Sensitized Solar Cells Organic
Sensitizers, Tandem Device Structures, and Numerical Device Modeling‖,
Doctoral Thesis, Lausanne, 2010.
22.T . Ameri, G. Dennler, and C. Lungenschmied et al.," Organic tandem solar
cells: a review", J. Brabec, Energy Environ. Sci., Vol. 2, P. 347-363, 2009.
23.Zekâi Sen, "Solar irradiation fundamentals", Solar energy conversion and
photoenergy system, vol. 2, 2009.

66
24.K. Wang, "Nanomaterials: from Interfacial Characteristics to Device
Applications", Ph.D. Dissertation, McMaster University, Canada (2011).
25.J . Nelson, solar cells by self-assembly, Science 293, no. 5532, P. 1059-1060,
(2001).
26.C . J. Brabec, S. Sariciftci, & J. C. Hummelen, Plastic Solar Cells, Adv. Funct.
Mater. Vol. 11, Issue 1, P. 15–26, 2001.
27.J . Li, & A. C. Grimsdale, Carbazole-based polymers for organic photovoltaic
devices, Chem. Soc. Rev., Vol. 39, P. 2399-2410, 2010.
28.U . Bach, D. Lupo, & P. Comte et al., Solid-state dye-sensitized mesoporous
TiO2 solar cells with high photon-to-electron conversion efficiencies, Nature,
Vol. 395,P. 583-585, 1998.
29.M . Gratzel, "Dye-Sensitized Solid-State Heterojunction Solar Cells", MRS
Bulletin, Vol. 30, P. 23-27, 2005.
30. A . Yella, H. Lee, and H. N. Tsao , "Porphyrin-sensitized solar cells with cobalt
(II/III)-based redox electrolyte exceed 12 percent efficiency", Science, Vol. 334,
P. 629, 2011.
31.K. Paulo lobato, ‟ Charge Transport and Recombination in Dye-Sensitized
Nano- crystalline Solar Cells‖, Dr. Thesis, University of Bath, United Kingdom,
2007.
32.V. Fthenakis, ‟ Sustainability metrics for extending thin-film photovoltaics to
terawatt levels‖, MRS bulletin. Vol. 37, 2012.
33.W. Shockley. H J. Queisser, ‟ Detailed Balance Limit of Efficiency of p‐n
Junction Solar Cells, ‖J. Appl. Phys. 32, p. 510, 1961.
34.V. Fthenakis, ‟ Third Generation Photovoltaics‖ , p. 232, intech, 2012
35.L. Wagner, ‟ Overview of the solar industry‖, Mora, Associated, 2007.
36.B. O’Regan, M. Grätzel, "A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO2 films", Nature, Vol. 353, P. 737-740, 1991.
37. M. Grätzel, "Conversion of sunlight to electric power by nanocrystalline dye-
sensitized solar cells, J. Photochem. Photobiol",Vol.3, P. 164, 2004.

67
38. P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. Nazeeruddin, T. Sekiguchi, M.
Grätzel, " A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic
ruthenium sensitizer and polymer gel electrolyte", Nat. Mater., Vol.2, P. 402,
2003.
39. P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin, and M. Grätzel,
"Stable ≥8% efficient nanocrystalline dye-sensitized solar cell based on an
electrolyte of low volatility", Appl. Phys. Lett., Vol. 86, 123508, 2005.
40. V. Fthenakis, ‟ Third Generation Photovoltaics‖ , p. 232, intech, 2012.
41.M. Grätzel, "Stable ≥ 8% efficient nanocrystalline dye-sensitized solar cell based
on an electrolyte of low volatility", Inorg. Chem., Vol. 44, P. 6841, 2005.
42.A. Hagfeldt," M. Grätzel, Light-Induced Redox Reactions in Nanocrystalline
Systems", Chem. Rev. Vol. 95, P. 49, 1995.
43.A. Hagfeldt, M. Gratzel, "Light-Induced Redox Reactions in Nanocrystalline
Systems", Chem. Rev. Vol. 95, P. 49-68, 1995.
44.J. Schnadt, P. A. Bruhwiler, L. Patthey, J. N. O’Shea, S. Sodergren.
"Experimental evidence for sub-3-fs charge transfer from an aromatic adsorbate
to a semiconductor", Nature Vol.418, P. 620-623, 2002.
45.S. Ito, P. Chen, P. Comte, M. K. Nazeeruddin, P. Liska, P. Pffechy, and M.
Gratzel, "Fabrication of screen-printing pastes from TiO2 powders for
dyesensitised solar cells", Progress in Photovoltaics: Research and Applications,
Vol. 15, P. 603-612, 2007.
46.P. Qin, H. Zhu, T. Edvinsson, G. Boschloo, A. Hagfeldt, and L. Sun, "Design of
an organic chromophore for p-type dye-sensitized solar cells.," Journal of the
American Chemical Society, Vol. 130, P. 8570-8571, July 2008.
47.A. Morandeira, J. Fortage, T. Edvinsson, L. LePleux, E. Blart, G. Boschloo, A.
Hagfeldt, L. Hammarstrom, and F. Odobel, "Improved Photon-to-Current
Conversion Efficiency with a Nanoporous p-Type NiO Electrode by the Use of a
Sensitizer-Acceptor Dyad," The Journal of Physical Chemistry C, vol. 112, pp.
1721-1728, Feb. 2008.

68
48.M. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Müller, P. Liska, N.
Vlachopoulos, and M. Gratzel, "Conversion of light to electricity by cis-
X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers
(X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes,"
Journal of the American Chemical Society, Vol. 115, P. 6382-6390, 1993.
49.M. Nazeeruddin, S. Zakeeruddin, R. Humphry-Baker, M. Jirousek, P. Liska, N.
Vlachopoulos, V. Shklover, C.-H. Fischer, and M. Gr• atzel, "Acid-Base
Equilibrium of (2,2'-Bipyridyl-4,4'-dicarboxylic acid)ruthenium(II) Complexes
and the Effect of Protonation on Charge-Transfer Sensitization of
Nanocrystalline Titania", Inorganic Chemistry, Vol. 38, P. 6298-6305, 1999.
50.T. Minami, "Transparent conducting oxide semiconductors for transparent
electrodes," Semiconductor Science and Technology, Vol. 20, P. 535-544, 2005.
51.S. Calnan, H. M. Upadhyaya, S. Buecheler, G. Khrypunov, A. Chiril, A. Romeo,
R. Hashimoto, T. Nakada, and A. N. Tiwari, "Application of high mobility
transparent conductors to enhance long wavelength transparency of the
intermediate solar cell in multi-junction solar cells," Thin Solid Films, Vol. 517,
P. 2340-2343, 2009.
52.K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, and H. Arakawa, "Inuence of
electrolytes on the photovoltaic performance of organic dye-sensitized Nano
crystalline TiO2 solar cells," Solar Energy Materials and Solar Cells, Vol. 70, P.
151-161, 2001.
53.K. Hara, T. Nishikawa, M. Kurashige, H. Kawauchi, T. Kashima, K. Sayama, K.
Aika, and H. Arakawa, "Inuence of electrolyte on the photovoltaic performance
of a dye-sensitized TiO2 solar cell based on a Ru(II) terpyridyl complex
photosensitizer," Solar Energy Materials and Solar Cells, Vol. 85, P. 21-30,
2004.
54.S. E. Koops, B. C. O'Regan, P. R. F. Barnes, and J. R. Durrant, "Parameters
inuencing the efficiency of electron injection in dye-sensitized solar cells",
Journal of the American Chemical Society, Vol. 131, P. 4808-4818, 2009.

78
55.G. Boschloo, L. Haggman, and A. Hagfeldt, "Quantification of the effect of 4-
tert-butylpyridine addition to I-/I-3 redox electrolytes in dye-sensitized
nanostructured TiO2 solar cells.," The Journal of Physical Chemistry B, Vol. 110,
P. 13144-13150, 2006.
56.B. Li, L. Wang, B. Kang, P. Wang, and Y. Qiu, \Review of recent progress in
solid-state dye-sensitized solar cells," Solar Energy Materials and Solar Cells,
vol. 90, P. 549-573, 2006.
57.P. Wang, S. M. Zakeeruddin, J-E. Moser, R. Humphry-Baker and M. Grätzel, "A
solvent-free, SeCN-/(SeCN)3- based ionic liquid electrolyte for high-efficiency
dye-sensitized nanocrystalline solar cells", J. Am. Chem. Soc. 2004, Vol. 126, P.
7164.
58.Y. Bai, Y. Cao, J. Zhang, M. Wang, R. Li, P. Wang, S. M. Zakeeruddin, M.
Grätzel," Bifacial dye-sensitized solar cells based on an ionic liquid electrolyte",
Nature Mater., Vol.7, P.626, 2008.
59.F. C. Krebs, M. Biancardo, " Dye sensitized photovoltaic cells: attaching
conjugated polymers to zwitterionic ruthenium dyes", Sol. Energy. Mater. Sol.
Cells., Vol.90, P. 142, 2006.
60.M. Biancardo, K. West, F. C. Krebs, "Optimizations of large area quasi-solid-
state dye-sensitized solar cells", Sol. Energy. Mater. Sol. Cells., Vol.90, P.2575,
2006.
61.S. Lu. R. Koeppe, S. Günes, N. S. Sariciftci, "Quasi-solid-state dye-sensitized
solar cells with cyanoacrylate as electrolyte matrix Sol". Energy. Mater. Sol.
Cells., Vol.91, P.1081, 2007.
62.M. Biancardo, K. West, F. C. Krebs, J. Photochem." Quasi-solid-state dye-
sensitized solar cells: Pt and PEDOT:PSS counter electrodes applied to gel
electrolyte assemblies", Photobiol. A:Chem., Vol.187, P.395, 2007.
63.K. Hara, K. Sayama, Y. Ohga, A. Shinpo, S. Suga, and H. Arakawa," ―A
coumarine-derivativedye sensitised nanocrystalline TiO2 solar cell having a high
solar-energy conversionefficiency up to5.6%", Chem. Commun., P.569, 2001.

78
64. L. Schmidt-Mende, U. Bach, R. Humphry-Baker, T. Horiuchi, H. Miura, S. Ito,
S. Uchida, M. Grätzel, " Organic Dye for Highly Efficient Solid‐State Dye‐
Sensitized Solar Cells", Adv. Mater., Vol.17, P.813, 2005.
65. S. Spiekermann, G. Smestad, J. Kowalik, L. M. Tolbert, M. Grätzel," Poly(4-
undecyl-2,2'-bithiophene) as a hole conductor in solid state dye-sensitized
titanium dioxide solar cells", Synth. Met., Vol.121, P.1603, 2001.
66.T. J. Savenije, J. M. Warman, A. Goossens," ―Visible light sensitization of ... a
phenylene vinylene polymer", Chem. Phys. Lett., Vol.287, P.148, 1998.
67.Y.-G. Kim, J. Walker, L. A. Samuelson, and J. Kumar," Efficient light
harvestingpolymers for nanocrystalline TiO 2 photovoltaic cells", Nano Lett., 3,
523, 2003.
68.G. K. R. Senadeera, K. Nakamura, T. Kitamura, Y. Wada, and S. Yanagida,"
Fabrication of highly efficient polythiophene-sensitized metal oxide photovoltaic
cells", Appl. Phys. Lett., Vol.83, P.5470, 2003.
69.S. Yahagida, G. K. R. Senadeera, K. Nakamura, T. Kitamura, and Y. Wada,"
Polythiophene-sensitized TiO2 solar cells", J. Photochem. Photobio. A: Chem.,
Vol.166, P.75, 2004.
70.J. K. Mwaura, X. Zhao, H. Jiang, K. S. Schanze, J. R. Reynolds, Chem. Mater.,
Vol.18, P. 6109, 2006.
71. X. Liu, R. Zhu, Y. Zhang, B. Liu, S. Ramakrishna, Chem. Commun., P. 3789,
2008.
72. Hongwei Zhu, Jinquan Weia, Kunlin Wanga and Dehai Wua, ―Applications of
carbon materials in photovoltaic solar cells‖, Solar Energy Materials and Solar
Cells Vol. 93, Issue 9 , P.1461-1470, 2009.
73. Ji Ung Lee, ―Photovoltaic effect in ideal carbon nanotube diodes‖, Appl. Phys.
Lett. Vol.87, P. 073101, 2005.
74.Carbon nanotubes in photovoltaics. From Wikipedia.
75.H. Pettersson and T. Gruszecki, "Long-term stability of low-power dye-
sensitised solar cells prepared by industrial methods", Solar Energy Materials &
Solar Cells, Vol.70, P.203-212, 2001.

78
76.Kohle et al., The Photovoltaic Stability of Bis(isothiocyanato) ruthenium(II)-bis-
2,2´-bipyridine-4,4´-dicarboxylic Acid and Related Sensitizers, Adv. Mater., 9,
11, 904-6,1997.
77.A. Kay,and M. Grätzel, "Low cost photovoltaic modules based on dye sensitized
nanocrystalline titanium dioxide and carbon powder, Solar Energy Materials &
Solar Cells", Vol.44, P.99-117, 1996.
78.S. K. Deb, "Photochemical Solar Cells Based on Dye-Sensitization of
Nanocrystalline TiO2, National Energy Laboratory", Presented at the 2nd World
Conference and Exhibition on Photovoltaic Solar Energy Conversion; Austria,
NREL/CP-590-250-25056. 1998
79.Burnside S. D., "Deposition and characterization of screen-printed porous multi-
layer thick film structures from semiconducting and conducting nanomaterials
for use in photovoltaic devices", J. Mater. Sci.: Mater. Electron., Vol.11, P.355-
362, 2000.
80.Krüger, J., "High efficiency solid-state photovoltaic device due to inhibition of
interface charge recombination", Appl. Phys. Lett., 79, 13, 2085-7, 2001.
81.M. Späth, et al., 1997, New Concepts of Nano-Crystalline Organic Photovoltaic
Devices, ftp: //ftp.ecn.nl/pub/www/library/report/1997/rx97060.pdf
82.Wolfbauer, G., et al., A channel flow cell system specifically designed to test the
efficiency of redox shuttles in dye sensitized solar cells, Solar Energy Materials
& Solar Cells, 70, 85-101, 2001.
83. J. Halme, ‟ Dye-sensitized nanostructured and organic photo voltaic cells:
technical review and preliminary tests ‖, M.Sc. thesis, Helsinki University of
Technology, P.115, 2002.
84.C. Brabec, V. D. Parisi, N. Sariciftci, ‟Organic Phofovoltaics Concepts and
Realization‖, Springer, 2003.
85.Brian O'regan and Michael Grӓtzel, "A low-cost, high-efficiency solar cell based
on dye-sensitized colloidal TiO2 films", Vol.353(6346), P.737-740, 1991.
86. M. K. Nazeeruddin, A. Kay, 1. Rodicio, R. Humpbry-Baker, E. Miiller, P.
Liska, N. Vlachopoulos, and M. Gratzel," Conversion of Light to Electricity by

78
 cis-XzBis(2,2’-bipyridyl-4,4’-dicarboxylate)ruthenium(11) Charge-Transfer
Sensitizers (X=C1-, Br-, I-, CN-, and SCN-) on Nanocrystalline Ti02 Electrodes",
J.Am. Chem. Soc. , Vol.115, P.6382-6390, 1993.
87. Greg P. Smestad," Education and solar conversion: Demonstrating electron
transfer", Solar Energy Materials and Solar Cells, Vol.55, P.157-178,1998.
88. Michael Grätzel,"Review Dye-sensitized solar cells", Journal of Photochemistry
and Photobiology C: Photochemistry Reviews, Vol.4, P.145–153, 2003.
89.Gavin E. Tulloch," Light and energy—dye solar cells for the 21st century",
Journal of Photochemistry and Photobiology A: Chemistry", Vol. 164, P.209–
219, 2004.
90.Kinji Onoda, Supachai Ngamsinlapasathian, Takuya Fujieda and Susumu
Yoshikawa," Application of Metallic Titanium as the Substrate for
Photoelectrode of Dye-sensitized Solar Cells", The 2nd Joint International
Conference on ―Sustainable Energy and Environment (SEE 2006)‖, P.21-23,
2006.
91. Jihuai Wu, Zhang Lan, Sanchun Hao, Pingjiang Li, Jianming Lin, Miaoliang
Huang, Leqing Fang, and Yunfang Huang," Progress on the electrolytes for dye-
sensitized solar cells", Pure Appl. Chem., Vol. 80, No. 11, P. 2241–2258, 2008.
92. S. Hasiah, K. Ibrahim, H.B. Senin and K.B.K. Halim,"Electrical Conductivity of
Chlorophyll with Polythiophene Thin Film on Indium Tin Oxide as P-N
Heterojunction Solar Cell", Journal of Physical Science, Vol. 19(2), P.77–92,
2008.
93. M.S. Roy, P. Balraju, Manish Kumar,and G.D. Sharma," Dye-sensitized solar
cell based on Rose Bengal dye and nanocrystalline TiO2", Solar Energy
Materials & Solar Cells, Vol.92, P. 909– 913, 2008.
94. Niyom Hongsith and Supab Choopun, "ZnO Nanobelts as a Photoelectrode for
Dye-Sensitized Solar Cell", Chiang Mai J. Sci.; Vol.37(1) : P.48-54, 2010.
95. Jae-Yup Kim, Soon Hyung Kang , Hyun Sik Kim and Yung-Eun Sung ,
"Preparation of Highly Ordered Mesoporous Al2O3/TiO2 and Its Application in
Dye-Sensitized Solar Cells", Langmuir, Vol.26 (4), P. 2864–2870, 2010.

78
96. Eva M. Barea, Javier Ortiz,Federico J. Paya, Fernando Fernandez-Lazaro,
Francisco Fabregat-Santiago, Angela Sastre-Santos and Juan Bisquert,"
Energetic factors governing injection, regeneration and recombination in dye
solar cells with phthalocyanine sensitizers", Energy & Environmental Science,
2010.
97. Voranuch Somsongkul, Chaiyuth Saekung, San H. Thang, Atchana
Wongchaisuwat and Marisa Arunchaiya, "Composite Poly(ethylene oxide)
Electrolyte Modifiedwith Ethanol for Dye-sensitized Solar Cells", Chiang Mai J.
Sci.,Vol.38(2) : P.223-230, 2011.
98. I.B. Karki, J.J. Nakarmi, P.K. Mandal and S. Chatterjee, "Study of Tea Aroma
Based onZinc oxide Nanorod Sensing Element", The Himalayan Physics, Vol. 3,
2012.
99. Seok Cheol Choi, Ho Suk Lee, Sang Jin Oh and Sang Ho Sohn, "Light scattering
TiO2 particles surface-modified by Al2O3 coating in a dye-sensitized solar cell",
Phys. Scr. Vol.85, 2012.
100. Kuei-Fu Chen, Chien-Hung Liu, Hsin-Kai Huang, Chun-Hung Tsai and Fu-Rong
Chen, "Polyvinyl Butyral-Based Thin Film Polymeric Electrolyte for Dye-
Sensitized Solar Cell with Long-Term Stability",Int. J. Electrochem. Sci., Vol.8,
P.3524 – 3539, 2013.
101. Souad A. M. Al-Bat’hi, Iraj Alaei,and Iis Sopyan, "Natural Photosensitizers for
Dye Sensitized Solar Cells", INTERNATIONAL JOURNAL of RENEWABLE
ENERGY RESEARCH, Vol.3, No.1, 2013.
102. Keisuke Kawata, Seng-Neon Gan, Desmond Teck-Chye Ang, Kavirajaa Pandian
Sambasevam, Sook-Wai Phang, and Noriyuki Kuramoto, "Preparation of
polyaniline/TiO2 nanocomposite film with good adhesion behavior for dye-
sensitized solar cell application", Polymer Composites, Vol. 34, Issue 11, P.
1884–1891, 2013.
103. Wanichaya Mekprasart, Sineenart Suphankij, Thanit Tangcharoen, Athapon
Simpraditpan and Wisanu Pecharapa, "Modification of dye-sensitized solar cell

78
 working electrode using TiO2 nanoparticle/N-doped TiO2 nanofiber
composites", Volume 211, Issue 8, P. 1745–1751, 2014.
104. ZhiPeng Shao,a Xu Pan, HaiWei Chen, Li Tao, WenJun Wang, Yong Ding, Bin
Pan, Shangfeng Yangc and Songyuan Dai, "Polymer based photocathodes for
panchromatic tandem dye-sensitized solar cells", Energy Environ. Sci., Vol.7,
P.2647-2651, 2014.
105. Kungliga Tekniska Högskolan, and Tannia Marinado, Do. thesis,
―Photoelectrochemical studies of dye-sensitized solar cells using organic dyes‖,
Physical Chemistry, Chemical Science and Engineering, KTH, Royal Institute of
Technology, SE-100 44 Stockholm, Sweden, 2009.
106. N. Jebbari1, N. Kamoun Turki1 and R. Bennaceur1, " Effect of SnCl4
concentration on SnO2:F, deposited by chemical spray pyrolysis", International
Renewable Energy Congress, Sousse, Tunisia, P.5-7, 2010 .
107. H. Liu, G. Yan, F. Liu, Y. Zhong, B. Feng, J. Alloys Compd, Vol.481, P. 385,
2009.
108. Thanyarat Sawatsuk, Anon Chindaduang, Chaiyuth Sae-kung, Sirapat Pratontep
and Gamolwan Tumcharern," Dye-sensitized solar cells based on TiO2–
MWCNTs composite electrodes: Performance improvement and their
mechanisms",Diamond and Related Materials, Vol. 18, P.524–527, 2009.
109. Jin Kawaki ta, "Trends of Research and Development of Dye-Sensitized Solar
Cells", Science and Technology Trends, Quarterly review, No. 35, 2010.
110. Dheyaa Badri Alwan, Ms. Thesis, "Preparation dye – Sensitized Solar Cell with
Tracking System", the University of Baghdad, College of Sciences, Department
of Physics, 2013.
111. Chandra Sekharan Nair Omana Amma Sreekala, Jinchu Indiramma, Kandala
Bala Subramanya Pavan Kumar,Karyaveettil Savithriamma Sreelatha and
Mahesh Saran Roy, " Functionalized multi-walled carbon nanotubes for
enhanced photocurrent in dye-sensitized solar cells", Journal Of Nanostructure in
Chemistry, P. 3:19, 2013.

77
112. N. Hongsith and S. Choopun," ZnO Nanobelts as a Photoelectrode for Dye-
Sensitized Solar Cell", Chiang Mai J. Sci.;Vol. 37(1) :P. 48-54, 2010.
113. Ameen S., Akhtar, M. S. & Husain M., Polyaniline and Its Nanocomposites:
Synthesis, Processing, Electrical Properties and Applications, Sci. Adv. Mater.,
Vol. 2, P. 441-462, 2010.
114. Sadia, A.M. Shaheer, S.K.Young and S. Hyung-Shik, ISBN: 978-953-307-735-2,
InTech, 2010.
115. Kareem Najim Abed," Preparation and Identification of TiO2 Nanotubes
(TNT,s)", M.Sc Thesis, the College of Science, University of Baghdad, 2014.
116. A M Pharhad Hussain and A. Kumar; "Electrochemical synthesis and
characterization of chloride doped polyaniline", Mater.sci. Vol. 26,No. 3,P.329-
334, 2003.
117. Andreas Elschner, Stephan Kirchmeyer, Wilfried Lövenich, Udo Merker and
Knud Reuter, "PEDOT Principles and Applications of an Intrinsically
Conductive Polymer", P. 139, Published by: Mario En-tech, 2012.
118. J. Vivekanandan, V. Ponnusamy, A. Mahudeswaran and P. S. Vijayanand, "
Synthesis, characterization and conductivity study of polyaniline prepared by
chemical oxidative and electrochemical methods", Archives of Applied Science
Research, Vol.3 (6):P.147-153, 2011.
119. SALMA MHAMMAD HASAN, "The Optical and Electrical Properties of
Prepared Polyaniline as A conductive Polymer", Doctor thesis, the College of
Science University of Baghdad, 2010.
120. A.Carter, M.Angelopoulos, S.Karg, P.J.Brock and J.C.scott. ― Polymeric Anodes
for Improved Polymer Light –Emitting Diode Performance‖ Applied Physics
Letter, Vol. 70(16), P.2067-2069, 1997.
121. D.A.Fungaro, "Sulfonated Polyaniline Coated Mercury Film Electrodes for
Voltametric Analysis of Metals in Water", Sensors, Vol. 1, P. 206-214, (2001).
122. AM Pharhad Hussain and A. Kumar, Mater.sci. Vol. 26,No. 3,P. 329-334, 2003.
123. Faris Yilmaz, Ms. thesies, University of middle east technical, 2007.
124. Mainfacier ,J.C., Demurcia, M. and Fillard ,J.B, Vol. 41 , p.127 , 1977.

76
125. Raad S. Sabri and Saeed. N.Turkey, "Journal of university of Anbar for Pure
science", vol. 3 , P. 91-94, ISSN: 1991-8941, 2009.
126. T. Seiyama, A. Kato, K. Fujiishi, M. Nagatan, ―A new detector for gaseous
components using semiconducting thin films‖, Anal Chem., Vol. 34, P. 1502,
1962.
127. Shailesh Pawar, Manik Chougule, Sanjay Patil, Bharat Raut, Dhanaji Dalvi,
Pramod Patil, Shashwati Sen, Pradeep Joshi, and Vikas Patil,"Fabrication of
Nanocrystalline TiO2 Thin Film Ammonia Vapor Sensor", Journal of Sensor
Technology, Vol. 1, P. 9-16, 2011.
128. Nirton Cristi Silva Vieira, Edson Giuliani Ramos Fernandes, Alvaro Antonio
Alencar de Queiroz, Francisco Eduardo Gontijo Guimarães and Valtencir
Zucolotto," Indium tin oxide synthesized by a low cost route as SEGFET pH
sensor", Mat. Res., Vol.16, 2013.
129. S.M.Sze "Semiconductor Devices physics and technology" Prentice-hall of India
private Limited, USA, p.245, 1985.
130. J. D. Patterson and B. C. Bailey "Solid State Physics" Introduction to the theory,
NY, P. 241, 2007.
131. M. Anwar and I.M. Ghauri, "The electrical properties of amorphous thin films of
Al-In2O3-Al deposited by thermal evaporation", Rom.Journ. Phys.,Vol. 50, P.7,
2005.
132. L.H. Vanviock, "Elements of materials science and engineering", 5 th edition,
Addison-Wesley publishing company, Inc. 1987. 17-140 J. Vivekanandan, V.
Ponnusamy, A. Mahudeswaran and P. S. Vijayanand1, Archives of Applied
Science Research, Vol. 3 (6), pp. 147-153, 2011.
133. I.E. Kelly, J.R. Owen, B.C.H. Steele, J. Electroanal. Chem., Vol. 168,P. 467,
1984.
134. Chandra Sekharan Nair Omana Amma Sreekala, Jinchu Indiramma, Kandala
Bala Subramanya Pavan Kumar,Karyaveettil Savithriamma Sreelatha and
Mahesh Saran Roy, "Functionalized multi-walled carbon nanotubes for enhanced

77
photocurrent in dye-sensitized solar cells", Journal Of Nanostructure in
Chemistry, Vol.3,P.19, 2013.

78
 ‫وزارة التعميم العالي والبحث العممي‬
‫جامعة بغـداد‬
‫كمية العموم‬
‫قسم الفيزياء‬

‫بوليمير موصل لتحسين كفاءة خليت شمسيت صبغيت‬

‫اطروحة‬
‫مقدمة الى مجمس كمية العموم في جامعة بغداد‬
‫كجزء من متطمبات نيل درجة ماجستير عموم في الفيزياء‬
‫(فيزياء ليزر و كهروبصريات)‬
‫من قبل‬

‫أحمد علي عاصي‬

‫بكالوريوس علوم (فيزياء)‬
‫جامعة بابل‪ -‬كلية العلوم ‪2102‬‬
‫بإشراف‬

‫األستاذ ألمساعد الدكتورة وسن رشيد صالح‬

‫‪ 2014‬م‬ ‫‪1435‬هـ‬
 ‫الخالصت‬

‫فييه ْييلب بن ذ ي تييى تذر ي خه ييش سًض ي ش ةي ش باصييدامبو ة ي اي ي م ييش يةييم ة ي ش بن ييياٌ‬
‫ٔة ش ٔردة بنكٕج بي‪ .‬بصداميت يٕبد تضاعم فه تذض ٍ بجزبء بناه ش بنشًضي ش (بنقطي بنويٕ ه‬
‫ٔبنًذهٕل بالنكد ٔن ده ٔبنقط بنجايع) ٔ باندانه تذض ٍ كفاءة بناه ش بنشًض ش بنُاتجش نٓلب بن ض‬
‫ثييى تييى تذو ي زجييا سييفام يٕةييم باصييدامبو ربيياعه كهٕريييم بنقيييمي بنًييا ه ‪SnCl4.5H2O‬‬
‫ٔي يقش بن ط بنك ً ا ه ندكٕيٍ غشاء بٔكض م بنقي ‪ SnO2‬باصدامبو بفوم س ٔي ٔكاَت بمرجش‬
‫د برة تد بٔح ب ٍ ‪ 646ٔ 626‬درجش يئٕييش ٔبًميمل ‪ 22‬رسياي كيم رسيش بشيمة رط ‪ 0.1mℓ‬نكيم‬
‫رسش عهى برتفاع ‪ 26‬صى ٔبزبٔيش ‪.˚45‬‬
‫بنًيٕبد بنديه تيى بصيدامبيٓا فيه تييُ ع خه يش بنيي ش بنًدذضضيش بنشًضي ش ْيه كيم ييٍ ثُيا ه بٔكضي م‬
‫بند ديياَ ٕو ‪ TiO2‬بنُييإَو ٔبَاب يي بنكيياربٌٕ بنُإَيييش يدمييمدة بنجييمربٌ )‪ٔ (MWCNT‬بَاب يي‬
‫بنكياربٌٕ بنُإَييش يدميمدة بنجيمربٌ بنًمانجيش بانًجًٕعيش بنك بٕكضي ه ش )‪ٔ (COOH‬كيلن د ياي‬
‫بنفوش بنُإَيش فه تذو بنقط بنوٕ ه‪ .‬تيى بصيدامبو بيٕنه بثهي ٍ بكميكيٕل بيٕزٌ جزيئيه ‪4666‬‬
‫ٔبثه ٍ كميكٕل ٔ يٕديم بن ٕتاص ٕو )‪ٔ (KI‬يٕديم )‪ (I2‬ندذو بنًذهٕل بالنكد ٔن ده‪ ,‬بيا فه بنقط‬
‫بنجييايع فقييم تييى بصييدامو بالَ ه ي ٍ (ندذو ي بييٕنه بَه ي ٍ) ٔبصييٕد بنكيياربٌٕ ٔبييٕن ً ‪poly (3,4-‬‬
‫)‪ ethylene dioxythiophene): poly(styrene sulfonate) (PEDOT:PSS‬بنًمييانب بي‬
‫)‪ dimethyl sulfoxide (DMSO‬د ي بٌ كيم يُٓيا رصي ت يي ِ عهيى زجيا يٕةيم يطهيه بي‬
‫‪ٔ SnO2‬ي ة ثاَ ش عهى زجا يطهه ب ‪ ITO‬بنًٕةم بنجاْز‪.‬‬
‫بيٕن ً بن يٕنه بَهي ٍ بالخوي بنًٕةيم تييى تذوي ة بط يقيش بن هًي ة بنكٓ ٔك ً ا يش نمَهي ٍ فييه‬
‫درجش د برة بن فش‪ .‬بٕن ً ‪ PEDOT:PSS‬بيوا بعطا َديا ب ج يمة كقطي جيايع نكيٍ بنًمهٕيياي‬
‫بنًدٕف ة عُش قه هش فه يجال بناميا بنشًض ش بنًمانجش بٕبصطش بٕن ً ‪ . PEDOT:PSS‬بفوم كفاءة‬
‫تى بنذيٕل عه ٓا ْه ‪ 0.72%‬بأصدامبو ة ش بن ياٌ بنط م يش ٔ قطي جيايع ييٍ بن يٕنه بَ هي ٍ ٔ‬
‫بالنكد ٔاليت بنضا م ٔقط ضٕ ه ‪.f-MWCNT/Ag/TiO2‬‬
‫تيييى بُجييياح ييييمء بنزجيييا بنًذوييي ‪ SnO2‬ب يييٕن ً بن يييٕنه بَهييي ٍ ٔ نييي باصيييدامبو بن هًييي ة‬
‫بنكٓ ٔك ً ا ش نمَه ٍ نيُع بدم بَٕبع بنقط بنجايع نهاه ش بني ش بنشًض ش‪ .‬كًا تى ييمء بن يٕنه‬
‫‪ ITO‬بنًٕةم بنجياْز ٔتيى بدخيال كيم يًُٓيا فيه تييُ ع بناه يش كأقطيا جايميش‬ ‫بَ ه ٍ عهى زجا‬
‫ٔكاَت بنكفاءة باصدامبو ‪ْ SnO2‬ه ‪ %6.55‬ب ًُا باصدامبو ‪ ITO‬كاَت ‪.%72‬‬
 ‫بنزجا بنًٕةم بنًذو باصدامبو ‪ SnO2‬بعطى قٕة بندياق بك يٍ بنزجا بنجاْز بنًطهيه‬
‫ب ‪ ITO‬باإلضافش بنى بٌ كهفش تذو ِ ْه بقم بُض ش ‪ 2:5‬يٍ كهفش بنزجا بنجاْز‪.‬‬
‫يٍ ْلب بنمًم ٔجم بٌ جض ًاي بنفوش بنُإَيش ‪ Ag‬تذضٍ يٍ كفاءة بناه يش بنشًضي ش عُيم ٔضيمٓا‬
‫يع جض ًاي ثُا ه بٔكض م بند داَ ٕو ‪ٔ TiO2‬كلن بضافش ‪ f-MWCNT‬يذضٍ بشكم ج م يٍ كفاءة‬
‫ٔبصييدق بريّ بناه ييش عُييم ٔضييمش يييع جض ي ًاي ثُييا ه بٔكض ي م بند ديياَ ٕو بنُإَيييش‪ .‬ن يٕدظ عُييم يييز‬
‫جضييي ًاي بنفويييش بنُإَييييش ييييع بَاب ييي بنكييياربٌٕ بنُإَييييش يدميييمد بنجيييمربٌ بنًمانجيييش بانًجًٕعيييش‬
‫بنك بٕكض ه ش )‪ ٔ (COOH‬بضافدٓا بنى عج ُش ‪ TiO2‬تمطه َدا ب بفوم يٍ بضافش كم ٔبديم عهيى‬
‫دمب‪ ,‬بفوم َض بضافش كاَت ‪ 1 mℓ/g‬نهفوش ٔ ‪ 0.5 mg/g‬ن ‪ f-MWCNT‬يع ‪0.83 ٔ TiO2‬‬
‫‪ g‬ن ‪ 0.083 g ٔ KI‬يع ‪ 10 mℓ‬بثه ٍ كميكٕل نمًم بنكد ٔاليت صا م ٔتى بضافش ‪40% W/Vol.‬‬
‫يٍ بٕنه بثه ٍ بكميكٕل بنى َفش بنًذهٕل بالنكد ٔن ده بنضا م نمًم يذهٕل بنكد ٔن ده ْمييه‪ .‬فيه‬
‫بنقط بنجايع ٔجم بٌ بن ٕنه بَ ه ٍ يمطه بفوم كفاءة باإلضافش نكَّٕ صٓم بندذو ‪ ,‬قه هش بنكهفش‪.‬‬
‫بنً ك ياي ٔبب زْيا بني‬ ‫بصدامو ق اس تٕزييع ‪ X-ray diffraction‬ندذمييم ت ك ي َٔيٕع بمي‬
‫باليدياةييي ش ن شييياء ‪ ٔ PANI ٔ ITO ٔ SnO2‬بنيييي ش‬ ‫‪ SnO2‬بنًذوييي ‪ .‬تيييى بخيييل ق ييياس ي ييي‬
‫بنشًضيه ٔخاةيشئ بنً يه يُٓيا ٔتيى تذمييم فجيٕة‬ ‫نًم فش بنًمياي بنده يًكيٍ بٌ تًدييٓا ييٍ بنط ي‬
‫كاَت ق ًدٓا ‪ ٔ 3.825 eV‬كلأن بخل ق ياس ‪ SEM ٔ AFM‬نًم فيش بنشيكم‬ ‫بنطاقش ن ‪ SnO2‬د‬
‫بنطٕبٕغ بفه نضطخ بغش ش بن ‪ ITO ٔ SnO2‬بنلو يدوًٍ بنذجى بنذ ه ٔبنلو كياٌ ‪222 ٔ 232‬‬
‫َإَيد عهى بندٕبنه ب ًُا ن ‪ PANI‬بخل قط بالَ يٕ ٔكياٌ بذيمٔد ‪َ 73‬يإَ يدي ٔخشيَٕش بنضيطخ‬
‫نده بالغش ش كاَت ‪ 0.934 ٔ 1.24‬عهى بندٕبنه‪.‬‬

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