Table of Contents

1. Chapter 1: Introduction
Construction
Operation
Efficiency
Advantages and drawbacks
2. Chapter 2: Polymers
Molecular Basis of Electrical Conductivity
Properties & Applications
Electroluminescence
Barriers to applications
Trends
Conductive Polymers in Solar Cells
3. Chapter 3: Polyaniline
Synthesis
Processing
4. Chapter 4
Literature Review
5. Chapter 5: Synthesis & Deposition of Polyaniline
Cross-linking of PVA film
Use of Surface Active agent
Synthesis of Polyaniline
Recovery of PANI by filtration
Soaking the film in APS
Results
Preparation of TiO2 coated glass
Assembling the cell
6. Chapter 6
Future scope of work

1
Chapter 1

Introduction
A solar cell, or photovoltaic cell, is an electrical device that converts the energy of light directly
into electricity by the photovoltaic effect, which is a physical and chemical phenomenon. It is a
form of photoelectric cell, defined as a device whose electrical characteristics, such as current,
voltage, or resistance, vary when exposed to light. Solar cells are the building blocks of
photovoltaic modules, otherwise known as solar panels.

A hetero-junction is the interface that occurs between two layers or regions of dissimilar
crystalline semiconductors. These semiconducting materials have unequal band gaps as opposed
to a homojunction. It is often advantageous to engineer the electronic energy bands in many
solid-state device applications, including semiconductor lasers, solar cells and transistors to
name a few.
Heterojunctions are most commonly created by forming a solution containing the two
components, casting (e.g. drop casting and spin coating) and then allowing the two phases to
separate, usually with the assistance of an annealing step. The two components will self-
assemble into an interpenetrating network connecting the two electrodes. They are normally
composed of a conjugated molecule based donor and fullerene based acceptor. The
nanostructural morphology of bulk heterojunctions tends to be difficult to control, but is critical
to photovoltaic performance.
A dye-sensitized solar cell (DSSC, DSC or DYSC) is a low-cost solar cell belonging to the group
of thin film solar cells. It is based on a semiconductor formed between a photosensitized anode
and an electrolyte, a photoelectrochemical system.

2
In a traditional solid-state semiconductor, a solar cell is made from two doped crystals, one
doped with n-type impurities (n-type semiconductor), which has "extra free" electrons, and the
other doped with p type impurities (p-type semiconductor), which is lacking free electrons.
When placed in contact, some of the electrons in the n-type portion flow into the p-type to "fill
in" the missing electrons, also known as electron holes. Eventually enough electrons will flow
across the boundary to equalize the Fermi levels of the two materials. The result is a region at the
interface, the p-n junction, where charge carriers are depleted and/or accumulated on each side of
the interface. In silicon, this transfer of electrons produces a potential barrier of about 0.6 to 0.7
V.
When placed in the sun, photons of the sunlight can excite electrons on the p-type side of the
semiconductor, a process known as photo excitation. In silicon, sunlight can provide enough
energy to push an electron out of the lower-energy valence band into the higher-energy
conduction band. As the name implies, electrons in the conduction band are free to move about
the silicon. When a load is placed across the cell as a whole, these electrons will flow out of the
p-type side into the n-type side, lose energy while moving through the external circuit, and then
back into the p-type material where they can once again re-combine with the valence-band hole
they left behind. In this way, sunlight creates an electrical current.

In any semiconductor, the band gap means that only photons with that amount of energy, or
more, will contribute to producing a current. In the case of silicon, the majority of visible light
from red to violet has sufficient energy to make this happen. Unfortunately higher energy
photons, those at the blue and violet end of the spectrum, have more than enough energy to cross
the band gap; although some of this extra energy is transferred into the electrons, the majority of
it is wasted as heat. Another issue is that in order to have a reasonable chance of capturing a
photon, the n-type layer has to be fairly thick. This also increases the chance that a freshly
ejected electron will meet up with a previously created hole in the material before reaching the p-

3
n junction. These effects produce an upper limit on the efficiency of silicon solar cells, currently
around 12 to 15% for common modules and up to 25% for the best laboratory cells (about 30% is
the theoretical maximum efficiency for single band gap solar cells).
By far the biggest problem with the conventional approach is cost; solar cells require a relatively
thick layer of doped silicon in order to have reasonable photon capture rates, and silicon
processing is expensive. There have been a number of different approaches to reduce this cost
over the last decade, notably the thin-film approaches, but to date they have seen limited
application due to a variety of practical problems. Another line of research has been to
dramatically improve efficiency through the multi-junction approach, although these cells are
very high cost and suitable only for large commercial deployments. In general terms the types of
cells suitable for rooftop deployment have not changed significantly in efficiency, although costs
have dropped somewhat due to increased supply.
A DSSC is composed of a porous layer of titanium dioxide nanoparticles, covered with a
molecular dye that absorbs sunlight, like the chlorophyll in green leaves. The titanium dioxide is
immersed under an electrolyte solution, above which is a platinum-based catalyst. As in a
conventional alkaline battery, an anode (the titanium dioxide) and a cathode (the platinum) are
placed on either side of a liquid conductor (the electrolyte).
Sunlight passes through the transparent electrode into the dye layer where it can excite electrons
that then flow into the titanium dioxide. The electrons flow toward the transparent electrode
where they are collected for powering a load. After flowing through the external circuit, they are
re-introduced into the cell on a metal electrode on the back, flowing into the electrolyte. The
electrolyte then transports the electrons back to the dye molecules.
Dye-sensitized solar cells separate the two functions provided by silicon in a traditional cell
design. Normally the silicon acts as both the source of photoelectrons, as well as providing the
electric field to separate the charges and create a current. In the dye-sensitized solar cell, the bulk
of the semiconductor is used solely for charge transport, the photoelectrons are provided from a
separate photosensitive dye. Charge separation occurs at the surfaces between the dye,
semiconductor and electrolyte.
The dye molecules are quite small (nanometer sized), so in order to capture a reasonable amount
of the incoming light the layer of dye molecules needs to be made fairly thick, much thicker than
the molecules themselves. To address this problem, a nanomaterial is used as a scaffold to hold
large numbers of the dye molecules in a 3-D matrix, increasing the number of molecules for any
given surface area of cell. In existing designs, this scaffolding is provided by the semiconductor
material, which serves double-duty.

4
Construction

The cell has 3 primary parts. On top is a transparent anode made of fluoride-doped tin dioxide
(SnO2:F) deposited on the back of a (typically glass) plate. On the back of this conductive plate
is a thin layer of titanium dioxide (TiO2), which forms into a highly porous structure with an
extremely high surface area. TiO2 only absorbs a small fraction of the solar photons (those in the
UV). The plate is then immersed in a mixture of a photosensitive ruthenium-polypyridine dye
(also called molecular sensitizers[7]) and a solvent. After soaking the film in the dye solution, a
thin layer of the dye is left covalently bonded to the surface of the TiO2.
A separate plate is then made with a thin layer of the iodide electrolyte spread over a conductive
sheet, typically platinum metal. The two plates are then joined and sealed together to prevent the
electrolyte from leaking. The construction is simple enough that there are hobby kits available to
hand-construct them. Although they use a number of "advanced" materials, these are inexpensive
compared to the silicon needed for normal cells because they require no expensive
manufacturing steps. TiO2, for instance, is already widely used as a paint base.

Operation
Sunlight enters the cell through the transparent SnO 2:F top contact, striking the dye on the
surface of the TiO2. Photons striking the dye with enough energy to be absorbed create an
excited state of the dye, from which an electron can be "injected" directly into the conduction
band of the TiO2. From there it moves by diffusion (as a result of an electron concentration
gradient) to the clear anode on top.
Meanwhile, the dye molecule has lost an electron and the molecule will decompose if another
electron is not provided. The dye strips one from iodide in electrolyte below the TiO2, oxidizing
it into triiodide. This reaction occurs quite quickly compared to the time that it takes for the
injected electron to recombine with the oxidized dye molecule, preventing this recombination
reaction that would effectively short-circuit the solar cell.

5
The triiodide then recovers its missing electron by mechanically diffusing to the bottom of the
cell, where the counter electrode re-introduces the electrons after flowing through the external
circuit.

Efficiency
Several important measures are used to characterize solar cells. The most obvious is the total
amount of electrical power produced for a given amount of solar power shining on the cell.
Expressed as a percentage, this is known as the solar conversion efficiency. Electrical power is
the product of current and voltage, so the maximum values for these measurements are important
as well, Jsc and Voc respectively. Finally, in order to understand the underlying physics, the
"quantum efficiency" is used to compare the chance that one photon (of a particular energy) will
create one electron.
In quantum efficiency terms, DSSCs are extremely efficient. Due to their "depth" in the
nanostructure there is a very high chance that a photon will be absorbed, and the dyes are very
effective at converting them to electrons. Most of the small losses that do exist in DSSC's are due
to conduction losses in the TiO2 and the clear electrode, or optical losses in the front electrode.
The overall quantum efficiency for green light is about 90%, with the "lost" 10% being largely
accounted for by the optical losses in top electrode. The quantum efficiency of traditional
designs vary, depending on their thickness, but are about the same as the DSSC.
In theory, the maximum voltage generated by such a cell is simply the difference between the
(quasi-)Fermi level of the TiO2 and the redox potential of the electrolyte, about 0.7 V under solar
illumination conditions (Voc). That is, if an illuminated DSSC is connected to a voltmeter in an
"open circuit", it would read about 0.7 V. In terms of voltage, DSSCs offer slightly higher V oc
than silicon, about 0.7 V compared to 0.6 V. This is a small difference, so real-world differences
are dominated by current production, Jsc.
Although the dye is highly efficient at converting absorbed photons into free electrons in the
TiO2, only photons absorbed by the dye ultimately produce current. The rate of photon
absorption depends upon the absorption spectrum of the sensitized TiO 2 layer and upon the solar
flux spectrum. The overlap between these two spectra determines the maximum possible
photocurrent. Typically used dye molecules generally have poorer absorption in the red part of
the spectrum compared to silicon, which means that fewer of the photons in sunlight are usable
for current generation. These factors limit the current generated by a DSSC, for comparison, a
traditional silicon-based solar cell offers about 35 mA/cm2, whereas current DSSCs offer about
20 mA/cm2.
Overall peak power production efficiency for current DSSCs is about 11%

Advantages and drawbacks

DSSCs are currently the most efficient third-generation solar technology available. Other thin-
film technologies are typically between 5% and 13%, and traditional low-cost commercial
silicon panels operate between 12% and 15%. This makes DSSCs attractive as a replacement for
existing technologies in "low density" applications like rooftop solar collectors, where the

6
mechanical robustness and light weight of the glass-less collector is a major advantage. They
may not be as attractive for large-scale deployments where higher-cost higher-efficiency cells are
more viable, but even small increases in the DSSC conversion efficiency might make them
suitable for some of these roles as well.
There is another area where DSSCs are particularly attractive. The process of injecting an
electron directly into the TiO 2 is qualitatively different to that occurring in a traditional cell,
where the electron is "promoted" within the original crystal. In theory, given low rates of
production, the high-energy electron in the silicon could re-combine with its own hole, giving off
a photon (or other form of energy) and resulting in no current being generated. Although this
particular case may not be common, it is easy for an electron generated in another molecule to hit
a hole left behind in a previous photoexcitation.
In comparison, the injection process used in the DSSC does not introduce a hole in the TiO 2,
only an extra electron. Although it is energetically possible for the electron to recombine back
into the dye, the rate at which this occurs is quite slow compared to the rate that the dye regains
an electron from the surrounding electrolyte. Recombination directly from the TiO 2 to species in
the electrolyte is also possible although, again, for optimized devices this reaction is rather slow.
On the contrary, electron transfer from the platinum coated electrode to species in the electrolyte
is necessarily very fast.
As a result of these favorable "differential kinetics", DSSCs work even in low-light conditions.
DSSCs are therefore able to work under cloudy skies and non-direct sunlight, whereas traditional
designs would suffer a "cutout" at some lower limit of illumination, when charge carrier mobility
is low and recombination becomes a major issue. The cutoff is so low they are even being
proposed for indoor use, collecting energy for small devices from the lights in the house.
A practical advantage, one DSSCs share with most thin-film technologies, is that the cell's
mechanical robustness indirectly leads to higher efficiencies in higher temperatures. In any
semiconductor, increasing temperature will promote some electrons into the conduction band
"mechanically". Such systems suffer noticeable decreases in efficiency as the cells heat up
internally. DSSCs are normally built with only a thin layer of conductive plastic on the front
layer, allowing them to radiate away heat much easier, and therefore operate at lower internal
temperatures.
The major disadvantage to the DSSC design is the use of the liquid electrolyte, which has
temperature stability problems. At low temperatures the electrolyte can freeze, ending power
production and potentially leading to physical damage. Higher temperatures cause the liquid to
expand, making sealing the panels a serious problem. Another major drawback is the electrolyte
solution, which contains volatile organic solvents and must be carefully sealed. This, along with
the fact that the solvents permeate plastics, has precluded large-scale outdoor application and
integration into flexible structure.

Chapter 2
Polymers:

7
Polymers shape our lives because polymers can be shaped. It is the major driving force behind
most research that tries to design plastics fit for electronic applications. Polymers have the
advantage that they are so much easier to be processed than metals. For example, one can very
easily cover large surfaces with a spin-coated polymer solution. Once the solvent has evaporated
one is left with a layer of polymer chains. Most plastics can be deformed reversibly and they also
do not break easily, which is not true for metals. These properties and the ease with which
polymers can be shaped into complex multi-polymer architectures are the reasons that have
enticed many scientists and industrialists looking for novel applications and new products.

Conductive polymers, or more precisely intrinsically conducting polymers (ICPs) are organic
polymers that conduct electricity. Such compounds may have metallic conductivity or can be
semiconductors. The biggest advantage of conductive polymers is their process ability, mainly
by dispersion. Conductive polymers are generally not thermoplastics, i.e. they are not thermo
formable. But, like insulating polymers, they are organic materials. They can offer high electrical
conductivity but do not show similar mechanical properties to other commercially available
polymers. The electrical properties can be fine-tuned using the methods of organic synthesis and
by advanced dispersion techniques.

One can distinguish between 3 types of conducting polymers:

1. Electron-conducting polymers

2. Proton-conducting polymers

3. Ion-conducting polymers

Each polymer type has already found widespread use in many, mainly optical and electronic
applications such as batteries, displays, plastic wires, optical signal processing, information
storage, solar energy conversion, etc.

Molecular Basis of Electrical Conductivity

The conductivity of such polymers is the result of several processes. E.g., in traditional polymers
such as polyethylenes, the valence electrons are bound in sp3 hybridized covalent bonds. Such
"sigma-bonding electrons" have low mobility and do not contribute to the electrical conductivity
of the material. However, in conjugated materials, the situation is completely different.
Conducting polymers have backbones of contiguous sp2 hybridized carbon centers. One valence
electron on each center resides in a p z orbital, which is orthogonal to the other three sigma-bonds.
The electrons in these delocalized orbitals have high mobility when the material is "doped" by
oxidation, which removes some of these delocalized electrons. Thus, the conjugated p-orbitals
form a one-dimensional electronic band, and the electrons within this band become mobile when
it is partially emptied. The band structures of conductive polymers can easily be calculated with
a tight binding model. In principle, these same materials can be doped by reduction, which adds

8
electrons to an otherwise unfilled band. In practice, most organic conductors are doped
oxidatively to give p-type materials. The redox doping of organic conductors is analogous to the
doping of silicon semiconductors, whereby a small fraction silicon atoms are replaced by
electron-rich (e.g., phosphorus) or electron-poor (e.g. boron) atoms to create n-type and p-type
semiconductors, respectively. Although typically "doping" conductive polymers involves
oxidizing or reducing the material, conductive organic polymers associated with a protic solvent
may also be "self-doped."

Undoped conjugated polymers state are semiconductors or insulators. In such compounds, the
energy gap can be > 2 eV, which is too great for thermally activated conduction. Therefore,
undoped conjugated polymers, such as polythiophenes, polyacetylenes only have a low electrical
conductivity of around 10−10 to 10−8 S/cm. Even at a very low level of doping (< 1%), electrical
conductivity increases several orders of magnitude up to values of around 0.1 S/cm. Subsequent
doping of the conducting polymers will result in a saturation of the conductivity at values around
0.1–10 kS/cm for different polymers. Highest values reported up to now are for the conductivity
of stretch oriented polyacetylene with confirmed values of about 80 kS/cm. Although the pi-
electrons in polyactetylene are delocalized along the chain, pristine polyacetylene is not a metal.
Polyacetylene has alternating single and double bonds which have lengths of 1.44 and 1.36 Å,
respectively. Upon doping, the bond alteration is diminished in conductivity increases. Non-
doping increases in conductivity can also be accomplished in a field effect transistor (organic
FET or OFET) and by irradiation. Some materials also exhibit negative differential resistance
and voltage-controlled "switching" analogous to that seen in inorganic amorphous
semiconductors.

Properties & Applications

Due to their poor processability, conductive polymers have few large-scale applications. They
have promise in antistatic materials and they have been incorporated into commercial displays
and batteries, but there have been limitations due to the manufacturing costs, material
inconsistencies, toxicity, poor solubility in solvents, and inability to directly melt process.
Literature suggests they are also promising in organic solar cells, printing electronic
circuits, organic light-emitting diodes, actuators, electrochromism, supercapacitors, chemical
sensors and biosensors, flexible transparent displays, electromagnetic shielding and possibly
replacement for the popular transparent conductor indium tin oxide.[28] Another use is
for microwave-absorbent coatings, particularly radar-absorptive coatings on stealth aircraft.
Conducting polymers are rapidly gaining attraction in new applications with increasingly
processable materials with better electrical and physical properties and lower costs. The new
nanostructured forms of conducting polymers particularly, augment this field with their higher
surface area and better dispersability.

9
Electroluminescence

Electroluminescence is light emission stimulated by electric current. In organic compounds,

electroluminescence has been known since the early 1950s, when Bernanose and coworkers first
produced electroluminescence in crystalline thin films of acridine orange and quinacrine. In
some cases, similar light emission is observed when a voltage is applied to a thin layer of a
conductive organic polymer film. While electroluminescence was originally mostly of academic
interest, the increased conductivity of modern conductive polymers means enough power can be
put through the device at low voltages to generate practical amounts of light. This property has
led to the development of flat panel displays using organic LEDs, solar panels, and
optical amplifiers.

Barriers to applications
Since most conductive polymers require oxidative doping, the properties of the resulting state are
crucial. Such materials are salt-like (polymer salt), which diminishes their solubility in organic
solvents and water and hence their processability. Furthermore, the charged organic backbone is
often unstable towards atmospheric moisture. The poor processability for many polymers
requires the introduction of solubilizing or substituents, which can further complicate the
synthesis.
Experimental and theoretical thermodynamical evidence suggests that conductive polymers may
even be completely and principally insoluble so that they can only be processed by dispersion.
Trends
Most recent emphasis is on organic light emitting diodes and organic polymer solar cells. The
Organic Electronics Association is an international platform to promote applications of organic
semiconductors. Conductive polymer products with embedded and improved electromagnetic
interference (EMI) and electrostatic discharge (ESD) protection have led to both prototypes and
products. Typical conductive polymers must be "doped" to produce high conductivity. As of
2001, there remains to be discovered an organic polymer that is intrinsically electrically
conducting.
Conductive Polymers in Solar Cells
Silicon-based solar cells are commercially available due to their high solar-to-electric energy
conversion efficiency. However, several disadvantages such as heavy weight, high cost and lack
of flexibility necessitated the development of organic photovoltaic cells and dye-sensitized solar
cells (DSSCs). DSSCs have a maximum energy conversion efficiency of ~10% and hence,
conducting polymers are used as electron transfer mediators or photoreceptors to increase the
efficiency.

The DSSC has a number of attractive features; it is simple to make using conventional roll-
printing techniques, is semi-flexible and semi-transparent which offers a variety of uses not

10
applicable to glass-based systems, and most of the materials used are low-cost. In practice it has
proven difficult to eliminate a number of expensive materials, notably platinum and ruthenium,
and the liquid electrolyte presents a serious challenge to making a cell suitable for use in all
weather. Although its conversion efficiency is less than the best thin-film cells, in theory its
price/performance ratio should be good enough to allow them to compete with fossil fuel
electrical generation by achieving grid parity.

11
Chapter 3
Polyaniline

Polyaniline (PANI) is a conducting polymer of the semi-flexible rod polymer family. Although
the compound itself was discovered over 150 years ago, only since the early 1980s has
polyaniline captured the intense attention of the scientific community. This interest is due to the
rediscovery of high electrical conductivity. Amongst the family of conducting polymers
and organic semiconductors, polyaniline has many attractive processing properties. Because of
its rich chemistry, polyaniline is one of the most studied conducting polymers of the past 50
years.

Polymerized from the inexpensive aniline monomer, polyaniline can be found in one of three
idealized oxidation states.

 leucoemeraldine – white/clear & colorless (C6H4NH)n

 emeraldine – green for the emeraldine salt, blue for the emeraldine base
([C6H4NH]2[C6H4N]2)n
 (per)nigraniline – blue/violet (C6H4N)n
Leucoemeraldine with n = 1, m = 0 is the fully reduced state. Pernigraniline is the fully oxidized
state (n = 0, m = 1) with imine links instead of amine links. Studies have shown that most forms
of polyaniline are one of the three states or physical mixtures of these components. The
emeraldine (n = m = 0.5) form of polyaniline, often referred to as emeraldine base (EB), is
neutral, if doped (protonated) it is called emeraldine salt (ES), with the imine nitrogen protonated
by an acid. Protonation helps to delocalize the otherwise trapped diiminoquinone-
diaminobenzene state. Emeraldine base is regarded as the most useful form of polyaniline due to
its high stability at room temperature and the fact that, upon doping with acid, the resulting
emeraldine salt form of polyaniline is highly electrically conducting. Leucoemeraldine and
pernigraniline are poor conductors, even when doped with an acid.
The colour change associated with polyaniline in different oxidation states can be used in sensors
and electrochromic devices. Although color is useful, the best method for making a polyaniline
sensor is arguably to take advantage of the dramatic changes in electrical conductivity between
the different oxidation states or doping levels. Treatment of emeraldine with acids increases the

12
electrical conductivity by ten orders of magnitude. Undoped polyaniline has a conductivity
of 6.28×10−9 S/m, while conductivities of4.60×10−5 S/m can be achieved by doping to 4% HBr.
The same material can be prepared by oxidation of leucoemeraldine.
Polyaniline is more noble than copper and slightly less noble than silver which is the basis for its
broad use in printed circuit board manufacturing (as a final finish) and in corrosion protection.

Synthesis
Although the synthetic methods to produce polyaniline are quite simple, the mechanism of
polymerization is probably complex. The formation of leucoemeraldine can be described as
follows, where [O] is a generic oxidant:
n C6H5NH2 + [O] → [C6H4NH]n + H2O
The most common oxidant is ammonium persulfate. The components are each dissolved in 1
M hydrochloric acid (other acids can be used), and the two solutions slowly combined. The
reaction is very exothermic. The polymer precipitates as an unstable dispersion with micrometer-
scale particulates.
(Per) nigraniline is prepared by oxidation of the emeraldine base, one typical oxidant being meta-
chloroperoxybenzoic acid:
{[C6H4NH]2[C6H4N]2}n + RCO3H → [C6H4N]n + H2O + RCO2H

Processing
Using special polymerisation procedures and surfactant dopants, the obtained polyaniline powder
can be made dispersible and hence useful for practical applications. Bulk synthesis of polyaniline
nanofibers has led to a highly scalable and commercially applicable form of polyaniline that has
been researched extensively since their discovery in 2002.
A multi-stage model for the formation of emeraldine base is proposed. In the first stage of the
reaction the pernigraniline PS salt oxidation state is formed. In the second stage pernigraniline
is reduced to the emeraldine salt as aniline monomer gets oxidized to the radical cation. In the
third stage this radical cation couples with ES salt. This process can be followed by light
scattering analysis which allows the determination of the absolute molar mass. Approximately
19% of the final polymer is made up of the aniline radical cation which is formed during the
reaction.
Polyaniline is typically produced in the form of long-chain polymer aggregates, surfactant (or
dopant) stabilized nanoparticle dispersions, or stabilizer-free nanofiber dispersions depending on
the supplier and synthetic route. Surfactant or dopant stabilized polyaniline dispersions have
been available for commercial sale since the late 1990s.

13
Chapter 4

Literature Survey

Natta et al (1958) first synthesized polyacetylene as a black powder. This was found to be a
semi-conductor with conductivity between 7 x 10 -11 to 7 x 10-3 Sm-1, depending upon how the
polymer was processed and manipulated. This compound remained a scientific curiosity until
1967, when a postgraduate student of Hideki Shirakawa at the Tokyo Institute of Technology
was attempting to synthesise polyacetylene, and a silvery thin film was produced as a result of a
mistake. It was found that 1000 times too much of the Ziegler-Natta catalyst, Ti (O-n-But)4 -
Et3Al, had been used. When this film was investigated it was found to be semiconducting, with a
similar level of conductivity to the best of the conducting black powders. Further investigations,
initially aimed to produce thin films of graphite, showed that exposure of this form of
polyacetylene to halogens increased its conductivity a billion fold.

Anand et al(1998) explained about the conducting polyaniline blends and its composites through
the various synthesis methods, characterization and its application. It was apparent that the
synthesis methods namely Chemical in situ polymerization, Counter-ion induced processibility,
Emulsion polymerization, Dispersion polymerization, Solution blending, Dry blending and Melt
processing of chemical method, Potentio-static polymerization, Galvanostatic polymerization
and Cyclic voltammetry of electrochemical were made available for the preparation of polymers.
Polyaniline was synthesized easily in both chemically(powered form) and electrochemically(as a
film) and it was stable in heat and air.From the study it was known that polyaniline was the first
commercially available conducting polymer.

Dutta et al(2001) reported dc and ac conductivity of polyaniline (PANI)-polyvinyl alcohol(PVA)

blends from room temperature to 80 K in the frequency range of 1kHz-5MHz.The dc
conductivity was described by the Variable Range Hopping (VRH) model. The large value of
VRH exponent was due to the hopping transport between the super-localized states of polymer.
From the study, it was known that the frequency dependence of conductivity satisfied the ω s
power law. The variation of s with temperature suggested that the ac conduction was due to the
correlated barrier hopping.

Bunz UHF (2000) reviewed the synthesis, properties, structures and applications of Poly arylene
ethylenes. Conjugated polymers were important organic semiconducting materials for
applications in electronic and photonic devices. The review covered the application of polymers
as molecularly wired sensors, polarizers for liquid crystalline (LC) display and light emitting
devices.I t was further noticed that the optical behavior of the polymers contained the aggregates

14
consisting of many polymer chains from the solid state, electronic communication of the π
system via tight packing and a π-π stacking effect.

Zaicheng Sun et al (1997) prepared polyaniline using hydrogen peroxide(H 2O2) as oxidant and
discussed the importance of use of H2O2 as oxidant in chemical polymerization of aniline.
Oxidative polymerization of aniline was carried out in the presence of H 2O2/Fe2+/HCL system.
The prepared PANI showed similar molecular structure compared with polyaniline prepared in
ammonium peroxydisulfate (NH4)2S2O8 system. The mechanism of polymerization of aniline
using H2O2 as oxidant and Fe2+ as catalyst was investigated and came to know that the
polymerization of aniline might be completed at room temperature or lower temperature using
H2O2 and Fe2+ as oxidant and catalyst respectively. The oxidant Fe 2+ was used to increase the
conversion rate of aniline into polyaniline in the system.

Gopal K. Mor et al (2005) describe the use of highly ordered transparent TiO 2 nanotube arrays in
dye-sensitized solar cells (DSCs). After crystallization by an oxygen anneal, the nanotube arrays
are treated with TiCl4 to enhance the photogenerated current and then integrated into the DSC
structure using a commercially available ruthenium-based dye. Voltage-decay measurements
indicate that the highly ordered TiO 2 nanotube arrays, in comparison to nanoparticulate systems,
have superior electron lifetimes and provide excellent pathways for electron percolation. Results
indicate that remarkable photoconversion efficiencies may be obtained, possibly to the ideal limit
of 31% for a single photosystem scheme, with an increase of the nanotube-array length to
several micrometers.
Zhong-Sheng Wang et al (2004) developed high efficiency dye-sensitized solar cells, and
investigated tuning of TiO2 photoelectrode morphology towards optimization of solar energy
conversion efficiency. TiO2 photoelectrodes with six different structures, with layers of
nanoparticles, light-scattering particles, and mixture of nanoparticles and light-scattering
particles on the conducting glass at a desirable sequence and thickness, were designed and
investigated. The data show that the multilayer structure is superior to the mono- and double-
layer structure, with ~85% of incident monochromatic photon-to-electron conversion efficiency
(IPCE) below 620 nm and ~45% of IPCE at 700 nm. The best efficiency of 10.2% under
illumination of simulated AM1.5 solar light (100 mW cm−2) was attained with a multilayer
structure using an anti-reflection film on the cell surface.

Takahashi et al (2003) fabricated a highly efficient solid-state solar cell (TiO 2/dye/CuI) with
improved stability by controlling the pore filling of the porous dyed TiO 2 layer with molten salt
capped CuI crystals and improving the TiO2 by necking with ZnO. The molten salt controls the
CuI crystal growth and acts as a protective coating for CuI nanocrystals, and necking with the
more conductive ZnO improves electrical contact between TiO 2 particles, both contributing to
improved cell performance. Cells achieved efficiency as high as 3.8% with improved stability
under continuous illumination for about 2 weeks.

15
Yamagucghi et al (2005) described the influence of acid pretreatment of TiO 2 mesoporous films
prior to dye sensitization on the performance of dye-sensitized solar cells based on
[(C4H9)4N]3[Ru(Htcterpy)(NCS)3], the so-called black dye. The HCl pretreatment caused an
increase in overall efficiency by 8%, with a major contribution from photocurrent improvement.
It is speculated, from the analysis of incident photon-to-electron conversion efficiency, UV−vis
absorption spectra, redox properties of the dye and TiO 2, and the impedance spectra of the dye-
sensitized solar cells, that photocurrent enhancement is attributed to the increases in electron
injection and/or charge collection efficiency besides the improvement of light harvesting
efficiency upon HCl pretreatment.

16
Chapter 5

Synthesis & Deposition of Aniline

Cross-linking of PVA film

The PVA polymer obtained was required to cross linked. The film was taken in a petridish &
was dipped in 20 ml Acetone, 8 drops of gluteraldehyde & 2 drops of HCl. Acetone was the
medium of the cross linking. Gluteraldehyde was the cross linking agent & was used to maintain
the acidic medium for the cross linking. It was kept for 30 minutes. Then it was cured in hot air
oven for 30 minutes at 40°C.

Use of Surface Active agent

After the crosslinking of PVA polymer pieces, some were directly dipped into the reaction
mixture which is discussed earlier. The second group was at first dipped into a solution of
surface active agent. This was done to increase the deposition of nanoparticles into the polymers.
By use of surfactant, more particles should be adhered to the surface of the polymer. Sodium
dodecyl benzene sulphonate solution was used as surfactant. PVA pieces were dipped in this
solution for l 0 minutes. Then the pieces were introduced in the reaction mixture.

Synthesis of Polyaniline

We have prepared aniline polymer in our laboratory by mixing Aniline hydrochloride with
ammonium persulphate. As the ammonium persulphate might get decomposed so we mix the
aniline hydrochloride with freshly prepared ammonium persulphate.

0.2 M Aniline Hydrochloride & 0.25 M ammonium persulphate

Requirements of Aniline Hydrochloride solution preparation:

1. 30 ml 1(N) HCL solution

2. 0.2(M) Aniline solution

Usually the HCL which we bought from the market has strength of 11(N). X ml of that HCL is
required to make the desired solution.

So. X ml of 11(N) HCL is equivalent to 30 ml of 1 (N) HCL

Therefore, X = 30/11= 2.727 ml

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Molecular weight of Aniline is 93.13 gm/mole

So, 1(M) 1000 ml of Aniline solution needs 93.13 gm

0.2(M) 1000 ml Aniline solution needs (93.13*0.2) gm

0.25(M) 30 ml Aniline solution needs (93.13*0.2*30/1000) gm= 0.558 gm

Now these two solutions are mixed and Aniline hydrochloride is freshly prepared.

Requirements of ammonium persulphate preparation:

30 ml 0.1(M) ammonium persulphate solution

Molecular weight of Aniline is 228.2 gm/mole

So, 1(M) 1000 ml APS solution needs 228.2 gm

0.25(M) 1000 ml Aniline solution needs (228.2*0.25)gm

0.25(M) 30 ml Aniline solution needs (228.2*0.25*30/1000)gm = 1.7115 gm

The volume ratio of APS solution to the aniline hydrochloride solution was kept 1.25, i.e. 30 ml
APS solution were added with 24 ml aniline hydrochloride solution. Then it was kept in ice bath
for 30 minutes.

Observation: Color change of the reaction mixture started about 10 minutes from the starting
time. At first the PANI formed was of blue shade but as the reaction proceeded, emeraldine
green color spread over the reaction mixture, which shows that the emeraldine PANI
nanoparticles were formed. Moreover, a light green shade was imposed on the wall of the
reaction beaker which implies that the particles formed had the very small dimension in the nano
article range.

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Recovery of PANI nanoparticles by filtration

A funnel is fitted with a beaker. A filter paper is folded in a cone shape and is fixed in the mouth
of the funnel. The deep green solution of polyaniline is gradually poured in the funnel. PANI
nanoparticles were deposited on the surface of the filter paper in form of a filter cake.

Washing:

• This cake is washed 2 times with demineralized water to remove unreacted aniline
hydrochloride.
• Another washing is done with acetonitrile to remove the last traces of unreacted
aniline hydrochloride.
• Final washing is done with ethanol to remove the acetonitrile.

The slurry obtained on the surface of the filter paper contains lots of moisture which should be
removed. So the cake is kept for 1 day and is allowed to dry. Idea was to scrap the dry cake of
PANI nanoparticles by using a doctor's knife. But the recovery of the cake from the filter paper
was very difficult and it was not completely recovered by this process.

Soaking the film in APS

Cross linked PVA films were also dipped in APS solution & kept in ice bath for 5 minutes.
Reason for keeping it in ice is that APS might get decomposed in room temperature. The film
was only kept in APS for five minutes rather than keeping overnight because of the same reason
that it might get decomposed. Then aniline hydrochloride was added to with. Initially the film

19
was very light colour. The film was taken out of the reaction mixture & then introduced to
another freshly prepared reaction mixture. It was kept for 30 minutes. This time the film obtained
was uniform green. Moreover, the film was not swollen & the thickness was moderate.

Results

⦁ Recovery of PANI nanoparticles by filtration was a very difficult job. So the particles were not
collected in adequate quantity so that it can be deposited in polymers in anyway. Though the
particles which were collected, were spread over a glass, the glass was at first washed with
surfactant to increase its surface activity. This way, glass containing PANI over it was obtained.
But the resistance of this glass was above 200KΩ. Moreover, the places where we touched the
probe to check its conductivity, lost the particles over it. This implies that the PANI particles
were loosely bound to the surface.

⦁ The PVA film which were soaked in surfactant was better than the other ones. Resistance was
in the range of 30-55KΩ & around 80KΩ on the edges.

⦁The film produced by soaking the film in APS was so far most satisfactory. Dispersion of the
particles were uniform throughout the film. Resistance of the film is 20-22KΩ. Resistance is
almost uniform throughout the film.

Preparation of TiO2 coated glass

We have a solution of Titanium propoxide, a little amount of that solution is taken & coated on
the surface of a coating glass. Now the glass piece is placed on an aluminium crucible and kept
in a furnace at 425˚C for around half an hour. After that we waited for another 15-20 minutes for
cooling and then its resistance is measured by multimeter.

Assembling the Cell

20
A layer of the chlorophyll was added on the surface of the TiO2 coated glass. The PANI was
sandwiched between the TiO2 glass & another glass. The whole assembly was kept together by
crocodile clip. Another crocodile clip was connected with the TiO2 glass & a last one with the
glass that was in contact with the PANI film. This assembly is the actual battery which was the
objective of this project.

Chapter 6

Future scope of work

Among conducting polymers which have emerged as a new class of materials of current research
terest world-wide, polyaniline occupies a prominent place owing to its possible wide spread
plications as compared with other polymers.
1. PANI exists in variety of forms (leucoemeraldine, emeraldine, nigraniline) that differ in
chemical and physical properties. The present work can be enhanced by various ways by
testing with the different forms of PANI.
2. The catalytic activity of PANI towards oxidation and reduction process can be studied.
3. In order to increase conductivity of PANI, metal oxalate complexes which are inorganic
in nature can be used as dopants and their effect on PANI can be studied.
4. PANI can be doped with various lithium salts other than that of LiClO4. These salts can
be LiPF6, LiAsF4, and LiBF4. By doping with these salts PANI can become applicable for
lithium batteries
in the last decade, large progress has been made in improving the power conversion efficiency of
Organic bulk heterojunctions(BHJ) solar cells. Today a single junction organic BHJ with an
efficiency of 10% is listed in the efficiency table of the Journal Progress in Photovoltaics.
Although this progress is impressive, the performance of BHJ has to be improved for larger scale
applications.

21
Considering atypical performance ratio of 0.6 (efficiency of commercial module divided by
record efficiency of single cell) often found for thin film technologies, a commercial BHJ-
module with ~6% efficiency appear economically unattractive to be used in power plants. On the
other hand, for niche applications like solar battery chargers or power supplies for sensors, an
output of 60 W per square meter under full solar radiation could be sufficient. Such an A4 sheet-
sized module would deliver up to 3.75 W, which would allow charging a state-of-the-art cell
phone in about 2 h.
Organic solar cells do have the potential to achieve higher power conversion efficiencies.
Empirical models set an upper limit at ~15% for single junction cells which should be reachable
by optimizing energetic levels, optical and electrical properties of the absorber layers and the
device design (e.g. light management concept for electrodes and substrate). Going beyond 15%
will require overcoming the non-radiative recombination of photo-induced charge carriers which
is the dominant loss process in today's bulk heterojunctions devices. In addition to predominant
radiative charge carrier recombination, materials with a more ordered nano-morphology, better
charge transport properties and less electronic traps will be required for improving BHJ cells.
Increasing the dielectric constant of organic absorber material would be another elegant approach
to increase the performance potential organic solar cells. Ultimately, for > 10 the donor-
acceptor concept could be abandoned as exciton could be split into free charge carriers at room
temperature via thermal activation.
A different approach to achieve power conversion efficiencies >15% with the OPV technology
would be the application of one of the so-called third generation concepts. Among those third
generation concepts a small area organic BHJ-type tandem cell with a certified efficiency of
10.6% has been reported in the progress in photovoltaics. Other high efficiency concepts like hot
carrier cells, multiple electron-hole pairs per photon devices or impurity photovoltaic and
multiband cells have not been investigated extensively in organic absorber layers by now. The
flexibility offered by organic chemistry to design semiconductors and engineer interfaces to
other inorganic or organic materials would offer various opportunities to explore 3rd generation
concepts.
In summary, bulk-heterojunction organic solar cells represent a promising technology which
could be an important player in the future PV-market. Substantial research and development
efforts are required to bring the technology to the necessary performance level.

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