Review: Dye sensitised solar cells

T. V. Arjunan1 and T. S. Senthil*2

Solar energy can be harvested either by deriving directly from sunlight or by indirect methods. A
variety of technologies have been developed to harness solar energy. Among them, utilisation of
solar energy by solar cell is an important and effective method and has a high potential in the
commercial market. Based on the techniques and materials used to fabricate solar cell, the solar
cells are classified into three generations. First generation solar cells are the larger, silicon based
photovoltaic cells. The disadvantages of these solar cells are limited availability of silicon, requires
expensive manufacturing technologies and higher energy photons are wasted as heat. The second
generation solar cells are called thin film solar cells, which are significantly cheaper than previous
generation cells but have lower efficiencies. The third generation solar cells are still in the research
phase, but the results are promising and encouraging. Generally, third generation cells include
nanocrystalline solar cells and dye sensitised solar cells, they do not have the pn junction as in
traditional solar cells. Third generation solar cells provide a technically and economically credible
alternative concept to present day pn junction solar cells. In the present study, the technology of
the dye sensitised solar cell is introduced with a short description about the operating principle of
the cell. After this, a more detailed study is carried out about the dye sensitised solar cell, taking into
account the key steps involved in photovoltaic energy conversion and also the other important
fundamental operational aspects of the solar cell physics and chemistry.
Keywords: Solar energy conversion, Silicon solar cell, Thin film solar cell, Dye sensitised solar cell

This paper is part of a special issue on Solar Energy

Introduction
Energy is the major factor in the development of
mankind. A nation that generates energy more than
muscular power can only attain a high level of industrial
and agricultural growth. National income is directly
proportional to the energy conserved by the nation.
Modern civilisation is completely dependent on cheap
and abundant energy. The economic wealth and the
material standards of living of a country are determined
by the technologies and fuels that are available.
There is a time for necessary research before our fuel
supplies are exhausted. Therefore, other systems based
on non-conventional and renewable sources are being
tried by many countries. They are as follows:
(i) marine energy
(ii) nuclear energy
(iii) solar energy, bio energy, wind energy, etc.
Conventional energy sources are in limited reservoir and
may be exhausted by the end of this century or the
beginning of next century. Nuclear energy poses safety
problems with regard to radioactivity leakage and
1

Department of Mechanical Engineering, Coimbatore Institute of

Engineering & Technology, Coimbatore, India
Department of Physics, Erode Sengunthar Engineering College, Erode,
India

*Corresponding author, email tssenthi@gmail.com

2013 W. S. Maney & Son Ltd.

Received 26 March 2012; accepted 26 July 2012
DOI 10.1179/1753555712Y.0000000040

disposal of nuclear ash. Among them, solar energy is

the major source of power because all life on earth
depends on the Sun. The Sun is a primary source of
energy, and all forms of energy on earth are derived
from it. Solar energy alone has the potential to fulfil all
the green energy demands of the next generation. Solar
energy with its endless origin and it being free from
pollution and not a safety hazard may be the answer to
the energy problems of the coming centuries.
Solar energy has the greatest potential of all the
sources of renewable energy, as only a small amount of
this form of energy could be used, especially when other
sources (coal, oil or gas) in the country have depleted.
Solar energy can be harvested either by deriving directly
from sunlight or by indirect methods. Directly, solar
energy can be obtained by
(i) solar thermal technology
(ii) photovoltaic energy conversion
(iii) solar hydrogen gas production technology.
The field of photovoltaics is of major importance among
renewable energy sources, since the first report about
direct conversion of solar energy into electricity with 6%
efficiency has been attracted by all the researchers.
However, first generation silicon solar cells hinder the
growth of production volume and module price because
of the limited availability of solar grade silicon.
A very promising alternative to classical, inorganic p
n junction solar cells is the concept of nanoporous, dye

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Dye sensitised solar cells

1 Energy band diagram of pn junction solar cell

sensitised solar cells (DSSCs), which were introduced by

ORegan and Gratzel in 1991.1 Those cells exhibit
impressive white light energy efficiencies of up to 12%
even if they are based on cheap starting materials and
simple techniques.2

Inorganic solar cell

Single crystalline silicon solar cell was developed using
the pn junction with an energy conversion efficiency of
6%.3 The efficiency was gradually increased, and current
state of the art laboratory scale single junction crystalline Si solar cell converts 24% of the incident solar light
into electric energy, a value close to the thermodynamical upper limit of 30%.4 A typical silicon solar cell is a p
n junction formed on a few hundred micrometre thick
(300500 mm) p type silicon wafer. By diffusing an n
type dopant, usually phosphors, onto the p type wafer,
the thin emitter layer is created. The diffusion of holes to
the n region and electrons to the p region causes nonequilibrium, which generates the space charge region
between the p and n type semiconductors, as shown in
Fig. 1. When the incident photons have an energy
greater than semiconductor band gap (hn.Eg), it creates
the electronhole pairs. The asymmetry in the device
structure facilitates the flow of electrons towards the n
type region while holes are collected at the p type region.
As the electrons and holes exist in a same bulk volume,
photovoltaic performance of the device is sensitive to
bulk properties of the materials. For efficient carrier
collection, a defect free semiconductor is very important,
but this makes solar cell more expensive.

Organic solar cell

In recent years, organic solar cells have received more
interest due to its potential applications like being
environmentally safe and economically viable. The high
optical absorption coefficient of organic semiconductors
offers the possibility of absorbing most of the incident
solar light by a few hundred nanometre thick active
layers. Hence, they have a potential for transparent,
lightweight and flexible applications.
The schematic structure of organic solar cell is shown
in Fig. 2. A bilayer of sequentially stacked donor and
acceptor material is sandwiched between two contacts:
transparent conductive oxide based front electrode and
metal back electrode. When the light is incident on the
device, absorption of a photon by donor material leads
to the formation of exciton (electronhole pair). Photo
generated excitons diffuse towards the donoracceptor

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2 Schematic layout of organic solar cell

interface and disassociate into free charge carriers; the

electrons are then accepted by the large electron affinity
material (acceptor), and holes are collected in the donor
phase.
Since the typical diffusion of excitons in organic
semiconductors and conductive polymers is around 10
20 nm, excitons generated in the vicinity of the donor/
acceptor interface only contribute to the photocurrent.
On the other hand, excitons generated far away from
the interface decay via radiative pathways. Therefore,
energy conversion efficiency of the bilayer device is
primarily limited by light absorption in the vicinity
(,10 nm) of donor/acceptor interface. The reported
maximum energy conversion efficiency of the bilayer
device stands ,1%.5
The performance of organic solar cell was achieved by
introducing the bulk heterojunction (BHJ) concept. The
BHJ concept is used to provide the donor/acceptor
interface within the range of exciton diffusion length.
Owing to this, the majority of the excitons can yield free
charge carriers. This can be achieved through the blend
of donoracceptor material. By carefully tailoring the
length scale of the blend (equivalent to the diffusion
length of exciton), most of the excitons can reach the
interface and dissociate into free electron and holes.
Provided that there is a continuous network between the
interface and the respective electrodes, photovoltaic
performance of the device is remarkably improved.
Although various combinations of donor and acceptor
materials were used to fabricate BHJ solar cells,
polymerfullerene blend based devices show promising
potential with ,5% solar to electric energy conversion
efficiency.6

Dye sensitised solar cells

Gratzel and his co-workers developed a solar cell by
combining nanostructured electrodes and efficient
charge injection dyes with energy conversion efficiency
exceeding 7% in 19911 and 10% in 1993.7 This solar cell
is called dye sensitised nanostructured solar cell or the
Gratzel cell after its inventor.
Dye sensitised solar cell is basically a type of BHJ
solar cell. The working of the DSSC is entirely different

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4 Charge carrier generation and transport in nanocrystalline TiO2 network

3 Schematic representation of nanocrystalline DSSC

from organic solar cells with respect to charge carrier

generation and transport mechanism. Figure 3 shows
the schematic diagram of DSSC. Wide band gap
semiconductor (TiO2) with an extremely high surface
area acts as a photo anode. TiO2 absorbs only a small
fraction of the solar photons (those in the UV), but it is
much easier to adjust the absorbance spectra compared
with silicon solar cell.8
By sensitising dye molecules with wide band gap
semiconductor, two fundamental processes take place:
photon absorption and carrier transport are separated
from each other. Therefore, the bulk properties of the
semiconductor exhibit less influence on the device
performance, and thus, the device made up of low grade
material exhibits reasonable efficiency.1
The main objective of this study is to update the
developments in solar cells and detail the study on
DSSCs.

Operating principle
In DSSCs, a porous network of nanocrystalline TiO2
particles formed on transparent conductive oxide substrate serves as a base (working electrode). The sensitiser
[semiconductor quantum dot (QD)/natural dye] is
chemically adsorbed on the TiO2 network and acts as
a light absorber. When the DSSC is placed in the
sunlight, photons in the sunlight can strike the working
electrode, and it gives more energy and produces photo
excitation. Absorption of photons with an energy higher
than the band gap results in the generation of excitons
that interact via columbic forces. Excitons recombine
after a certain time under emission of photons or heat,
unless they are separated by an electric field. Therefore,
only excitons created in the space charge layer or close
to it will contribute to the photocurrent. The absorption
of light by a monolayer of dye is always weak, due to the
very small cross-section for light absorption of the dye

molecules compared to the area they occupied on the

surface. A respectable photovoltaic efficiency cannot
therefore be obtained using a flat semiconductor surface
but rather using a porous, nanostructured film of very
high surface roughness. When light penetrates the photo
sensitised semiconductor sponge, it crosses hundreds of
absorbed dye monolayers. The nanocrystalline structure
equally allows a certain spreading of the radiation. The
final result is a greater absorption of light and its
efficient conversion into electricity. Recombination
between the injected electron in the conduction band
of the semiconductor and the hole on the oxidised dye
is indeed very slow compared to the reduction in the
latter by the redox mediator in solution. Moreover,
the electronhole recombination in the semiconductor,
which is not favourable for the efficiency of the classical
photovoltaic cells, does not exist here, because no hole in
the valence band corresponds to the electron in the
conduction band. Upon excitation, the dye injects
electrons from the photo excited dye into the conduction
band of the titanium oxide. The photo induced electrons
diffuse through the porous TiO2 network and are
extracted at the ITO substrate. The holes move towards
the counter electrode. The dye itself is regenerated by
the electrolyte containing the redox pair I{ =I{
3 . The
electronic circuit is closed by the reduction in the iodide
couple at the platinised ITO counter electrode.
The dye sensitised light to electron conversion process
differs fundamentally from the one in the conventional
solar cells. In DSSC, excitons are generated right at the
hetro interface between the dye attached semiconductor
particle and the redox electrolyte. The ultra fast injection
of electrons and the lack of exciton diffusion into the
TiO2 conduction band make DSSC more efficient than
any other excitonic solar cell.9 Figure 4 shows the charge
generation and transport in dye modified nanocrystalline TiO2 network. The nanocrystalline TiO2 network
acts as a supporting media for dye molecule as well as
a conductive path way between the site of electron
injection (TiO2/dye) and collection (ITO/TiO2). The
transport of electrons produces charge imbalance and
creates the electric field, which in turn drags the cations
in the electrolyte.

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Oxidation and reduction in redox couple

The photovoltaic performance of DSSC depends on the
properties of redox electrolyte available to regenerate
the dye molecule following the ultra fast electron
injection. The electron transfer of the redox system
must be fast enough at counter electrode and very slow
at the working electrode side. Compared with other
electrolytes I{ =I{
3 shows best efficiency; this is due to
the slow electron transfer process from the TiO2 to I{
3
ions in the electrolyte and rapid generation of I2 from
I{
3 at counter electrode.
The reduction in I{
3 ions at counter electrode is
{
{
I{
3 z2e '3I

Fluorine doped tin oxide and indium tin oxide are the
mostly used conducing substrates in DSSC. These
conducing substrates exhibit very slow electron transfer
kinetics in electrolytes, and they produce large charge
transfer resistance at conducing substrate/redox electrolyte interface.10 It causes the internal resistance of the
solar cell and appears as voltage loss. In order to minimise
such losses, the conducting substrate is modified by
means of Pt coating and used to catalyse the I{
3 reduction
reaction at counter electrodes.
Iodide ions present in the electrolyte diffuse towards
the electrode and adsorbed on the unoccupied surface
state of Pt; release the electron and thus become
molecular iodine I(Pt). The desorption of intermediate
products from the Pt surface leads to the formation of I2,
which subsequently react with iodide and become I{
3 ions
I{ zPt'I{ (Pt)
I{ (Pt)'I(Pt)ze{
I(Pt)zI(Pt)'I2 z2Pt
I2 zI{ 'I{
3
To catalyse the I{
3 reduction for the maximum performance of DSSC, a few nanometre thick Pt layer is
sufficient. By decomposing platinum (II) chloride solution, Pt nanoclusters were formed on conducting
substrate.
The operating cycle can be summarised in chemical
reaction terminology as11
Anode : Szhn?S  absorption
S  ?S z ze{ (TiO2 ) electron injection
2S z z3I{ ?2SzI{
3 regeneration
{
{
Cathode : I{
3 z2e (Pt)?3I

Cell : e{ (Pt)zhn?e{ (TiO2 )

Important drawbacks of the DSSC are the volatility of
the electrolyte and the corrosive action of the iodide
redox couple. Correspondingly, long term application of
DSSC is limited by the electrolyte permeability of the
encapsulation and its inertness towards the iodine. A lot
of effort has therefore been invested in finding less volatile
electrolytes while maintaining sufficient hole transport.
Approaches to replace the liquid electrolyte include

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application of ionic conducting polymer gels,12,13 electrolyte gellated with amino acid derivatives14 or room
temperature molten salts.15

Sensitisers
Dye sensitised solar cells fabricated from nanocrystalline
TiO2 particles sensitised with commercially available
ruthenium based dyes made a significance in the energy
conversion efficiency of the solar cells from ,1 to 11%.
Owing to the high cost of ruthenium complexes and the
scarce availability of these noble metals, an investigation
on low cost, readily available dyes as efficient sensitisers
(both semiconductor QDs and naturally available
organic dyes) for DSSCs has been expedited but still
remains a scientific challenge.16
These dyes/QDs are very attractive because of its
abundant availability and simple processing methods.
However the energy conversion efficiency of the QD/
natural dye sensitised based DSSC is always less than that
of ruthenium based dyes. This is due to the less absorbing
area present in the nanocrystalline TiO2 thin films; it was
increased by doing some surface modifications. To
produce high efficiency DSSC, it is very important to
know about the various pigments present in the natural
dyes and suitable QDs in detail.

Natural dyes
While the high efficiency of the DSSC arises from a
collective effect of numerous well tuned physical
chemical nanoscale properties, which will become apparent later, the key issue is the principle of dye sensitisation
of large band cap semiconductor electrodes. As already
mentioned, in the DSSC, this is accomplished by coating
the internal surfaces of the porous TiO2 electrode with
special dye molecules tuned to absorb the incoming
photons. There are a large number of natural dyes
available; among them, three dyes can be considered as
the backbone of currently applied sensitisers in DSSC.
Natural dyes extracted from fruits, flowers and leaves
of plants have several advantages over rare metal
complexes and other organic dyes. The natural dyes
are readily available, easy to extract, no need of further
purification, environment friendly and of less cost. All
over the world, there are several research groups
working to utilise the natural dyes as sensitisers in
DSSCs.17 Natural pigments, including chlorophyll,18
carotenoids,19 anthocyanin,20 nasunin21 and crocetin16
are freely available in plant leaves, flowers and fruits and
have the potential to be used as sensitisers. Among
these, anthocyanins are a group of naturally occurring
phenolic compounds responsible for the colour of many
flowers, fruits leaves, stems, roots and vegetables. The
most common anthocyanidins (Fig. 5a) found in flowers
and fruits are cyanidin (orange red), delphinidin (blue
red), malvidin (blue red), pelargonidin (orange), peonidin (orange red) and petunidin (blue red).22
The hydroxyl groups present in anthocyanidins chelating with TiO2 are shown in Fig 5b. Delonix regia used in
the present study is having anthocyanin as cyanidin 3-Oglucoside23 and Eugenia jambolana has anthocyanins (as
cyanidin-3-glucoside equivalents), which occur as diglucosides of five anthocyanidins/aglycons: delphinidin,
cyanidin, petunidin, peonidin and malvidin.24,25 The
structure of the cyanidin 3-O-glucoside is shown in the

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helps in electron transfer from the anthocyanin molecule

to the conduction band of TiO2.
Organic dyes in DSSC are attractive because they are
relatively cheap and can have high extinction coefficients.
Organic structures that have been popular include
anthocyanins, porphyrins and phthalocyanines. These
molecules with good photocurrents were difficult to
obtain due to absorbance in wrong parts of the spectrum
and aggregation respectively. However, recently, a
porphyrin dye reached an efficiency of 7?1%.26 There
have been other organic dyes that reach high efficiencies
(69%) such as coumarin and cyanine dyes, which have
donor and acceptor parts.
Natural dye sensitised TiO2 solar cells have been
observed to exhibit an efficiency of 7?1% with high
stability.21 Efficiency .8?0% has been obtained using
similar synthetic organic dyes.27 Because of the simple
preparation technique, ease of availability and cheap
cost, natural dye is found to emerge as an alternative
potential photosensitiser for DSSCs. The efficiency of
the cell is found to depend strongly on parameters like
the absorption spectrum of the dye and anchoring of the
dye to the surface of TiO2. Many researchers have
studied about the usefulness of natural dyes as
sensitisers for DSSC applications.28

Semiconductor QDs

5 a basic chemical structure of anthocyanidins, b hydroxyl groups present in anthocyanidins chelating with
TiO2 and c structure of cyanidin 3-O-glucoside

Fig. 5c. The other important anthocyanidins and their

substitutions are given in Table 1. The carbonyl and
hydroxyl groups present in the anthocyanin molecule can
attach itself to the surface of a porous TiO2 film. This

Table 1 Selected anthocyanidins and their substitutions

Anthocyanidin R1

R2

R3

R4

R5

R6 R7

Cyanidin
Delphinidin
Malvidin
Peonidin
Petunidin

OH
OH
OH
OH
OH

H
OH
OCH3
H
OCH3

OH
OH
OH
OH
OH

OH
OH
OH
OH
OH

H
H
H
H
H

OH
OH
OCH3
OCH3
OH

OH
OH
OH
OH
OH

Similar to organic dye molecules, a new development so

called semiconductor QDs can be used as sensitisers to
extend the photo response of the TiO2 electrode into the
visible region.28 However, using organic dye sensitiser has
some problems. It is well known that organic dyes
deteriorate easily due to the oxidation on the surface of
semiconductor electrodes under irradiation. An alternate
strategy to improve the DSSCs stability is replacing the
organic dye sensitiser by inorganic semiconductor QDs.29
The use of inorganic semiconductor QDs as sensitisers
has received more attention in recent years because of
their interesting properties like the shift of excitonic
peak to higher energy,30 blue shift in absorption band
edge31 and below picosecond radiative rates of optical
transitions.32 Owing to the quantum confinement effect,
the band gap and optical properties of QD can be
adjusted by changing the size of the QDs.33 Another
advantage of using QD is that they generate hot electrons
or multiple electronhole pairs (excitons) with one single
photon through the impact ionisation effect.34 Compared
with conventional dyes, the semiconductor QDs have
high extinction coefficient, which reduces the dark current
and increases the overall efficiency of the solar cell. Since
the semiconductor QDs are composed of crystalline
semiconductor, the dots should be inherently more stable
than dyes. This technology may be important for solid
state cells, as a liquid electrolyte would lead to corrosion
of the semiconductor nanoparticles.28
Among the various semiconductor QDs, CdS is one of
the most studied semiconductor because it is a promising
material for applications in fast optoelectronic devices
and has a suitable band gap energy of 2?42 eV at room
temperature, which corresponds to the intrinsic absorption at 512 nm, the most intensive area of solar
spectrum.35,36 The energy conversion efficiency of a
QD sensitised solar cell is ,2%.37 The reason for the low
efficiency is the problems associated with the assembly
of QDs into the nanocrystalline TiO2 film. The properties of CdS QD sensitised TiO2 electrodes are closely

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related to the CdS particle preparing process and the

adsorption way of CdS QDs to electrodes.38

Conclusions
Nanocrystalline DSSC has become a validated and
credible competitor to solid state junction devices for the
conversion of solar energy into electricity. These solar
cells are the prototype of a series of optoelectronic
devices using the specific characteristics of innovative
structure for oxide films. The conversion efficiency
depends on the sensitisers, so the recent developments
in this lead to dyes that absorb across the visible
spectrum leading to higher efficiencies. This review
clearly shows that the DSSCs only hold additional
potential for further cost reduction and simplification of
the manufacturing of solar cells, and also, they are
alternate for all solid state heterojunction solar cells.

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