CONTENT

⮚ Introduction

⮚ Dye sensitized solar cells

⮚ Counter electrode metal

⮚ Morphology

⮚ Stoichiometric

⮚ Construction

⮚ Advantage

⮚ Disadvantage

⮚ Conclusion

⮚ Bibliography
 Introduction
A dye-sensitized solar cell (DSSC, DSC, DYSC or Grätzel cell) is a low-cost solar
cell belonging to the group of thin film solar cells. It is based on a
semiconductor formed between a photo-sensitized anode and an
electrolyte, a
photoelectrochemical system. The modern version of a dye solar cell, also
known as the Grätzel cell, was originally co-invented in 1988 by Brian
O’Regan
and Michael Grätzel at UC Berkeley and this work was later developed by
the
aforementioned scientists at the École Polytechnique Fédérale de Lausanne
(EPFL) until the publication of the first high efficiency DSSC in 1991. Michael
Grätzel has been awarded the 2010 Millennium Technology Prize for this
invention.
 Dye-sensitized solar cells

Aim:
To learn the Advantage and Disadvantage about the dye-sensitized solar
cells

Theory:
● 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 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.
Commercial applications, which were held up due to
chemical stability problems,had been forecast in the
European Union Photovoltaic Roadmap to significantly
contribute to renewable electricity generation by 2020.

A dye-sensitized solar cell (DSSC, DSC, DYSC or Grätzel cell) is a low-cost solar
cell belonging to the group of thin film solar cells It is based on
a semiconductor formed between a photo-sensitized anode and
an electrolyte, a photoelectrochemical system. The modern version of a dye
solar cell, also known as the Grätzel cell, was originally co-invented in 1988
by Brian O'Regan and Michael Grätzel at UC Berkeley and this work was later
developed by the aforementioned scientists at the École Polytechnique
Fédérale de Lausanne (EPFL) until the publication of the first high efficiency
DSSC in 1991. Michael Grätzel has been awarded the 2010 Millennium
Technology Prize for this invention

A selection of dye-sensitized solar cells.

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 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. Commercial applications, which were held up due to
chemical stability problems had been forecast in the European Union
Photovoltaic Roadmap to significantly contribute to renewable
electricity generation by 2020.

the late 1960s it was discovered that illuminated organic dyes can generate
electricity at oxide electrodes in electrochemical cells. In an effort to
understand and simulate the primary processes in photosynthesis the
phenomenon was studied at the University of California at Berkeley with
chlorophyll extracted from spinach (bio-mimetic or bionic approach).On the
basis of such experiments electric power generation via the dye sensitization
solar cell (DSSC) principle was demonstrated and discussed in 1972. The
instability of the dye solar cell was identified as a main challenge. Its
efficiency could, during the following two decades, be improved by

optimizing the porosity of the electrode prepared from fine oxide powder,
but the instability remained a problem.

A modern n-type DSSC, the most common type of 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).

The working principle for n-type DSSCs can be summarized into a few basic
steps. Sunlight passes through the transparent electrode into the dye layer
where it can excite electrons that then flow into the conduction band of the
n-type semiconductor, typically titanium dioxide. The electrons from
titanium dioxide then 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, also known
as the counter electrode, and flow into the electrolyte. The electrolyte then
transports the electrons back to the dye molecules and regenerates the
oxidized dye.
The basic working principle above, Is similar in a p-type DSSC, where the dye-
sensitised semiconductor is of p-type nature (typically nickel oxide).
However, instead of injecting an electron into the semiconductor, in a p-type
DSSC, a hole flows from the dye into the valence band of the p-type
semiconductor.

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.

Counter Electrode Materials:

One of the most important components of DSSC is the counter electrode. As
stated before, the counter electrode is responsible for collecting electrons
from the external circuit and introducing them back into the electrolyte to
catalyze the reduction reaction of the redox shuttle, generally I3− to I−. Thus,
it is important for the counter electrode to not only have high electron
conductivity and diffusive ability, but also electrochemical stability, high
catalytic activity and appropriate band structure. The most common counter
electrode material currently used is platinum in DSSCs, but is not sustainable
owing to its high costs and scarce resources. Thus, much research has been
focused towards discovering new hybrid and doped materials that can
replace platinum with comparable or superior electrocatalytic performance.
One such category being widely studied includes chalcogen compounds of
cobalt, nickel, and iron (CCNI), particularly the effects of morphology,
stoichiometry, and synergy on the resulting performance. It has been found
that in addition to the elemental composition of the material, these three
parameters greatly impact the resulting counter electrode efficiency. Of
course, there are a variety of other materials currently being researched,
such as highly mesoporous carbons, tin-based materials,gold nanostructures,
as well as lead-based nanocrystals.However, the following section compiles a
variety of ongoing research efforts specifically relating to CCNI towards
optimizing the DSSC counter electrode performance.

Morphology:
Even with the same composition, morphology of the nanoparticles that make
up the counter electrode play such an integral role in determining the
efficiency of the overall photovoltaic. Because a material’s electrocatalytic
potential is highly dependent on the amount of surface area available to
facilitate the diffusion and reduction of the redox species, numerous
research efforts have been focused towards understanding and optimizing
the morphology of nanostructures for DSSC counter electrodes.

In 2017, Huang et al. utilized various surfactants in a microemulsion-assisted

hydrothermal synthesis of CoSe2/CoSeO3 composite crystals to produce
nanocubes, nanorods, and nanoparticles. Comparison of these three
morphologies revealed that the hybrid composite nanoparticles, due to
having the largest electroactive surface area, had the highest power
conversion efficiency of 9.27%, even higher than its platinum counterpart.
Not only that, the nanoparticle morphology displayed the highest peak
current density and smallest potential gap between the anodic and cathodic
peak potentials, thus implying the best electrocatalytic ability.
With a similar study but a different system, Du et al. in 2017 determined that
the ternary oxide of NiCo2O4 had the greatest power conversion efficiency
and electrocatalytic ability as nanoflowers when compared to nanorods or
nanosheets.Du et al. realized that exploring various growth mechanisms that
help to exploit the larger active surface areas of nanoflowers may provide an
opening for extending DSSC applications to other fields.

Stoichiometry:
Of course, the composition of the material that is used as the counter
electrode is extremely important to creating a working photovoltaic, as the
valence and conduction energy bands must overlap with those of the redox
electrolyte species to allow for efficient electron exchange.

In 2018, Jin et al. prepared ternary nickel cobalt selenide (NixCoySe) films at
various stoichiometric ratios of nickel and cobalt to understand its impact on
the resulting cell performance. Nickel and cobalt bimetallic alloys were
known to have outstanding electron conduction and stability, so optimizing
its stoichiometry would ideally produce a more efficient and stable cell
performance than its singly metallic counterparts. Such is the result that Jin
et al. found, as achieved superior power conversion efficiency (8.61%), lower
charge transfer impedance, and higher electrocatalytic ability than both its
platinum and binary selenide counterparts.

Synergy:

One last area that has been actively studied is the synergy of different
materials in promoting superior electroactive performance. Whether through
various charge transport material, electrochemical species, or morphologies,
exploiting the synergetic relationship between different materials has paved
the way for even newer counter electrode materials.
In 2016, Lu et al. mixed nickel cobalt sulfide microparticles with reduced
graphene oxide (rGO) nanoflakes to create the counter electrode.Lu et al.
discovered not only that the rGO acted as a co-catalyst in accelerating the
triiodide reduction, but also that the microparticles and had a synergistic
interaction that decreased the charge transfer resistance of the overall
system. Although the efficiency of this system was slightly lower than its
platinum analog (efficiency of NCS/rGO system: 8.96%; efficiency of Pt
system: 9.11%), it provided a platform on which further research can be
conducted.

Construction:

In the case of the original Grätzel and O’Regan design, 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 , which forms into a highly
porous structure with an extremely high surface area. The is chemically
bound by a process called sintering. 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-polypyridyl dye (also called molecular
sensitizersnand 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 . The bond is
either an ester, chelating, or bidentate bridging linkage.

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. , for instance, is already
widely used as a paint base.
One of the efficient DSSCs devices uses ruthenium-based molecular dye, e.g.
[Ru(4,4’-dicarboxy-2,2’-bipyridine)2(NCS)2] (N3), that is bound to a
photoanode via carboxylate moieties. The photoanode consists of 12 μm
thick film of transparent 10–20 nm diameter nanoparticles covered with a 4
μm thick film of much larger (400 nm diameter) particles that scatter photons
back into the transparent film. The excited dye rapidly injects an electron
into the TiO2 after light absorption. The injected electron diffuses through
the sintered particle network to be collected at the front side transparent
conducting oxide (TCO) electrode, while the dye is regenerated via reduction
by a redox shuttle, I3−/I−, dissolved in a solution. Diffusion of the oxidized
form of the shuttle to the counter electrode completes the circuit.

Mechanism of DSSCs:
The following steps convert in a conventional n-type DSSC photons (light) to
current:
The incident photon is absorbed by the photosensitizer (eg. Ru complex)
adsorbed on the surface.
The photosensitizers are excited from the ground state (S) to the excited
state (S∗). The excited electrons are injected into the conduction band of the
TiO2 electrode. This results in the oxidation of the photosensitizer (S+).
The injected electrons in the conduction band are transported between TiO2
nanoparticles with diffusion toward the back contact (TCO). And the
electrons finally reach the counter electrode through the circuit.
The oxidized photosensitizer (S+) accepts electrons from the redox mediator,
typically I− ion redox mediator, leading to regeneration of the ground state
(S), and two I—Ions are oxidized to elementary Iodine which reacts with I− to
the oxidized state, I3−.

The oxidized redox mediator, I3−, diffuses toward the counter electrode and
then it is reduced to I− ions.
The efficiency of a DSSC depends on four energy levels of the component: the
excited state (approximately LUMO) and the ground state (HOMO) of the
photosensitizer, the Fermi level of the TiO2 electrode and the redox potential
of the mediator (I−/I3−) in the electrolyte.

Nanoplant-like morphology:

In DSSC, electrodes consisted of sintered semiconducting nanoparticles,

mainly TiO2 or ZnO. These nanoparticle DSSCs rely on trap-limited diffusion
through the semiconductor nanoparticles for the electron transport. This
limits the device efficiency since it is a slow transport mechanism.
Recombination is more likely to occur at longer wavelengths of radiation.
Moreover, sintering of nanoparticles requires a high temperature of about
450 °C, which restricts the fabrication of these cells to robust, rigid solid
substrates. It has been proven that there is an increase in the efficiency of
DSSC, if the sintered nanoparticle electrode is replaced by a specially
designed electrode possessing an exotic ‘nanoplant-like’ morphology.

Operation:
In a conventional n-type DSSC, sunlight enters the cell through the
transparent SnO2: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.

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.

Advantages:
DSSCs are currently the most efficient third-generation[33] (2005 Basic
Research Solar Energy Utilization 16) solar technology available. Other thin-
film technologies are typically between 5% and 13%, and traditional low-cost
commercial silicon panels operate between 14% and 17%. This makes DSSCs
attractive as a replacement for existing technologies in “low density”
applications like rooftop solar collectors, where the mechanical robustness
and light weight of the glass-less collector is a major advantage. They may
not be as attractive for large-scale deployments where higher-cost higher-
efficiency cells are more viable, but even small increases in the DSSC
conversion efficiency might make them suitable for some of these roles as
well.

There is another area where DSSCs are particularly attractive. The process of
injecting an electron directly into the TiO2 is qualitatively different from that
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) which does not result in current being generated.
Although this particular case may not be common, it is fairly easy for an
electron generated by another atom to combine with a hole left behind in a
previous photoexcitation.

In comparison, the injection process used in the DSSC does not introduce a
hole in the TiO2, only an extra electron. Although it is energetically possible
for the electron to recombine back into the dye, the rate at which this occurs
is quite slow compared to the rate that the dye regains an electron from the
surrounding electrolyte. Recombination directly from the TiO2 to species in
the electrolyte is also possible although, again, for optimized devices this
reaction is rather slow.[34] 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 which DSSCs share with most thin-film technologies, is

that the cell’s mechanical robustness indirectly leads to higher efficiencies at
higher temperatures. In any semiconductor, increasing temperature will
promote some electrons into the conduction band “mechanically”. The
fragility of traditional silicon cells requires them to be protected from the
elements, typically by encasing them in a glass box similar to a greenhouse,
with a metal backing for strength. Such systems suffer noticeable decreases
in efficiency as the cells heat up internally. DSSCs are normally built with only
a thin layer of conductive plastic on the front layer, allowing them to radiate
away heat much easier, and therefore operate at lower internal
temperatures.
Disadvantages:
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, halting power production and potentially leading
to physical damage. Higher temperatures cause the liquid to expand, making
sealing the panels a serious problem. Another disadvantage is that costly
ruthenium (dye), platinum (catalyst) and conducting glass or plastic (contact)
are needed to produce a DSSC. A third major drawback is that the electrolyte
solution contains volatile organic compounds (or VOC’s), solvents which must
be carefully sealed as they are hazardous to human health and the
environment. This, along with the fact that the solvents permeate plastics,
has precluded large-scale outdoor application and integration into flexible
structure.

Replacing the liquid electrolyte with a solid has been a major ongoing field of
research. Recent experiments using solidified melted salts have shown some
promise, but currently suffer from higher degradation during continued
operation, and are not flexible.
 Conclusion
Researchers have investigated the role of surface plasmon
resonances present on gold nanorods in the performance of
dye-sensitized solar cells. They found that with an increase
nanorod concentration, the light absorption grew linearly;
however, charge extraction was also dependent on the
concentration. With an optimized concentration, they found
that the overall power conversion efficiency improved from
5.31 to 8.86% for Y123 dye-sensitized solar cells.

The synthesis of one-dimensional TiO2 nanostructures

directly on fluorine-doped tin oxide glass substrates was
successful demonstrated via a two-stop solvothermal
reaction Additionally, through a TiO2 sol treatment, the
performance of the dual TiO2 nanowire cells was enhanced,
reaching a power conversion efficiency of 7.65%.

Stainless steel based counter-electrodes for DSSCs have

been reported which further reduce cost compared to
conventional platinum based counter electrode and are
suitable for outdoor application.
Researchers from EPFL have advanced the DSSCs based on
copper complexes redox electrolytes, which have achieved
13.1% efficiency under standard AM1.5G, 100 mW/cm2
conditions and record 32% efficiency under 1000 lux of
indoor light.

Researchers from Uppsala University have used n-type

semiconductors instead of redox electrolyte to fabricate
solid state p-type dye sensitized solar cells

Bibliography :
● Chemistry 12th text book
● https://en.m.wikipedia.org/wiki/Dye-
sensitized_solar_cell