Modern Third Generation Solar Photovoltaic

Technology: Dye Sensitized Solar Cell (DSSC)

Harshal A. Shete Satyajeet N. Shinde Desai

Department of mechanical engineering Department of mechanical engineering
KIT’s College of Engineering KIT’s College of Engineering
Kolhapur, India Kolhapur, India
shete712@gmail.com satyajeetsd17@gmail.com

Abstract: Depleting conventional energy resources are forcing annually 42.5 GWh of electricity assuming present PV cell
the world to search for new and renewable energy resources. Solar efficiency of 15%.
energy is one of the potent and abundant energy resource .To use the
solar energy to its fullest along with conventional technology has
specific limitations. These limitations can be eliminated by use of
Dye Sensitized Solar Cell (DSSC). DSSC can be seen as promising Solar Power Generation
future technology. It is advantageous over Silicon (Si) based
Photovoltaic (PV) cell in terms cost, easy manufacturing, stability at
Capacity[GW] 2013
higher temperature, aesthetics, etc. Also it works in indoor conditions
Germany
i.e. diffused sunlight which nearly not feasible with conventional PV
other 29%
cells. Now Research and Development Departments of many
countries like Japan, Germany, USA, Switzerland, India, China and 44%
many firms like G-Cell, Oxford PV, Sony, TATA-Dyesol are Japan
working on DSSC to improve its various aspects so as to make it 4%
China
more applicable in various conditions. The paper will discuss the India7%
concept, construction, working of DSSC. Also it will illustrate
Italy 2%
current applications of DSSC.
14%

Keywords: Photovoltaic, Dye Sensitized Solar Cell (DSSC),

Silicon (Si) based Photovoltaic (PV) cell, Solar energy.
Germany Japan China India Italy other

I. INTRODUCTION
The earth receives more energy from the Sun in just one hour
than the world's population uses in a whole year. The total solar
energy flux intercepted by the earth on any particular day is
4.2x1018 Watt hours or 1.5x1022 Joules. This is equivalent to
burning 360 billion tons of oil per day. In fact the world's total
energy consumption of all forms in the year 2000 was only
4.24x1020. With about 37.1 GW of solar PV power installed in
2013, world solar PV power capacity increased about 35% to
136.697 GW. In solar power, Germany is leading country in
the world with approximately 40 GW installed capacity almost
half of its total power requirement, Italy 19 GW, China 10 GW,
Japan 5.5 GW. The worlds largest fossil fuel producer Saudi
Arab is also having ambitious plan of 41 GW of solar power by
2032 and UK 22 GW by 2020. [1]
It is known that India is a rarest of the countries rich
with sunlight radiation and offers the best hope to revolutionize
solar energy in the world. It receives about 5000 trillion kWh
of radiation per year. For every square kilometer 50MW of
solar power can be commissioned that can yield average
Fig 1
India's current power requirement is 1102900 GWh as per
Central electricity authority. This means an area of 26000 sq.
Km is required to meet countries annual electricity demand
using solar energy. The area is meagerly 0.82%. Such is the
gravity of sunlight which India receives. Presently the country
has more than 2500 MW of grid connected power plants and
additional 200MW of off grid systems. The national solar
mission targets 20000 MW grid connected solar power and
additional 2000 MW of grid solar by the year 2022. [2]
II. SOLAR ENERGY HARNESSING TECHNOLOGY :
We can harness solar energy in various ways. Solar energy
to thermal energy and solar to electrical. We will discuss solar
to electrical energy conversion. The solar energy can be
directly converted into electricity with the help of photovoltaic
cells. The photovoltaic cells are described below.
 Photovoltaic cells are the devices that convert solar
radiation into electricity. They receive photons and use this
energy of photons to excite electrons and these electrons
gaining energy produces current. There are following broad
categories of PV cells.
A. First Generation Solar Cells
Traditional solar cells are made from silicon, are currently
the most efficient solar cells available for residential use and
account for around 80+ percent of all the solar panels sold
around the world. Generally silicon based solar cells are more
efficient and longer lasting than non Silicon based cells.
However, they are more at risk to lose some of their efficiency
at higher temperatures (hot sunny days), than thin-film Solar
cells. There are currently four types of silicon based cells used
in the production of solar panels for residential use. The types
are based on the type of silicon used, specifically:
 Monocrystalline Silicon Cells
The oldest solar cell technology and still the most popular
and efficient are solar cells made from thin wafers of silicon.
These are called monocrystalline solar cells because the cells
are sliced from large single crystals that have been
painstakingly grown under carefully controlled conditions.
Typically, the cells are a few inches across, and a number of
cells are laid out in a grid to create a panel.
Relative to the other types of cells, they have a higher
efficiency (up to 24.2%), meaning you will obtain more
electricity from a given area of panel. This is useful if you only
have a limited area for mounting your panels, or want to keep
the installation small for aesthetic reasons. However, growing
large crystals of pure silicon is a difficult and very energy-
intensive process, so the production costs for this type of panel
have historically highest of all the solar panel types. Production
methods have improved though, and prices for raw silicon as
well as to build panels from monocrystalline solar cells have
fallen a great deal over the years, partly driven by competition
as other types of panel have been produced. Another issue to
keep in mind about panels made from monocrystalline silicon
cells is that they lose their efficiency as the temperature
increases about 25˚C, so they need to be installed in such a
way as to permit the air to circulate over and under the panels
to improve their efficiency.
 Polycrstalline Silicon Cells
It is cheaper to produce silicon wafers in molds from
multiple silicon crystals rather than from a single crystal as the
conditions for growth do not need to be as tightly controlled. In
this form, a number of interlocking silicon crystals grows
together. Panels based on these cells are cheaper per unit area
than monocrystalline panels - but they are also slightly less
efficient (up to 19.3%).Many of the leading firms make both
monocrystalline and polycrystalline solar cells for their panels.
 Amorphous Silicon Cells
Most solar cells used in calculators and many small
electronic devices are made from amorphous silicon cells.
Instead of growing silicon crystals as is done in making the two
previous types of solar cells, silicon is deposited in a very thin
layer on to a backing substrate such as metal, glass or even
plastic. Sometimes several layers of silicon, doped in slightly
different ways to respond to different wavelengths of light, are
laid on top of one another to improve the efficiency. The
production methods are complex, but less energy intensive than
crystalline panels, and prices have been coming down as panels
are mass-produced using this process. One advantage of using
very thin layers of silicon is that the panels can be made
flexible. The disadvantage of amorphous panels is that they are
much less efficient per unit area (up to 10%) and are generally
not suitable for roof installations you would typically need
nearly double the panel area for the same power output. Having
said that, for a given power rating, they do perform better at
low light levels than crystalline panels - which is worth having
on a dismal winter's day, and are less likely to lose their
efficiency as the temperature climbs. However, there flexibility
makes them an excellent choice for use in making building
integrated PV (e.g., roofing shingles), for use on curved
surfaces, or even attached to a flexible backing sheet so that
they can even be rolled up and used when going camping /
backpacking, or put away when they are not needed.
 Hybrid Silicon Cells
One recent trend in the industry is the emergence of hybrid
silicon cells and several companies are now exploring ways of
combining different materials to make solar cells with better
efficiency, longer life, and at reduced costs. Recently, Sanyo
introduced a hybrid HIT cell whereby a layer of amorphous
silicon is deposited on top of single crystal wafers. The result is
an efficient solar cell that performs well in terms of indirect
light and is much less likely to lose efficiency as the
temperature climbs.
B. Second Generation Solar Cells
Second-generation solar cells are usually called thin-film
solar cells because when compared to crystalline silicon based
cells they are made from layers of semiconductor materials
only a few micrometers thick. The combination of using less
material and lower cost manufacturing processes allow the
manufacturers of solar panels made from this type of
technology to produce and sell panels at a much lower cost.
There are basically three types of solar cells that are considered
in this category, amorphous silicon (mentioned above), and two
that are made from non-silicon materials namely cadmium
telluride (CdTe), and copper indium gallium diselenide
(CIGS). Together they accounted for around 16.8% of the
panels sold in 2009. First Solar, the number one producer and
seller of solar panels in the world currently makes their solar
cells using cadmium telluride. The big appeal of these type of
solar cells is that the are inexpensive (currently below $1.00 /
watt to produce and heading towards $0.70 / watt). However,
as we discuss in the accompanying articles about cadmium
telluride (CdTe) and First Solar there are some concerns about
this technology. Venture capitalists love CIGS solar cells (or at
least used to – as they have invested over $2.3 billion into
companies developing these cells but have yet to see them be a
commercial success) as they have been able to reach efficiency
levels of 20% in the laboratory. Unfortunately it has turned out
to be much more difficult to produce CIGS solar cells in mass
quantities at competitive prices with anywhere near than
efficiency level, so the jury is still out on this technology. New
Recently a Company based in Idaho has come up with a thin-
film monocrystalline solar cell - that uses about 20% of the
crystalline silicon in current silicon based cells and has number
of advantages. To learn more visit our page on Transform
Solar.
 Third Generation Solar Cells
Currently there is a lot of solar research going on in what is
being referred to in the in the industry as Third-generation solar
cells. In fact according to the number of patents filed last year
in the United States solar research ranks second only to
research in the area of fuel cells. This new generation of solar
cells is being made from variety of new materials besides
silicon, including nanotubes, silicon wires, solar inks using
conventional printing press technologies, organic dyes, and
conductive plastics. The goal of course is to improve on the
solar cells already commercially available by making solar
energy more efficient over a wider band of solar energy (e.g.,
including infrared), less expensive so it can be used by more
and more people, and to develop more and different uses.
Currently, most of the work on third generation solar cells is
being done in the laboratory, and being developed by new
companies and for the most part is not commercially available.
[3]
III. DYE SENSITIZED SOLAR CELL (DSSC)
A. Introduction to DSSC
Michael Grätzel and Brian O’Regan invented “Dye-
sensitized solar cells”, also called “Grätzel cells”, in 1991.A
dye-sensitized solar cell (DSSC) 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 photo electrochemical system. The modern
version of a dye solar cell, also known as the Grätzel cell, was
originally co-invented in 1988 by Brian O'Regan and Michael
Grätzel at UC Berkeley and this work was later developed by
the aforementioned scientists at the École Polytechnique
Fédérale de Lausanne until the publication of the first high
efficiency DSSC in 1991. Michael Grätzel has been awarded
the 2010 Millennium Technology Prize for this invention.
B. Principle
Figure in the below illustrates the operation principal of
DSSC. In DSSC, the
separation of electron-hole pair occurs on the surface of
nano particle semiconductor oxide electrode chemically
absorbed with dye molecules. The sunlight is absorbed to
generate electron succession from dye molecule’s HOMO
(Highest Occupied Molecular Orbital) energy lever to LUMO
(Lowest Unoccupied Molecular Orbital) and this electron is
injected to the semiconductor oxide’s conduction band. Here,
the electron injection occurs at a fast pace of femto second to
pico second and the oxidized dye is regenerated within several
nano seconds. On the other hand, the recombination or back
reaction, of which the electron undergoes the surface state to be
lost as electrolyte or absorbed dye molecule, occurs somewhat
slow that most photoelectrons are injected to the
semiconductor’s conduction band to participate in electron
delivery and, hence, to promote the photoelectric energy
conversion efficiency. The injected electron moves to the
conductive film through inter phase between particles of oxide
electrode and creates electric current. Here, dye molecule’s
HOMO is reduced by the electrolyte to complete the operation
process of solar cell. Unlike the semiconductor junction type,
the DSSC is a photoelectric chemical type of solid/liquid
junction. It especially includes oxidation-reduction electrolyte
that is expressed differently from the ideal semiconductor
junction diode based equation.
.
(1)
(2)
The observed lph photoelectric current is determined by the
Iinj electric current which subtracts Ir, the electric current lost
by surface recombination. In other words, Iph ＝ Iinj - Ir and the
open-circuit voltage is expressed in equation (1).
Fig.3
Here, nso is the concentration of electron on TiO2 surface
and kET corresponds to speed constant equation (2) which
combines the electron injected to TiO2 with electrolyte’s
oxidation (or I3 -). The voltage decrease can be prevented when
the speed of reduction from I3 - to I- is slow. The
recombination process passing through technology to regulate
the nano particle’s surface state which is closely related to the
energy conversion efficiency.
C. 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 (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)
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.
One of the efficient DSSCs devices uses ruthenium-
based molecular dye, e.g. [Ru(4,40-dicarboxy-2,20-
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 TiO2 nanoparticles
covered with a 4 μm thick film of much larger (400 nm
diameter) particles that scatter photons back into the
transparent film. Then on this a liquid electrolyte is applied
which is typically I3 . [6]
3. The injected electrons in the conduction band of TiO2 are
transported between TiO2 nanoparticles with diffusion toward
the back contact (TCO). And the electrons finally reach the
counter electrode through the circuit.
4. The oxidized photosensitizer (S+) accepts electrons from
the I− ion redox mediator leading to regeneration of the ground
state (S), and the I− is oxidized to the oxidized state, I3−.
S+ + e− → S (3)
5. The oxidized redox mediator, I3−, diffuses toward the
counter electrode and then it is reduced to I− ions.
I3− + 2 e− → 3 I− (4)
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.
[7]
E. Characteristics Of DSSC
1 Open circuit voltage
A-Si has a relatively high open circuit voltage while the
corresponding MPPT voltage decreases above 1000lux. For the
DSSC module, Voc and Vmpp both increase over the range.

Fig 4

D. Working:
The following primary steps convert photons to current:
1. The incident photon is absorbed by Ru complex
photosensitizers adsorbed on the TiO2 surface.
2. The photosensitizers are excited from the ground state
(S) to the excited state (S∗). The excited electrons are injected
into the conduction band of the TiO2 electrode. This results in
the oxidation of the photosensitized (S+).
S + hν → S∗ (1)
S∗ → S+ + e− (TiO2) (2)
 effects produce an upper limit on the efficiency of
silicon solar cells
 Solar cells require a relatively thick layer of doped
silicon in order to have reasonable photon capture
rates; however silicon processing in terms of growing
crystal is expensive. Thus overall cost increases.
 Purity of Si plays a very important role in efficiency.
 Most of solar energy is not converted into electricity
but absorbed as heat by PV cell. In general a PV cell
absorbs more than 80% of incident energy as heat in
the cell. Hence temperature of cell increases.
 At elevated temperatures the efficiency of PV cell is
affected adversely.
 Solar Si PV are incapable to convert in diffused
sunlight into electricity. So operation of Si PV is
nearly impossible in indoor and cloudy conditions.
Fig 5
 Though PV panels have no considerable maintenance
or operating costs, they are fragile and can be
damaged relatively easily.

B. DSSC as Solution:
2 Absorption Spectrum of dyes  Due to separate and favourable kinetics of electron
ejection, collection, transportation theoretically there
is no bar for efficiency.
 DSSCs use low-cost materials; are simple to
manufacture, and are technically attractive.
 DSSC cell manufactured by using Role To Role
Printing technology. That means all the manufacturing
processes are done at single work station with faster
rate and final DSSC role is produced. This is very cost
effective method.
 Components of DSSC are easily available and there is
no requirement of materials with stringent
specifications.
 DSSCs are normally built with only a thin layer of
conductive plastic on the front layer, allowing them to
radiate away heat much easier without raising
temperature of cell, and therefore operate at lower
internal temperature.
 At elevated temperature working is not affected as
Fig 6 efficiency improves with temperature.

IV. Comparison: DSSC with Si PV Cells

A. Problems with conventional PV cell:

 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-n junction. These

Fig 7
 As a result of these favourable "differential kinetics"
(the reaction rate), DSSCs work even in low-light
conditions, allowing them to work under cloudy skies
and non-direct sunlight when traditional designs
would suffer a "cut out".
Fig 8
 During this day direct sunlight was incident to the
room through a window for around 30 minutes. The
modules did not receive direct light, but did get
indirect benefit from wall reflection. The DSSC
module generated 8.06 mWh (29J) of energy over the
day compared to 3.80mWh (13.6J) from the A-Si
module.
 DSSCs offer flexibility and hence do not get
damaged easily.
 DSSCs can be replacements for existing technologies
in "low density" applications like rooftop solar
collectors, where mechanical reliability and light
weight of the glass-less collector are important
factors.
[8]
C. Disadvantages
• Current efficiency is still relatively low compare with
traditional semiconductor solar cells.
• Dyes will degrade when exposed to ultraviolet
radiation(depending upon dye used) that limits the lifetime and
stability of the cells adding a barrier layer will increase the cost
and may lower the efficiency.
• Generally, DSSC technology uses liquid electrolyte that
has temperature stability problems. At low temperatures, the
electrolyte can freeze, stopping power production and
potentially leading to physical damage. Higher temperatures
cause the liquid to expand, making sealing the panels a serious
problem.
• The electrolyte solution contains volatile organic solvents
and must be carefully sealed. This, along with the fact that the
solvents permeate plastics, precludes large-scale outdoor
application and integration into flexible structures.
• Although the dye is highly efficient at converting
absorbed photons into free electrons in the TiO2, only photons
absorbed by the dye will produce electric current. The rate of
photon absorption depends on the absorption spectrum of the
sensitized TiO2 layer and upon the solar flux spectrum. The
overlap between these two spectra determines the maximum
possible photocurrent. Typically, dye molecules have poorer
absorption in the red part of the spectrum compared to silicon,
which means that fewer of the photons in sunlight can be used
for electrical current generation. These factors limit the current
generated by a DSSC; for example, a traditional silicon-based
solar cell offers about 35 mili-ampere per square centimeter
(mA/cm2), whereas current DSSCs offer about 20 mA/cm2.
[9]
V. Case Study
Basically manufacturing of DSSC is very difficult when it
comes to mass production. Also various issues related to DSSC
are currently in research phase. The firms involved in
manufacturing of DSSC are
1) G-Cell
2) Oxford
3) Dyesol
 Out of this only G-Cell is producing DSSC commercially
on mass production basis.
A. G-Cell :
•The Solar Powered Keyboard Folio for iPad Air 2 &
iPad Air allows users to type with an iPad from the home, the
office or on a daily commute without the need to change
batteries or revert to a mains powered charger. The total cost in
UK is £79.9 (5014 INR)
•The Graetzel solar backpack is a collectable all- weather
bag that is durable, rugged and lightweight. This innovative
design includes a Dye Sensitized Solar Cell (DSSC) that will
power your mobile phone, GPS, iPod or small electronic
device. The solar cell harvests energy from the sun and stores it
in the Power Bank battery (provided) for continuous access to
power. DSSC Specification: Power (Pmax) 0.5W minimum
Operating Current (Imp) 100mA typical Operating Voltage
(Vmp) 5.5V typical (Solar specification @ 1000w/m²) £60.00
(4238 INR)
•GCell sample DSSC module – 1/2 watt module, 200mm x
150mm active aperture Power (Pmax) 0.5W minimum
Operating Current (Imp) 100mA typical Operating Voltage
(Vmp) 5.5V typical (Solar specification @ 1000w/m²) .Its cost
is £50.00 ([3529 INR) [10]
B. Dyesol
Dyesol has developed a complete range of equipment for
production and testing of DSSC devices which ensure optimum
performance and reproducibility. The equipment can be
utilized for both rigid and semi-flexible substrates, and is
available for manual or semi-automatic operation. We provide
proven training procedures, simple and straightforward process
instructions, quality & testing procedures, and easy-to-use
equipment manuals. [11]
C. Oxford PV
Oxford PV is developing a solid state solar cell which is
optimized to drive a paradigm shift in the aesthetics,
performance and cost of Building Integrated Photovoltaic
(BIPV) systems. [12]
D. Sony
Sony has announced conceptual DSSC models that
demonstrate both output advances and intriguing design
possibilities. The models also hint at future lifestyles, with the
potential of one day satisfying electricity needs by generating
our own power.[13]
VI. Scope:
Dye-sensitized solar cells have become an incredible
alternative to solid-state p-n- junction devices. With conversion
efficiencies of over 11% having already been obtained, DSCs
have a bright future in becoming a major contributor to
renewable electricity generation, and with ongoing research,
the efficiencies can only improve. Future research will focus on
improving the short circuit current density by extending the
light response of the sensitizers in the near-infrared spectral
region, and substantial gains are expected from introducing
ordered oxide mesostructures and controlling the interfacial
charge recombination by manipulating the cell on the
molecular level.
VII. Conclusion:
Companies like OxfordPV, Dyesol are well established in
this area of the industry. However, there are problems that
prevent the mass production and wide use of DSSC
technology. DSSCs are still in the early stages of the
development cycle. Efficiency gains are possible and more
widespread studies are underway. These include the use of
quantum dots (small particles of semi-conductor materials) for
conversion of higher-energy (higher frequency) light into
multiple electrons and changing the doping of the TiO2 to
better match it with the electrolyte being used. Replacing the
liquid electrolyte with a solid is an ongoing area 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.
Overall, DSSC technology may not be attractive for
large-scale deployments where higher-efficiency cells are more
viable, although more expensive. But, even small increases in
the DSSC conversion efficiency may make them suitable for
some of these roles.
The dye sensitized solar cell is a brilliant idea because
it applies different mechanisms and has many advantages
compare with traditional semiconductor solar cell. Though it is
far from mature, DSSCs technology will be an important
renewable energy source in future if some technology
breakthroughs are made. It may be possible to use mixed dye to
overcome the band absorption limits of each dye to improve
the overall efficiency.
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