DYE SENSITIZED SOLAR

CELLS

Dileep V Raj

Mtech Renewable Energy Technologies

Amrita Vishwa Vidyapeetham,Coimbatore

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 What’s Solar Energy?

• Solar energy Originates with the thermonuclear fusion

reactions occurring in the sun.
• Represents the entire electromagnetic radiation (visible light,
infrared, ultraviolet, x-rays, and radio waves).
• This energy consists of radiant light and heat energy from
the sun.
• Out of all energy emitted by sun only a small fraction of
energy is absorbed by the earth.
• Just this tiny fraction of the sun’s energy is enough to meet
all our power needs.

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• Energy produced Photovoltaic (solar)
panel
by the sun
• Clean, renewable
source of energy
• Harnessed by solar
collection methods
such as solar cells
• Converted into
usable energy such
as electricity Set of solar panels
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 What is a Photovoltaic Cell

• A device that can convert sunlight directly in

electricity.

• Traditional types are based on two types of silicon

sandwiched together (n-type and p-type).

• Based on using photons to separate charges:

electron-hole pairs

• Many new types are in research/production stage.

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Solar cell: Solar cell is a photovoltaic device that converts
the light energy into electrical energy based on
the principles of photovoltaic effect

Recap : Photo means light in Greek and Volt is the name of a

pioneer in the study of electricity Alessandro Volta

Albert Einstein was awarded the 1921 Nobel Prize in physics

for his research on the photoelectric effect—a phenomenon
central to the generation of electricity through solar cells.

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 Solar Panel Use Today
• Large companies like
Google, Walmart, and
Microsoft use solar
energy to partially power
some of their facilities

Solar panels being tested

on Walmart store
Solar panels on Microsoft building 6
• Renewable energy sources such as solar energy are
considered as a feasible alternative because
“More energy from sunlight strikes Earth in 1 hour than all
of the energy consumed by humans in an entire
year.”(Lewis, 2007).

• The use of natural dye extracts provides natural, non toxic

and low cost dye sources with high absorbance level of
UV, visible and near IR.

• Examples of such dye sources are Bahraini Henna

(Lawsonia inermis L.) and Bahraini raspberries (Rubus spp.).
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 Disadvantages of Conventional Solar
cells
o Inefficient and costly equipment
o Environmental Impact of PV Cell Production
o Initial cost is very high
o Requires expert hand and equipment in
manufacture

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 Semiconductor Solar DSSC
Cells

Transparency Opaque Transparent

Environment(Material& Normal Great

Process)

Power Generation cost High Low

Power Generation High Normal

efficiency

Color Limited Various

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 What is a DSSC?

A dye sensitized solar cell is a new kind of

relatively low cost solar cell with great
potential as its materials are considerably
cheaper and it is simple to make.

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 Past
• Michael Grätzel and Brian O’Regan invented “Dye-
sensitized solar cells”, also called “Grätzel cells”, in
2005.
• The first cells were only capable of using light at the
Ultraviolet and Blue end of the spectrum.
• By the turn of the century, advances in technology
were able to broaden the frequencies in which these
cells were able to respond.
• The most efficient of the dyes were simply known as
“Black dyes” due to their very dark colors.
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 So What Does this Mean for Solar Cells?
• In dye-sensitized solar cells…
– Talk about highest occupied
molecular orbital (HOMO) and
lowest unoccupied molecular
orbital (LUMO)

• In single-crystal silicon solar

cells…
– Talk about “conduction
band” (excited states) and
“valence band” (ground
states)
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 How does a DSSC function?
A DSSC functions due to the interactions
between the cell's anode and the cathode,
and the nanoparticles of titanium oxide,
coated with light sensitive dye and
surrounded by electrolyte.

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 Components Of DSSC
• Transparent conducting and counter conducting
electrodes
• The nanostructured wide band gap
semiconducting layer
• The dye molecules (sensitizer)
• The electrolyte.

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 Schematic of the structure of the dye sensitized solar cell.

Dye Sensitized Solar Cells - Working Principles, 15

Challenges and Opportunities Khalil Ebrahim Jasim Department of Physics, University of Bahrain Kingdom of Bahrain
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1. Transparent substrate for both the conducting
electrode and counter electrode
• Clear glass substrates are commonly used as substrate because of
their relative low cost, availability and high optical transparency in
the visible and near infrared regions of the electromagnetic
spectrum.
• TCFs for photovoltaic applications have been fabricated from both
inorganic and organic materials.
• Inorganic films typically are made up of a layer of transparent
conducting oxide (TCO),generally in the form of indium tin oxide
(ITO), fluorine doped tin oxide (FTO), and doped zinc oxide.

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 2.Nanostructured photoelectrode
• In the old generations of photo electro chemical solar
cells (PSC) photo electrodes were made from bulky
semiconductor materials such as Si, GaAs or CdS.

• However, these kinds of photo electrodes when

exposed to light they undergo photo corrosion that
results in poor stability of the photoelctrochemical cell.

• The use of sensitized wide bandgap semiconductors

such as TiO2, or ZnO resulted in high chemical stability
of the cell due to their resistance to photo corrosion.
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• The problem with bulky single or poly-crystalline
wide band gap is the low light to current
conversion efficiency mainly due to inadequate
adsorption of sensitizer because of limited surface
area of the electrode.
• One approach to enhance light-harvesting
efficiency (LHE) and hence the light to current
conversion efficiency is to increase surface area (the
roughness factor) of the sensitized photo electrode.

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• One of the important factors that affect the cell's efficiency is
the thickness of the nanostructured TiO2 layer which must be
less than 20 nm to ensure that the diffusion length of the
photoelectrons is greater than that of the nanocrystalline TiO2
layer.
• TiO2 is the most commonly used nanocrystalline semiconductor
oxide electrode in the DSSC as an electron acceptor to support
a molecular or quantum dot QD sensitizer is TiO2 (Gratzel,
2003).
• Other wide band gap semiconductor oxides is becoming
common is the zinc oxide ZnO. ZnO possesses a band gap of
3.37 eV and a large excitation binding energy of 60 meV.

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 3.Photosensitizer
• Dye molecules of proper molecular structure are used to
sensitized wide bandgap nanostructured photoelectrode.

• Upon absorption of photon, a dye molecule adsorbed to

the surface of say nanostructured TiO2 gets oxidized and
the excited electron is injected into the nanostructured
TiO2.

• Sensitizations of natural dye extracts such as shiso leaf

pigments, Black rice, Fruit of calafate, Rosella ,Natural
anthocyanins ,Henna and wormwood have been
investigated and photovoltaic action of the tested cells
reveals some opportunities. 21
 Photosensitizer

Fig. (a) Ruthenium based red or "N3" dye adsorbed onto a titanium dioxide
surface (from Martinson et al., 2008), and
(b) Proposed structure of the cyanin dye adsorbed to one of the titanium metal
centers on the titanium dioxide surface (From Smestad, 1988).
N3 dye it has been an outstanding solar light absorber and charge-transfer
sensitizer.
The red dye or N3 dye is capable of absorbing photons of wavelength ranging
from 400 nm to 900 nm. 22
 Dye-sensitizers

‘Increasing the Efficiency of Solar Cells by Combining Silicon- and Dye Sensitized Devices’ B. Ohms, A. Kleine and U. Hilleringmann International
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Conference on Renewable Energies and Power Quality (ICREPQ’12) Santiago de Compostela (Spain), 28th to 30th March, 2012
 Natural Dye Performances

Measured absorbance of some extracted natural dyes in methanol as solvent.

Dye-Sensitized Solar Cells: A Successful Combination of Materials : Claudia Longo and Marco-A. De Paoli* Instituto de Química, Universidade Estadual
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de Campinas, CP 6154, 13084-971 Campinas - SP, Brazil
 Redox electrolyte
• Electrolyte containing I-/I3 redox ions is used in DSSC to regenerate the
oxidized dye molecules

• This will complete the electric circuit by mediating electrons between the
nanostructured electrode and counter electrode.

• Cell performance is greatly affected by ion conductivity in the electrolyte

which is directly affected by the viscosity of the solvent.

• NaI, LiI and R4NI (tetraalkylammonium iodide) are well known examples
of mixture of iodide usually dissolved in nonprotonic solvents such as
acetonitrile, propylene carbonate and propionitrile to make electrolyte.

• The redoxing electrolyte needs to be chosen such that the reduction of

I3ions by injection of electrons is fast and efficient

Dye-Sensitized Solar Cells: A Successful Combination of Materials Claudia Longo and Marco-A. De Paoli* Instituto de Química, 25
Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas - SP, Brazil
How Does DSSC Work?

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 TiO2 Dye Electrolyte Cathode

Wide band-gap
semiconductor

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Electron energy
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
S*
-0.5

0.5 Red Ox

1.0 e-
S°/S+

Wide band-gap
semiconductor

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Electron energy
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
e- S*
-0.5 1. Light absorption

0 1
hν
0.5 Red Ox

1.0 h+
S°/S+

Wide band-gap
semiconductor

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Electron energy
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
2
3 S*
-0.5 e- 1. Light absorption
2. Injection to
0 1 semiconductor
hν 3. Percolation
0.5 Red Ox

1.0 h+
S°/S+

Wide band-gap
semiconductor

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Electron energy
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
2
3 S*
-0.5 e- 1. Light absorption
2. Injection to
0 1 semiconductor
hν 3. Percolation
h+
0.5 Red Ox
4. Regeneration of
4 oxidized dye
1.0
S°/S+

Wide band-gap
semiconductor

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Electron energy
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
2
3 S*
-0.5 e- 1. Light absorption
2. Injection to
0 1 semiconductor
hν h+ 3. Percolation
0.5 Red Ox
4. Regeneration of
5
4 oxidized dye
1.0 5. Regeneration of
S°/S+
oxidized species
Wide band-gap
semiconductor

e- h+
External circuit
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LOAD
Electron energy
Maximum Voltage in DSSCs
(eV vs. NHE)
TiO2 Dye Electrolyte Cathode
-1.0
S*
-0.5 The voltage is
Maximum determined
0 Voltage mainly by the
0.5 Red Ox titania and
redox couple
1.0 e- in the
S°/S+
electrolyte.
Wide band-gap
semiconductor

e- h+
External circuit
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LOAD
 34
Gratzel, M. (2005). Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells. Inorg. Chem., Vol. 44, pp. 6841-6851.
Illustration of operation principle of dye sensitized solar cell

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Summary of Dye Sensitized Solar
Cell

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DSSC Preparation

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Image Source : www.thesolarpark.co.uk

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Commercialization of DSSC

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HOOC COOH HOOC HOOC

COOH COOH COOH

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 Applications Of DSSC
• Because of the physical nature of the dye sensitized solar cells, inexpensive,
environment friendly materials, processing, and realization of various colors,
power window and shingles are prospective applications in building integrated
photovoltaics

• The availability of lightweight flexible dye sensitized cells or modules are

attractive for applications in room or outdoor light powered calculators,
gadgets, and mobiles.

• Flexible dye sensitized solar modules opens opportunities for integrating them
with many portable devices, baggage, gears, or outfits.

• In power generation, dye sensitized modules with efficiency of 10% are

attractive choice to replace the common crystalline Si-based modules.

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 Applications of DSSC
(a) 200 m2 of DSSC panels installed in Newcastle (Australia)– the first
commercial DSSC module

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(c) flexible DSSC-based solar module developed by Dyesol (http://www.dyesol.com)

(d) jacket commercialized by G24i (http://www.g24i.com).

D
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 Source:http://www.tiberlab.com/dsc-dye-solar-cell.html

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 Source:http://www.tiberlab.com/dsc-dye-solar-cell.html

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Aesthetic Advantages of DSSCversus
conventional Solar Cells
• Dyes determine the
color of the device.

• Can be transparent

• Can be flexible

• Easy to make
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 Solar Powered Solar Panel Sun Glasses
The SIG, or “Self-Energy Converting Sunglasses” are quite simple. The lenses of the glasses have
dye solar cells, collecting energy and making it able to power your small devices through the power jack
at the back of the frame. “Infinite Energy: SIG”
Courtesy: Sony Corp.

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 The DSC vs. Conventional Silicon PV

̶ TiO2 n-type
+ ̶ Silicon
Dye + ̶
+ ̶
+ ̶
p-type
+ Electrolyte Silicon

Cathode
• Charge carriers (excited
• Light absorption and charge
electrons) are produced
transport are decoupled
throughout the semiconductor
• Relaxed constraints on individual
• Semiconductor considerations:
components (each can be
• Precise doping
separately tuned)
• high purity
• Only monolayer of dye on TiO2
• high crystalinity
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Solar Cell Efficiencies
Silicon Solar Cell Efficiencies:
Theoretical Maximum: 26%
Best in Lab: 25% (Green, UNSW)
Modules: 15-22%

Thin Film Solar Cell Efficiencies:

Theoretical Maximum: >22%
Best in Lab: 20% (Noufi, NREL)
Modules: 9-12%

Dye-Sensitized Solar Cell Efficiencies:

Theoretical Maximum: 14-20%
Best in Lab: 12% (Grätzel, EPFL)
Modules: 6-9%
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 Conclusions
• In short, compared to Si based solar cells dye sensitized solar
cells are of
– low cost and ease of production,
– their performance increases with temperature,
– possessing bifacial configuration - advantage for diffuse light,
have transparency for power windows, color can be varied by
selection of the dye, invisible PV-cells based on near-IR sensitizers
are feasible, and they are outperforms amorphous Si.
• Moreover, DSSC shows higher conversion efficiency than
polycrystalline Si in diffuse light or cloudy conditions.
• It is believed that nanocrystalline photovoltaic devices are
becoming viable contender for large scale future solar
energy converters.
• The search for green sources or generators of energy is
considered one of the priorities in today's societies and
occupies many policy makers' agendas.
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 Reference
• Gratzel, M. (2005). Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells. Inorg.
Chem., Vol. 44, pp. 6841-6851.
• Lewis, N. S. (2007). Toward Cost-Effective Solar Energy Use. Science, Vol 315, pp. 798-801.
• Meyer, G. J. Inorg. Chem. 2005, 44, 6852.
• Mallouk, T. E.; Hoertz, P. G. Inorg. Chem. 2005, 44, 6828.
• Nakade, S.; Kubo, W.; Saito, Y.; Kanzaki, T.; Kitamura, T.; Wada, Y.; Yanagida, S. J. Phys.
Chem. B 2003, 107.
• Plass, R.; Pelet, S.; Kruger, J.; Gratzel, M.; Bach, U. J. Phys. Chem. B 2002, 106, 7578.
• Nozik, A. J. Quatum dot solar cells. Next Gener. Photovoltaics 2004, 196.
• Liska er al. 2006, 88, 203103. Marcus, R. A. 1992, Nobel Lecture.
• Bernards, D. A.; Samuel, F. T.; Hector, D. A.; George, G. M. Science, 2006, 313, 1416.
• Amao, Y. & Komori, T. (2004).
• Bio-photovoltaic conversion device using chlorine-e6 derived from chlorophyll from Spirulina
adsorbed on a nanocrystalline TiO2 film electrode. Biosensors Bioelectronics, Vol. 19, Issue 8,
pp. 843-847.
• Harding, H.E.; Hoke, E.T.; Armistrong, P.B.; Yum, J.; Comte, P.; Torres, T.; Frechet, J.M.J.;
Nazeeruddin, M.K.; Gratzel, M. & McGehee, M.D. (2009). Increased light harvesting in dye-
sensitized solar cells with energy relay dyes. Nature Photonics, Vol. 3, pp. 406-411. 72