Dye Sensitized Solar Cells

a review and commentary

by
Adil Hassib
Physics &Astronomy Dept. King Saud University


Addison: There is a better way. Find it!!
Bohr: Never express yourself more clearly than you are able to t o think.
Aristotle: The essentials of a phenomenon are best understood if one tries
to explore their rise from the very beginnings.



1839 Edmund Becquerel, a French physicist
observed the photovoltaic effect.

(E. Becquerel,"Mmoire sur les effets
lectriques produits sous l'influence des rayons
solaires", C. R. Acad. Sci. Paris, 1839, 9, 561-
567)
1914 The existence of a barrier layer in photovoltaic
devices was noted.
1916 Robert Millikan provided experimental proof of the
photoelectric effect.
The Phenomenon
Interactions of Photons and Electrons

History

Photovoltaics
Bequerel, 1839. Electrochemical
Fritts, 1883. Selenium cells
RCA, 1950 1960 p-n junctions SC.
Today's commercially available silicon solar cells have efficiencies of about 18-19%.

Photoelectrics
Einstein 1904-5, photon theory
Progress in solar cell efficiencies (1976 to 2003) for various
research or laboratory devices. All these cell efficiencies have been
confirmed and were measured under standard reporting conditions.
Source:Thomas Surek, National Renewable Energy Laboratory
2. SOLAR RADIATION AND AIR MASS

2.1. RADIATION PROPERTIES OF THE
ATMOSPHERE
P=1.367kWm
-2
- the
solar constant solar
radiation power outside
the Earths atmosphere
Taken from: S. M. SZE; Physics of Semiconductor Devices; Second Edition; John
Wiley & Sons;New York; 1981
2.3. SOLAR SPECTRAL IRRADIANCE
3. THE PHOTOVOLTAIC CHARACTERISTICS
OF THE SOLAR CELLS
How the device works?
.
The p-n junction under illumination (on the right). A photon induced hole-electron pair
is separated by the local field of the junction. Taken from: F. C. TREBLE (Editor); Generating
Electricity from the Sun; Pergamon Press, Inc.;New York; 1991
3.1. Simplified equivalent circuit of a solar cell
I
G
: generated current
I
J:
juncktion current

Introduction
Main Theme:
How (& why) can biopolymers (melanins) be used to harvest photons and
produce photoelectrons across the UV and Visible, and do they have
the potential to be viable solar photovoltaic biomaterials?

What Makes a Good Solar Photovoltaic Material?
1. High photon capture cross-section in the UV and Visible
2. Efficient production of photoexcited charges
3. Efficient transfer of photoexcited charges to some external circuit (i.e. able to
be integrated into a suitable PV device platform)
4. Cheap, biocompatible (preferably bioavailable), processable, stable
(chemically and photochemically), etc.

The perfect world: q
ex
=1, low $/watt, short payback, positive
environmental impact
Introduction
Melanin Basics
Eumelanins: Basic Physical & Chemical Properties vs. PV
Requirements
Photon capture
Photoexcited charge generation
Photoexcited charge collection and transfer to the external circuit

Eumelanins: Basic Technological Considerations vs. PV
Requirements
Synthesis & bioavailability
Solid thin film fabrication & processability
Suitable electrode surfaces (device engineering)

Challenges (current and future work)

Summary & Acknowledgements
Melanin Basics
Specific class of polycyclic
biopolymer related to the humic acids
& found throughout nature very
important in humans
Biological roles: photoprotectants,
pigments, free radical scavengers,
antioxidants, charge transport
mediators
Implicated in melanoma skin cancer
and Parkinsons disease
Chemically stable, redox active,
strong chelating power
Random heteropolymers of
indolequinones
Often found intimately associated
with melanoproteins

Important biologically unique set of
solid state properties:



N
O
O
H
H
H
N
O
O
H
2e,2H+
N
O
O
H
Monomer Redox Cycling
Photoexcited Charge Collection
The photogenerated electron (or hole) must be able to diffuse to a suitable electrode
surface in order to be transferred into an external circuit - this requires:
o adequate electron / hole mobility within the photoactive material (i.e. a reasonable
electrical conductivity)
o efficient coupling of the photoactive material to some host electrode
o (plus - for regenerative devices - the usual establishment of an intrinsic electric field
/ charge separation mechanism, and the efficient transport of the electron / hole
through the electrode to the external circuit)

Melanin electrical conductivity (o)
pressed pellets of synthetic or natural material o~10
-8
Scm
-1
molecularly continuous thin films (electropolymerised) o~10
-5
-10
-6
Scm
-1
o dependent upon doping, water content and polymer composition (MW)
Coupling melanin to a host electrode
possible to functionalise the polymer in order to manufacture a strong covalent
coupling to the host electrode
Photoexcited Charge Collection Coupling to a
Suitable Electrode (e.g. TiO
2
)
Photoelectrochemical technology approach
(Gratzel) regenerative test device:
cheap, biocompatible materials
nano structuring to increase total surface
area for photon absorption
melanin provides sensitisation of titania
(photoanode) into visible (in theory)
Nano structured photoanode
(titanium dioxide + photosenstising biopolymer)
hu
I
TCE TCE
Redox Electrolyte (Liquid)
Carbon / platinum counter cathode
S
0
/S
+
S*

mediator
red
ox
sensitiser

photoanode

e-
E
E
c
E
v
Schematic energy level diagram
for a sensitised PEC solar cell
Photoexcited Charge Collection Coupling to a
Suitable Electrode (e.g. TiO
2
)
0.00
0.01
0.10
1.00
10.00
100.00
1000.00
300 350 400 450 500 550 600
Wavelength (nm)
L
o
g

N
o
r
m
a
l
i
s
e
d

P
h
o
t
o
c
u
r
r
e
n
t
TiO2
TiO2 + Melanin
TiO2 + AnthoCyanine
Photoaction spectra show:
- expected UV photo-response for TiO
2
- evidence of visible light photoresponse
in melanin sensitised system
- evidence of photoexcited carrier
injection into the titania after absorption
of a visible photon by the melanin
- demonstration of coupling of the
melanin to a suitable electrode

PLUS

Regenerative PV action:
- small but measurable
- I-V characterisation yields a visible light
power conversion efficiency of 0.1%
Evidence for photo-excited
carrier injection
Technological Considerations - Biopolymer
Design, Synthesis & Availability
O H
NH
2
COOH
O H
O H
NH
2
COOH
COOH
NH
2
O
O
N
H
O H
O H
COOH
O
COOH
N
O H
N
H
O H
O H
N
H
O H
O H
COOH
tyrosine
dopa dopaquinone
leucadopachrome dopachrome
5,6, dihydroxyindole
(DHI)
5,6-dihydroxyindole-2-carboxylic acid
(DHICA)

Melanins
Goals:
Controlled composition DHI/DHICA polymers
Ready supply of natural material various sources
Technological Considerations - Biopolymer
Thin Film Fabrication & Processing
Thin films of DHI / Dopa melanin have been synthesised by electropolymerisation from
precursor solutions onto conducting glass substrates
Melanin thin films prepared from dl-Dopa
by electropolymerisation
fracture
surface
film
surface
Chemical analysis vs. Dopa melanin
-solid state nmr
-XPS
-elemental analysis
Confirms that the material is melanin
Physical analysis
-XRD
-SEM
-TEM
-Conductivity
Structurally continuous, amorphous
semiconducting, free standing thin film
Challenges
Current
Produce good quality material powders, composites, molecularly continuous thin films
(of controlled composition & MW)
Better chemical characterisation
Understand electronic and optical properties (especially band structure and charge
transport) are they really condensed solid state amorphous semiconductors?
Learn how to modify electronic properties (band gap, conductivity) Cu doping
Understand how to maximise photogeneration, collection, and coupling to suitable
electrodes (minimise phonon related de-excitation pathways)
Maximise efficiency in two regenerative PV platforms (Gratzel and p-i-n all soft solid
state) goal 1% in Gratzel platform by end 2003

Future
Other photonic, optoelectronic, electronic device & sensor applications (e.g. broad band
photodetectors, humidity sensors)
Interactions of pigment and host melanoproteins
Studies on malignant melanoma pigment (early cancer detection?)
Summary & conclusions
Melanins are a class of biopolymers with unique physical and chemical
properties
They possess the prerequisite properties to act as broad band solar photon
harvesting materials and PV materials in regenerative devices
They offer the added advantages of being soft solids, biocompatible and
bioavailable (also relatively easy to produce synthetic analogues)

Its by no means clear if they will prove viable as PV materials, but they are
certainly interesting from a technological perspective
Many challenges understand / manipulate mesoscopic properties, and
maximise efficiency within a regenerative PV platform
For a successful technology,
reality must take precedence over
public relations,
for Nature cannot be fooled

Dick Feynman
Absorbance:
Broadband
Increases exponentially towards UV.
350 400 450 500 550 600 650
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
A
b
s
o
r
b
a
n
c
e

(
c
m
-
1
)
Wavelength (nm)
0.001%
0.0025%
0.005%
Absorbance of Synthetic Melanin Solutions at Various Concentrations
PL: Re-absorption Correction
350 400 450 500 550 600 650
-50000
0
50000
100000
150000
200000
250000
300000
350000
400000
Pumping at 380nm
After Re-absorption Correction
E
m
i
s
s
i
o
n

(
c
p
s
)
Wavelength (nm)
0.001%
0.0025%
0.005%
350 400 450 500 550 600 650
0
50000
100000
150000
200000
250000
300000
350000
400000
E
m
i
s
s
i
o
n

(
c
p
s
)
Wavelength (nm)
0.001%
0.0025%
0.005%
Before Re-absorption Correction
Pumping at 380nm
Strong re-absorption.
Strong, broad emission.
Emission increases linearly with
concentration.
Fit to two gaussians (in frequency
space)
- Two dominant transitions
Peaks do not shift with
concentration (yay!).
Peaks do shift with pump
wavelength (multiple dominant
transitions).
PLE:
280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580
0
200000
400000
600000
800000
1000000
1200000
1400000
1600000
1800000
E
m
i
s
s
i
o
n

(
c
p
s
)
Wavelength (nm)
477nm
485nm
546nm
578nm
PLE detecting at various wavelengths
0.005% Synthetic
Melanin Solution
Re-absorption Corrected
PLE profiles
Change shape when detect at different wavelengths.
Fit to three gaussians (in frequency space).
- Three dominant excitation wavelengths.
Summary of Learnings from Steady
State Spectroscopy
Very strong absorber
Must (and can!) correct emission measurements for re-
absorption.
Strong emission!
Once re-absorption corrected shows expected trends.
Broad, fits to two gaussians (two dominant transitions?).
PL peaks shift with pump wavelength (multiple transitions).
PLE profiles fit three gaussians (three dominant excitation
wavelengths).
Error analysis
Errors due to re-absorption correction process very small in
comparison to error from PL and PLE scans themselves.

Synthesis of the Nanotitanium
Suspension
Procedure:
Add 9 ml (in 1 ml increments) of
nitric or acetic acid (ph3-4) to six
grams of titanium dioxide in a
mortar and pestle.
Grinding for 30 minutes will
produce a lump free paste.
1 drop of a surfactant is then added
( triton X 100 or dish washing
detergent).
Suspension is then stored and allow
to equilibrate for 15 minutes.
Coating the Cell
After testing to determine which
side is conductive, one of the
glass slides is then masked off 1-
2 mm on THREE sides with
masking tape. This is to form a
mold.
A couple of drops if the titanium
dioxide suspension is then added
and distributed across the area
of the mold with a glass rod.
The slide is then set aside to dry
for one minute.
Calcination of the Solar Cells
After the first slide has dried the tape
can be removed.
The titanium dioxide layer needs to
be heat sintered and this can be done
by using a hot air gun that can reach
a temperature of at least 450 degrees
Celsius.
This heating process should last 30
minutes.
Dye Absorption and Coating the
Counter Electrode
Allow the heat sintered slide to cool
to room temperature.
Once the slide has cooled, place the
slide face down in the filtered dye
and allow the dye to be absorbed
for 5 or more minutes.
While the first slide is soaking,
determine which side of the second
slide is conducting.
Place the second slide over an open
flame and move back and forth.
This will coat the second slide with a
carbon catalyst layer
Dye Absorption and Coating the
Counter Electrode
Allow the heat sintered slide to cool
to room temperature.
Once the slide has cooled, place the
slide face down in the filtered dye
and allow the dye to be absorbed
for 5 or more minutes.
While the first slide is soaking,
determine which side of the second
slide is conducting.
Place the second slide over an open
flame and move back and forth.
This will coat the second slide with a
carbon catalyst layer
Assembling the Solar Cell
After the first slide had absorbed
the dye, it is quickly rinsed with
ethanol to remove any water. It
is then blotted dry with tissue
paper.
Quickly, the two slides are
placed in an offset manner
together so that the layers are
touching.
Binder clips can be used to keep
the two slides together.
One drop of a liquid
iodide/iodine solution is
then added between the
slides. Capillary action will
stain the entire inside of
the slides
How Does All This Work?
1. The dye absorbs
light and transfers
excited electrons to
the TiO
2.
2. The electron is
quickly replaced by
the electrolyte added.
3. The electrolyte in
turns obtains an
electron from the
catalyst coated
counter electrode.
TiO
2
=electron acceptor; Iodide = electron donor;
Dye = photochemical pump
Ionic Liquids in General
Ionic liquids are liquids
formed only of ions.
Ionic liquids do not
have a solvent
component.
Ionic liquids have a low
vapor pressure so they
are non-volatile.
Picture taken from Chem. World. June 2004, V:1(6)
Martin Earle-Quill
Room Temperature Ionic Liquids (RTILs)
A RTIL is an ionic material that is
liquid at room temperature.
They are based primarily on
asymmetric organic cations paired
with inorganic anions.
By changing the ions, a countless
variety of RTILs can be obtained.
The asymmetric shape of the cations
prevents the packing and the
formation of solids at RT.
Air and water resistant.
Can be hydrophilic or hydrophobic.

Possible Applications of Ionic Liquids
Applications as Solvent: They are non volatile
and recyclable. Suitable for extraction processes
without loss of solvent.
Chemically Active Solvent: Catalytic activity.
New Propellants and Fuels: High energy density
that may be used in propulsion.
Application as electrolyte in Solar Cells: non-
leaking and good charge transport properties
Dye-sensitized solar cells: Components

1. Granular TiO
2
forming a nanoporous
structure.

2. A dye, which is a light sensitive
substance spread on the TiO
2

surface.

3. A redox couple (I
-
/I
3
-
), located in the
space between the dye and the
cathode.

4. A solvent for the redox couple, e.g.
a Room temperature Ionic Liquid.
TiO
2

Electrolyte
Relevant issues concerning RTILs

RTIL in confined geometries
RTIL in the presence of charged walls
Dye-sensitized solar cells: Operation

1. Dye electrons are excited by solar
energy absorption.

2. They are injected into the
conduction band of TiO
2
.

3. Get to counter-electrode (cathode)
through the external circuit.

4. : Redox regeneration at
the counter-electrode (oxidation).

5. : Dye regeneration
reaction (reduction).

6. Potential used for external work:

- -
3
I 3 2 I +

+ e 2 I I 3
-
3
-
redox F ext
V E V A = A
Red=I
-

Ox =I
3
-

Ionic Liquid
[bmim]
+
I
-
The Solar Constant
Check yourself: Does everyone know what a
watt (W) is? A milliwatt (mW)?
We call this number The Solar Constant
and designate it by the Greek letter sigma
(o).
When we measure the midday intensity of
sunlight at the Earths surface, we find that
about 136.7 mW fall on every square
centimeter.
At 1 A.U.: o = 136.7 mW/cm
2
.
An A.U. is the average Earth-Sun
separation, ~ 150,000,000 km.
I
V
Dark Characteristic Light Characteristic
I
V
Power
Generating
Region
Power
Dissipating
Region
Power
Dissipating
Region
The VI characteristic of a solar cell is
usually displayed like this:
V
I
V
I
The coordinate system is flipped around the
voltage axis.

Set #1: I
SC
, P
MAX
, V
OC

(0.5V, 0 mA)
V I = 0 mW
(0.43 V, 142 mA)
V I = 61 mW
I
SC

V
OC

P
MAX

(0V, 150 mA)
V I = 0 mW
Some typical
values
Nanocrystalline Solar Cells: The
Materials
Materials:
1. (2) F-SnO
2
glass
slides
2. Iodine and Potassium
Iodide
3. Mortar/Pestle
4. Air Gun
5. Surfactant (Triton X
100 or Detergent)
6. Colloidal Titanium
Dioxide Powder
7. Nitric Acid
8. Blackberries,
raspberries, green
citrus leaves etc.
9. Masking Tape
10. Tweezers
11. Filter paper
12. Binder Clips
13. Various glassware
14. Multi-meter

Preparation of Nanotitanium and
Electrolyte Solution
Nanotitanium
1. Add 2-ml of 2,4 Pentanedione (C
5
H
8
O
2
) to 100-ml of anhydrous
isopropanol [ (CH
3
)
2
CHOH ] and stir covered for 20 minutes.
2. Add 6.04-ml of titanium isopropoxide (Ti[(CH
3
)
2
CHO]
4
to the
solution and stir for at least 2 hours.
3. Add 2.88-ml of distilled water and stir for another 2 hours.
4. The solution must then age for 12 hours at room temperature.
5. Since you now have a collodial suspension, the solvent must be
evaporated off in an oven to collect the powder.
Electrolyte solution
1. Measure out 10-ml of ethylene glycol
2. Weigh out 0.127-g of I
2
and add it to the ethylene glycol and
stir.
3. Weigh out 0.83 g of KI and add it to the same ethylene glycol.
4. Stir and sore in a dark container with a tight lid.
Silicon Crystals Comparison
Type Efficiency in Lab Efficiency in Production
Monocrystalline 24 14-17
Polycrystalline 18 13-15
Amorphous 13 5-7
Source: Solar Server.de
Solar Energy Spectrum
Power reaching earth 1.37 KW/m
2
Solar cell Working Principle
Operating diode in fourth quadrant generates power
CdTe/CdS Solar Cell
CdTe : Bandgap 1.5 eV; Absorption coefficient 10 times
that of Si
CdS : Bandgap 2.5 eV; Acts as window layer
Limitation :
Poor contact quality with p-CdTe (~ 0.1 Ocm
2
)

PV: The Technology

$

coal nuclear gas oil wind solar
2.1 2.3
3.6
3.9
5.5
22
Nuclear Energy Institute, American Wind Energy Association, American Solar Energy Society
Today: Production Cost of Electricity
By Sylvia Tulloch
Actual or forecast market acceptance to market
decline for the important PV technologies
Timing
PV Technology PV
Generation
Forecast time from market
acceptance to decline
Silicon Crystalline 1 1970 - 2020
Silicon Amorphous 2 1983 - 2025
Silicon Thin Film 2 2001 - 2050
CdTe 2 1995 - 2010
CIS/CIGS other 3/5, 2/4/6 2 2000 - 2050
DSC 3 2003 - 2055
DSC - hybrid 3+ 2015 - 2100
Organic - hybrid 3+ 2015 - 2100
Biological 4 2030 - 2100+
Gratzel Cell

Photo-electrochemical Cell
Artificial photosynthesis

Solid State Analogue


SnO 2
SnO 2
Electrolyte

TiO 2
10 m
Platinum
Dye/biopolymer/quantum dots

Indium Tin Oxide
On Glass Support
Polymer Quantum Dot
Matrix
Aluminium
Energy
Regan and Gratzel, Nature 353 (1991) p737
Huynh et al. Science 29 295 (2002) p2425

DYES
Main Theme:
How (& why) can biopolymers (Dyes) be used to harvest photons and
produce photoelectrons across the UV and Visible, and do they have
the potential to be viable solar photovoltaic biomaterials?

What Makes a Good Solar Photovoltaic Material?
1. High photon capture cross-section in the UV and Visible
2. Efficient production of photoexcited charges
3. Efficient transfer of photoexcited charges to some external circuit (i.e. able
to be integrated into a suitable PV device platform)
4. Cheap, biocompatible (preferably bioavailable), processable, stable
(chemically and photochemically), etc.

Solar spectrum
Natural Dye Absorption
Photosynthetic Process
Sunlight is trapped by
chloroplasts
Water is transported from soil
to leaf
Carbon dioxide enters
through stomata
Water and light combine to
form chemical energy
Chemical energy and carbon
dioxide rearrange to form
carbohydrates and oxygen
Sugar is stored in plant and
oxygen is released through
stomata



Operationally
Basics I
Melanin: Basic Physical & Chemical Properties vs. PV Requirements
Photon capture
Photoexcited charge generation
Photoexcited charge collection and transfer to the external circuit

melanins: Basic Technological Considerations vs. PV Requirements
Synthesis & bioavailability
Solid thin film fabrication & processability
Basics II
Photon Capture (Solar)
Very strong, broad band UV & visible
absorption eumelanins are black
Monotonic behaviour vs.
Fits a simple exponential:
o extended conjugation & phonon
coupling: continuum of states within
the t and t* manifolds
o an amorphous semiconductor
displaying an exponential Urbach
tail near the absorption edge?:



Consistent with photoprotective
function, and potentially useful for
solar photon harvesting


( ) E E E

o = o
0 0
Tauc Plot:
( ) ( ) 5 0. Linear E . vs E = o

Band Structure
Narrow Bandgap (1.4eV) Amorphous Semiconductor
(Condensed Solid State)?
Amorphous model for melanin
powders:
narrow bandgap consistent with
broad band UV & Vis absorption
high density of states at the Fermi
level & sub band
two activation energies (0.1 and
0.78eV) below and above 311K
respectively (lower activation
energy related to localised density
of states at Fermi Level)
thermopower measurements: p-
type conductivity for T~293K and
n-type for T~325K !

Consistent with structural
observations no crystallinity

E
F
E
V
E
C
E

N(E)

1.40eV
0.78eV
0.2eV
{From DC conductivity measurements
of amorphous powders}
Amorphous electronic behaviour?
t*
t
Conduction
Photoexcited Charge Generation
Melanins photoconduct with a
photo-action spectrum which
matches their absorption
spectrum
Photoactivity of Thin Film Dopa Melanin
(Electropolymerised)
20
25
30
35
40
45
50
0 30 60 90 120 150 180 210 240 270 300 330
Time (s)
R
e
s
i
s
t
a
n
c
e

(
M

O
h
m
s
)
Lamp On
Lamp Off
Rapid light induced
decrease in resistance (ambient
conditions, 19V bias voltage,
illumination by a Hg-vapour
lamp ~300mW/cm
2
)
Photoactivity of Thin Film Dopa Melanin
(Electropolymerised): +19V Bias
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0 30 60 90 120 150 180 210 240 270 300 330
Time (s)
P
h
o
t
o
c
u
r
r
e
n
t

(
m
i
c
r
o
A
)
Lamp Off
Lamp On
Charge coupling
Photoexcited Charge Collection Coupling to a Suitable Electrode (e.g. TiO
2
)
Photoelectrochemical technology approach
(Gratzel) regenerative test device:
cheap, biocompatible materials
nano structuring to increase total surface
area for photon absorption
melanin provides sensitisation of titania
(photoanode) into visible (in theory)
Nano structured photoanode
(titanium dioxide + photosenstising biopolymer)
hu
I
TCE TCE
Redox Electrolyte (Liquid)
Carbon / platinum counter cathode
S
0
/S
+
S*

mediator
red
ox
sensitiser

photoanode

e-
E
E
c
E
v
Schematic energy level diagram
for a sensitised PEC solar cell
Challenges
( short range?)
Better chemical characterisation
Understand electronic and optical properties (especially
band structure and charge transport) are they really
condensed solid state amorphous semiconductors?
Learn how to modify electronic properties (band gap,
conductivity) e.g. via doping
Understand how to maximise photogeneration, collection,
and coupling to suitable electrodes (minimise phonon
related de-excitation pathways)
Produce good quality, suitable materials powders,
composites, molecularly continuous thin films (of
controlled composition & MW)
Interactions of pigment and host