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, 561567) 1914 The existence of a barrier layer in photovoltaic devices was noted.

1916 Robert Millikan provided experimental proof of th 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

2.3. SOLAR SPECTRAL IRRADIANCE

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

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

IG: generated current IJ: 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: 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:

O H O H O N H O O N H 2e,2H+ H O N

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 () pressed pellets of synthetic or natural material ~10-8Scm-1 molecularly continuous thin films (electropolymerised) ~10-5-10-6Scm-1 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. TiO2)

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)
E

h
TCE TCE

eS* Ec S0/S+ sensitiser Ev photoanode red mediator ox

I
Redox Electrolyte (Liquid)

Schematic energy level diagram for a sensitised PEC solar cell

Nano structured photoanode (titanium dioxide + photosenstising biopoly Carbon / platinum counter cathode

Photoexcited Charge Collection Coupling to a Suitable Electrode (e.g. TiO2)

Evidence for photo-excited carrier injection
TiO2 1000.00 TiO2 + Melanin TiO2 + AnthoCyanine

Log N a d Photocurre orm lise nt

100.00

10.00

1.00

0.10

Photoaction spectra show: - expected UV photo-response for TiO2 - 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

0.01

0.00 300 350 400 450 500 550 600

W ve ngth (nm a le )

Regenerative PV action: - small but measurable - I-V characterisation yields a visible light power conversion efficiency of 0.1%

Technological Considerations Biopolymer Design, Synthesis & Availability

tyrosine
COOH HO NH2 HO HO

dopa
COOH NH2

dopaquinone
O O COOH NH2

HO HO N H

O COOH HO N

HO COOH HO N H

5,6, dihydroxyindole (DHI)

HO COOH HO N H

dopachrome Melanins

leucadopachrome

5,6-dihydroxyindole-2-carboxylic acid (DHICA) 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
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

fracture surface film surface

Melanin thin films prepared from dl-Dopa by electropolymerisation

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

 Broadband Increases exponentially towards UV.

0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 350 400 450

Absorbance:

Absorbance of Synthetic M elanin Solutions at Various Concentrations

Absorbance (cm-1)

0.001% 0.0025% 0.005%

500

550

600

650

Wavelength (nm)

PL: Re-absorption Correction

400000 350000

Before Re-absorption Correction

Pumping at 380nm

300000

250000 200000 150000 100000 50000 0 350

0.001% 0.0025% 0.005%

Strong re-absorption. Strong, broad emission. Emission increases linearly with concentration. Fit to two gaussians (in frequency space) - Two dominant transitions
After Re-absorption Correction
400000 350000 300000

Emission (cps)

400

450

500

550

600

650

Wavelength (nm)
Emission (cps)

0.001% 0.0025% 0.005% Pumping at 380nm

250000 200000 150000 100000 50000 0 -50000 350 400 450 500 550

Peaks do not shift with concentration (yay!). Peaks do shift with pump wavelength (multiple dominant transitions).

600

650

Wavelength (nm)

PLE:
PLE detecting at various wavelengths
1800000 1600000 1400000

0.005% Synthetic Melanin Solution 477nm 485nm 546nm 578nm Re-absorption Corrected

Emission (cps)

1200000 1000000 800000 600000 400000 200000 0

280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580

Wavelength (nm)

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 TiO2. The electron is quickly replaced by the electrolyte added. The electrolyte in turns obtains an electron from the catalyst coated counter electrode.

2.

3.

TiO2=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: nonleaking and good charge transport properties

Dye-sensitized solar cells: Components

1. 1. Granular TiO2 forming a nanoporous structure. A dye, which is a light sensitive substance spread on the TiO2 surface. A redox couple (I-/I3-), located in the space between the dye and the cathode. A solvent for the redox couple, e.g. a Room temperature Ionic Liquid.
Relevant issues concerning RTILs RTIL in confined geometries RTIL in the presence of charged walls

2.

TiO2
Electrolyte

3.

Dye-sensitized solar cells: Operation

1. 2. 3. Dye electrons are excited by solar energy absorption. They are injected into the conduction band of TiO2. Get to counter-electrode (cathode) through the external circuit.
Red=IOx =I3-

Ionic Liquid [bmim]+ I -

4. I 3 + 2e 3I : Redox regeneration at the counter-electrode (oxidation).

5. 1.

3I - I 3 + 2e

: Dye regeneration reaction (reduction). Potential used for external work:

Vext = E F Vredox

The Solar Constant When we measure the midday intensity of sunlight at the Earths surface, we find that about 136.7 mW fall on every square centimeter. We call this number The Solar Constant and designate it by the Greek letter sigma (). At 1 A.U.: = 136.7 mW/cm2. Check yourself: Does everyone know what a watt (W) is? A milliwatt (mW)?

1 A. U.

An A.U. is the average Earth-Sun separation, ~ 150,000,000 km.

Power Dissipating Region

V
Power Generating Region

Power Dissipating Region

Dark Characteristic

Light Characteristic

The VI characteristic of a solar cell is usually displayed like this: V I

I The coordinate system is flipped around the voltage axis.

Set #1: ISC , PMAX , VOC ISC

(0V, 150 mA) V I = 0 mW (0.43 V, 142 mA) V I = 61 mW

PMAX

Some typical values

(0.5V, 0 mA) V I = 0 mW

VOC

Nanocrystalline Solar Cells: The Materials: Materials

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. (2) F-SnO2glass slides Iodine and Potassium Iodide Mortar/Pestle Air Gun Surfactant (Triton X 100 or Detergent) Colloidal Titanium Dioxide Powder Nitric Acid Blackberries, raspberries, green citrus leaves etc. Masking Tape Tweezers Filter paper Binder Clips Various glassware Multi-meter

Nanotitanium
1. 2. 3. 4. 5.

Preparation of Nanotitanium and Electrolyte Solution

Add 2-ml of 2,4 Pentanedione (C5H8O2) to 100-ml of anhydrous isopropanol [ (CH3)2CHOH ] and stir covered for 20 minutes. Add 6.04-ml of titanium isopropoxide (Ti[(CH3)2CHO]4 to the solution and stir for at least 2 hours. Add 2.88-ml of distilled water and stir for another 2 hours. The solution must then age for 12 hours at room temperature. Since you now have a collodial suspension, the solvent must be evaporated off in an oven to collect the powder.

Electrolyte solution
1. 2. 3. 4. Measure out 10-ml of ethylene glycol Weigh out 0.127-g of I2 and add it to the ethylene glycol and stir. Weigh out 0.83 g of KI and add it to the same ethylene glycol. Stir and sore in a dark container with a tight lid.

Silicon Crystals Comparison

Type Monocrystalline Polycrystalline Amorphous Efficiency in Lab 24 18 13 Efficiency in Production 14-17 13-15 5-7

Source: Solar Server.de

Solar Energy Spectrum

Power reaching earth 1.37 KW/m2

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 cm2)

PV: The Technology

$
Today: Production Cost of Electricity 22

2.1

2.3

3.6

3.9

5.5

coal

nuclear

gas

oil

wind

solar

Nuclear Energy Institute, American Wind Energy Association, American Solar Energy Society

Timing
Actual or forecast market acceptance to market decline for the important PV technologies
PV Technology PV G eneration Silicon Crystalline 1 Silicon Am orphous 2 Silicon Thin Film 2 CdTe 2 CIS/CIG S other 3/5, 2/4/6 2 DSC 3 DSC - hybrid 3+ O rganic - hybrid 3+ Biological 4
By Sylvia Tulloch

Forecast tim e from m arke acceptance to decline 1970 - 2020 1983 - 2025 2001 - 2050 1995 - 2010 2000 - 2050 2003 - 2055 2015 - 2100 2015 - 2100 2030 - 2100+

Gratzel Cell
SnO2

Photo-electrochemical Cell Artificial photosynthesis Solid State Analogue

TiO2

Platinum

Electrolyte Dye/biopolymer/quantum dots

10m SnO2

Regan and Gratzel, Nature 353 (1991) p737

Energy

Aluminium Polymer Quantum Dot Matrix

Huynh et al. Science 29 295 (2002) p2425

Indium Tin Oxide On Glass Support

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. 2. 3.

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

4.

Solar spectrum
Natural Dye Absorption

Photosynthetic Process

Operationall y

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

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 and * manifolds an amorphous semiconductor displaying an exponential Urbach tail near the absorption edge?:

= 0 ( E E0 ) E

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

Tauc Plot:

( E ) vs. E

Linear ( = 0.5)

Band Structure
Narrow Bandgap (1.4eV) Amorphous Semiconductor (Condensed Solid State)? Amorphous electronic behaviour? E EC
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: ptype conductivity for T~293K and n-type for T~325K !

*
1.40eV

EF

0.2eV

0.78eV EV

N(E) {From DC conductivity measurements of amorphous powders}

Consistent with structural observations no crystallinity

Conduction
Photoexcited Charge Generation
Melanins photoconduct with a photo-action spectrum which matches their absorption spectrum
Photoactivity of Thin Film Dopa Melanin (Electropolymerised): +19V Bias
Photocurrent (microA)
0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 30 60 90 120 150 180 210 240 270 300 330
Lamp On Lamp Off

Photoactivity of Thin Film Dopa Melanin (Electropolymerised)

Resistance (M Ohms)
50 45 40 35 30 25 20 0 30 60 90 120 150 180 210 240 270 300 330
Lamp On Lamp Off

Time (s)

Time (s)

Rapid light induced decrease in resistance (ambient conditions, 19V bias voltage, illumination by a Hg-vapour lamp ~300mW/cm2)

Charge coupling
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)
E

Photoexcited Charge Collection Coupling to a Suitable Electrode (e.g. TiO2

h
TCE TCE

eS* Ec S0/S+ sensitiser Ev photoanode red mediator ox

I
Redox Electrolyte (Liquid)

Schematic energy level diagram for a sensitised PEC solar cell

Nano structured photoanode (titanium dioxide + photosenstising biopoly Carbon / platinum counter cathode

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