National Workshop on Solar Photovoltaic Components, Systems and Design NWSPCSD-2011

Organic Semiconductor based photovoltaic systems

M.N.Kamalasanan Scientist G Centre for organic electronics National Physical Laboratory, New Delhi
ITS Engineering College Greater Noids 26-3-2011

Solar cells
Converts solar light in to electric power 95% solar cells are made of silicon Conversion process is based on the photoelectric effect discovered by Alexander Bequerel in 1839 The photoelectric effect describes the release of positive and negative charge carriers in a solid state when light strikes its surface.

Why Organic?
Cheap materials Low cost processing at low temperature Large area Flexible, Light weight New processing technologies like printing, roll to roll processing
10 x 15 cm ; Active area : 80 cm2 University of Linz

Structure of Solar Cell

electrode

AR coating

electrode

N type

P-type

Light

Light is absorbed in silicon Electron-hole pairs are created At the junction, an interior electric field is built up which leads to the separation of the charge carriers that are released by light. Through metal contacts, an electric charge can be tapped. .

ORGANIC SOLAR CELLS

It consists of donor and acceptor which are similar in concept to the two types of doped silicon . Glass ITO Donor Acceptor PPV C60

E L H Donor

Acceptor

Basic operation of organic solar cells

1. Optical absorption and formation of excitons 2. Exciton diffusion to donor-acceptor interface 3. Charge separation 4. Charge transport to the respective electrodes (Diffusion as well as drift) 5. Charge collection

Optical absorption and exciton formation

A photon hitting either donor or acceptor molecule is absorbed if its energy matches the band gap Max. solar energy is emitted at 1.1 eV. solar cells should have maximum absorbance at this energy for high energy conversion Organic materials have high absorbance Silicon is an indirect bandgap material and hence a poor absorber Most conducting polymers absorb ~2eV Band gap to be engineered to match with solar emission maximum Electron is excited from HOMO to LUMO produce an exciton rather than a free electron hole pair due to its strong binding energy

Glass ITO

e h

Donor Acceptor

Electronic band gap= Optical bandgap+ exciton binding energy

Binding energy 0.4 eV

Excitons
Wannier exciton Frankel exciton

Bohr Radius~10nm rB = r0 (me/meff )

Radius~1nm

Meff depend on the degree of localization

Exciton Diffusion
In order to generate a free electron hole pair the exciton travels/diffuse to the junction

Glass

ITO

Donor e

Acceptor

Diffusion length 10 nm L H Donor Acceptor

Exciton dissociation
Glass ITO

Donor

Acceptor

Excitons has to be dissociated to get free charge carriers. At rectifying contacts (single layer devices) At donor-acceptor interfaces Low diffusion length in OS is a limitation Larger interface area -larger dissociation

E L H Donor Acceptor

Charge transport
Glass ITO

Donor

Acceptor

Hopping transport produce Low Carrier mobility Affect charge transport Charge trapping reduce current Carrier recombination also reduces efficiency

Charge extraction
Glass ITO

Donor

Acceptor

Non ohmic contacts and Interface barriers produce band bending Depletion layers Reduces charge collection

Different types of organic solar cells

Single layer cells Double layer structure Blend structure Laminated devices

Types of organic solar cells

Single layer devices

Double layer structure

OPV [ITO/(25 nm)CuPc/(45 nm)PTCBI/Ag]. (From Tang, C. W. Appl. Phys. Lett. 1986, 48(2), 183185

Photoinduced Charge generation and separation

N. SERDAR SARICIFTCI Prog. Quant. Electr. 1995, Vol. 19, pp. 131-159 University of California, Santa Barbara,

Donor (D)

Acceptor (A)

Photophysics of polymer fullerene mixtures show a photoinduced Charge generation and separation

Charge separation time ultra fast (~10-14 s) Charge recombination time relatively ultra slow (~10-3 s) Ensure internal quantum efficiency ~100%

Active region and optical filter effect .

Glass Optical filter

Donor
ITO

Acceptor

Absorbing layer

Active region

Exciton diffusion length~10nm

Bulk heterojunction concept

Photoinduced charge separation is near unity. Small exciton diffusion limits the photoactivity to a very small thickness of 10-20nm. An interpenetrating phase separated D-A network has been introduced by Heeger and co-workers This solved the problem of small diffusion length and substantially increased the efficiency of organic solar cells.

Bulk heterojunction concept

Three different types of polymer solar cells

Methods of growth of organic materials

Small Molecules

Methods of growth of organic materials

Conducting Polymers Screen Printing

Characterization of solar cells cell

Where Voc

open circuit voltage

Current density voltage curve

(voltage when no current is flowing) Isc FF -Short circuit current (Current with no external load) - Fill Factor

Factors affecting Voc , Isc and FF

Voc depends on band gap in inorganic materials In organic materials it usually depends on the energy difference between the Ip of donor and Ea of acceptor. It can decrease if the shunt resistance is low due to recombination of charge carriers near the dissociation site A large difference in WF also increases Voc Current depend of the series resistance which in tern depend of the charge carrier mobility, charge collection efficiency etc.

E L H Donor Acceptor
Voc depends on the donor acceptor ratio also

OPV materials
1. Donor acceptor propertiesDonor to have lower ionization potential and acceptor to have higher electron affinity helps in charge transfer Optical absorption-Direct band gap materials Band gap-matching with max. solar flux Solubility- high solubility for solution processing E L H Donor Acceptor

2. 3. 4.

Conjugated Polymers

PPV,MEH-PPV, CN-PPV, MDMO-PPV, P3HT, POPT, and EHH-PpyPz

Small molecules

PTCDA

H2-Pc

PCBM

MDMO-PPV/PCBM system

How to control morphology

Selecting suitable solvent Composition between polymer and fullerene Solution concentration Controlling solvent drying rate Post deposition thermal treatment Controlled phase separation Chemical structure of materials

Effect of Solvent on morphology and efficiency of MDMO-PPV:PCBM organic solar cells

~09%
Toluene cast film

~2.5%
Cholorobenzene cast film

AFM Image showing surface morphology and derivative of actual surface height of MDMO-PVV:PCBM (1:4 by wt)
S. E. Shaheen, et al. Appl Phys. Lett, 78, 841 (2001).

Effect of thermal annealing on P3OT film

(a) (b)

(c)

(d)

SEM micrographs of P3OT films annealed at 373 K for different intervals of time (a) untreated, (b) 5hrs (c) 24 hrs (d) 72 hrs

Enhanced Thermal Stability and Efficiency of Polymer Bulk-Heterojunction Solar Cells by Low-Temperature Drying of the Active Layer
Adv. Funct. Mater. 2010, 20, 834839

Main challenges
Photon loss( most photons emitted by sun is in the range of 1.2-1.5eV).Optical absorption of OSCs are in the range of 2eV) Exciton loss (charge separation occurs at interfaces. Excitons have to reach the interfaces before they decay.Diffusion length ~10-70nm) Power loss: due to energy level difference between LUMO of donor and acceptor Charge carrier loss( traps, recombination,poor mobility, large interface barriers) Carrier collection loss (due to non-ohmic contacts)

Degradation
Photochemically: intrinsic property of the molecules or an extrinsic one (photooxydation with oxygen for instance) Electrochemically: ionic impurities or water may promote redox reactions at the electrodes. Structurally: low-Tg materials may reorganise, recrystallise, or diffuse one into another, owing to repeated heating and cooling in outdoor conditions Electrodes: they can react with the molecules, metal diffusion from ITO into polymers for instance

Effect of oxygen on the conductivity of fullerene

Thin Solid Films 441 (2003) 187191

Suggestions for stable of OPVs

Improvement of the stability of organic PV cells requires the choice of intrinsically stable materials (stable under storage, under sunlight and under reduction or oxidation conditions), the use of efficient purification methods, the choice of high-Tg materials and structures (stable under outdoor cooling or heating), a water an oxygen free fabrication technique (under a glove box, for instance), encapsulation of the structures after fabrication, etc. Proper heat dissipation, because unconverted light heats and eventually damages the cells

Future of OPVs
Organic photovoltaic have a great future. The efficiency of 8% has already been reported New tailor made materials with low band gap and high charge carrier mobility are being introduced. The rate of progress achieved is very high. In the near future we can expect highly efficient PV cells based on organic materials.

Thank you