Opto-Electronic Materials Section DCT,TNW Delft …March 20, 2008 1 Organic solar cells...
Transcript of Opto-Electronic Materials Section DCT,TNW Delft …March 20, 2008 1 Organic solar cells...
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March 20, 2008
1
Organic solar cells
Opto-Electronic Materials, DCT
Tom J. Savenije
Opto-Electronic Materials SectionDCT,TNW
Delft University of TechnologyThe Netherlands
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March 20, 2008 2
Outline
Why using organic materials
Fundamental aspects of organic semiconductors- energy levels in molecular materials- excitations in inorganic and organic SCs- exciton diffusion
Examples of organic solar cells- Dye sensitised solar cells- Polymer bulk heterojunction cells
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March 20, 2008 3
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties
O
O
*S*
n
C8H17 C8H17 NS
N
*
n
MDMO-PPV
rr poly (3,hexyl)thiophene
NC *
MeO
OR
CN
n
MeO
OR
CN-PPV
F8BT
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March 20, 2008 4
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties
- Variation of optical band-gap: colour- optimisation of the energy levels
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March 20, 2008 5
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties- large areas - low temperatures (RT)- processing from solution- roll to roll manufacturing- low substrate costs
From experience with organic LEDS
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March 20, 2008 6
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties- large areas - low temperatures (RT)- processing from solution- roll to roll manufacturing- low substrate costs
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March 20, 2008 7
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties- large areas - low temperatures (RT)- processing from solution- roll to roll manufacturing- low substrate costs
(Possible) problems- low mobility of charge carriers (p3.13)
vi = µiξv : velocityµ :mobilityξ : electric field
µn (c-Si) > 1000 cm2/Vsµh (polymer) ≈ 0.1 cm2/Vs
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March 20, 2008 8
Organic materials in Photovoltaic cells
Advantages- tailoring of opto-electronic properties- large areas - low temperatures (RT)- processing from solution- roll to roll manufacturing- low substrate costs
(Possible) problems- low mobility of charge carriers- photovoltaic performance (plastic cells: 5%, DSSC’s: 10%)- stability (10,00 hours minimum operational lifetime)
Crystalline silicon solar cells have efficiencies up to 20%combined with a lifetime > 20 years
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March 20, 2008 9
Cross section of typical c-Si solar cells(3.2)
n-type layer
absorber layer
Back contact
Front grid
Junction
p-type layer
ar layer
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March 20, 2008 10
Cross section of typical Si solar cells
n-type layer
Back contact
Incident light
Junction
p-type layerelectron/hole pairform on photon absorption
absorber layer
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March 20, 2008 11
Cross section of typical Si solar cells
n-type layer
Back contact
Junction
p-type layer
Diffusion of charge carriers
absorber layer
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March 20, 2008 12
Cross section of typical Si solar cells
n-type layer
Back contact
Junction
p-type layerCollection byinternal electric field
Front grid
absorber layer
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Homo Junction structure Va = 0 V(p 4.5 Chp 4)Internal electric field
n-type layer
ECB
EVB
Fermi level
p-type
Depletion layer
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March 20, 2008 14
Homo Junction structure Va = 0 V
Internal electric field
p-type n-type layer
ECB
EVB
Fermi level
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March 20, 2008 15
Homo Junction structure Va = 0 V
Internal electric field
p-type n-type layer
ECB
EVB
Fermi level
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March 20, 2008 16
Photovoltaic device based on molecular semiconductors?
Metal back contact
p-type organic layer
n-type organic layer
TCO
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March 20, 2008 17
Semiconductors (3.11)
Vacuum level
ECB
EVB
intrinsic
Electron affinity
Ionisation potential
Fermi levelForbidden gap
empty
1-3 eV
energy
Doping leads top-type orn-type SCs
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March 20, 2008 18
Molecular semiconductors
ECB
EVB
Inorganic semiconductor
Forbidden gap1-3 eV
HOMO
LUMO
molecular semiconductor
Highest occupied molecular orbital
Lowest unoccupied molecular orbital
Vacuum level
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March 20, 2008 19
Energy levels
Vacuum level
ECB
EVB
Inorganic semiconductor
Electron affinity
Ionisationpotential
HOMO
LUMO
molecular semiconductor
Oxidation potential
Reduction potential
NHE level
EHOMO ≈ -4.5 - e VOX
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March 20, 2008 20
n- or p-type molecular semiconductors
Molecular material with a high electron affinity:electron acceptor ⇒n-type semiconductor
Molecular material with a low ionisation potential:electron donor ⇒p-type semiconductor
HOMO
LUMO
ener
gy
Vacuum level
Ionisationpotential
Electron affinity
HOMO
LUMO
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March 20, 2008 21
Junction based on molecular semiconductors
n-type semiconductor:Electron acceptor
p-type semiconductor:electron donor
HOMO
LUMO
ener
gy
HOMO
LUMONo free charge carriers:no depletion layer no internal electric field
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March 20, 2008 22
Excitations in inorganic and molecular semiconductors
(isc vs msc)
A charge carrier becomes free from its Coulomb attraction to an opposite charge if the energy of attraction is less than kBT
E = q2
4πεε0rc
rc =q2
4πεε0kBT
q = electronic chargeε0 = permittivity of free spacerc = critical distance
If E =kBT
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March 20, 2008 23
Dependence of Rc
2
3
4
5
6
7
89
10
2
3
4
5
ε r
5 6 7 8 9100
2 3 4 5 6 7 8 91000
Temperature
1e-07
5e-08
4e-08 3e-08 2e-08 1e-08
5e-09 4e-09
3e-09 2e-09
1e-09
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March 20, 2008 24
Bohr radius
rB = r0ε
me
meff
rB = Bohr radius of carriersr0 = Bohr radius of hydrogen atom in the groundstate (0.53Å)ε = dielectric constantme = mass of free electron in vacuummeff = effective mass of electron in SC
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March 20, 2008 25
Bohr radius
rB = r0ε
me
meff
rB = Bohr radius of carriersr0 = Bohr radius of hydrogen atom in the groundstate (0.53Å)ε = dielectric constantme = mass of free electron in vacuummeff = effective mass of electron in SC
Excitation leads in case of
- isc to free charge carriers and
- msc to excitons (coulomb bound electron/hole pair)
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March 20, 2008 26
Photovoltaic device based on molecular semiconductors?
Metal back contact
p-type organic layer
n-type organic layer
TCO
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March 20, 2008 27
Excitation in organic junction
n-type semiconductor:Electron acceptor
p-type semiconductor:electron donor
HOMO
LUMO
Exciton: Coulombic bound electron hole/hole pair
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March 20, 2008 28
organic junction
n-type semiconductor:Electron acceptor
p-type semiconductor:electron donor
HOMO
LUMO
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March 20, 2008 29
Excitation near interface
n-type semiconductor:Electron acceptor
p-type semiconductor:electron donor
HOMO
LUMO∆G > Eexc
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March 20, 2008 30
Molecular based organic photovoltaic device
Phthalocyanine
p-type material
Perylenediimiden-type material
Tang, C.W., Two-layer organic photovoltaic cell. Appl. Phys. Lett, 1986. 48(2): p. 183-185.
η <=1%
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March 20, 2008 31
Voltage of molecular based organic photovoltaic devices
Tang, C.W., Two-layer organic photovoltaic cell. Appl. Phys. Lett, 1986. 48(2): p. 183-185.
n-type SCp-type SC
HOMO
LUMO
Opticalbandgap
Opticalbandgap
Effectivebandgap
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March 20, 2008 32
Current of molecular based organic photovoltaic device
n-type semiconductor:Electron acceptor
p-type semiconductor:electron donor
HOMO
LUMO
LEXC = DEXCτEXC
Transport of excitonsby diffusion (Chp 3):
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March 20, 2008 33
Molecular based organic photovoltaic device
p-type organic layer
n-type organic layer
TCO
LEXC LEXC
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March 20, 2008 34
Molecular based organic photovoltaic device
p-type organic layer
n-type organic layer
TCO
LEXC
Solution:increase the interfacial area
LEXC
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March 20, 2008 35
Outline
Why using organic materials
Fundamental aspects of organic semiconductors- excitations inorganic and organic SCs- energy levels in molecular materials- exciton diffusion
Examples of organic solar cells- Dye sensitised solar cells- Polymer bulk heterojunction cells
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March 20, 2008 36
Dye sensitised solar cells (Graetzel cells)
5 - 20 nm thicknanocrystalline TiO2
ElectrolyteSubstrate
TCO Dye:ruthenium complex
load
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March 20, 2008 37
Primary Processes
3S1
S 0
CB
dye
21
TiO2
VB
1: photo-excitation2: (non)radiative decay3: electron transfer
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March 20, 2008 38
Secondary Processes
3 S1
S 0
CB
dye
21
TiO2
VB
1: photo-excitation2: (non)radiative decay3: electron transfer
4: electron transport5: hole transport
6: recombination
4
5
6
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March 20, 2008 39
Electron transport via particles
5 - 20 nm thicknanoporous TiO2
ElectrolyteSubstrate
Negative pole Dye:ruthenium complex
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March 20, 2008 40
Hole transport by redox couple
Electrolyte Dye:ruthenium complex
2Dye+ + 2I- 2Dye + I2
Pt metal contactPositive pole
At dye/electrolyte interface
I2 + 2e- 2I- At electrolyte/Pt interface
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March 20, 2008 41
DSSCs on the market
dye_solar_cells.htm
•Copyright © Solaronix SA All Rights Reserved
•First large area dye solar cell modules •made with industrial materials & methods •45 x 45 cm surface, 33 serially connected cells
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March 20, 2008 42
Present developments on DSSC
- improvement of absorption of dye molecules to absorb all sun light with λ < 1000 nm
- omit the liquid phase by using solid state hole conductor to avoid leakage
- usage of ordered nanowires to optimize electron transport properties
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March 20, 2008 43
Polymer solar cells
Electron acceptor (A)
MDMO-PPV
hν
e-OMe
O
O
O
n
PCBM
Electron donor (D)
*S*
nP3HT
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March 20, 2008 44
Photovoltaic Cell
(Flexible) substrate
Blend: bulk heterojunction
Metal contact
- η: ca 5 %- Flexible - Cheap materials- Simple processing- Tunable color- Thin layers
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March 20, 2008 45
Nano morphology of bulk heterojunction (TEM)
PCBM
polymer
crystalline P3HT domain
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March 20, 2008 46
Polymer solar cells
PPVPCBM
1
2
4 6
5
3
7
1: Excitation2: Exciton migration3: (Non)radiative decay4: Charge separation5: Charge recombination6: Electron transport7: Hole transfer
VOC = 0.6 VIsc = 0.97 mA/cm2
FF = 0.68η = 5%
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March 20, 2008 47
Plastic solar cells on the market
•http://www.konarkatech.com
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Present developments on polymer solar cells
- Reduce bandgap of polymeric materials to absorb all sun light with λ < 1000 nm
- Optimize energy levels to avoid additional energy loss during charge separation
- enhance crystallinity of materials to improve charge carrier transport
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Questions
• Which factors do affect the potential in a polymer solar cell?• Calculate the critical distance in a photoactive blend layer with ε=4.5 at
room temperature• Calculate the minimum thickness of an organic blend layer consisting of a
1 tot 1 mixture of a conjugated polymer and a wide bandgap SC in order to absorb 90 % of the incident light. Neglect the reflection; the polymer has an α = 18x106m-1
• Calculate the average period it takes for an exciton to cross 5 nm in a molecular material. The exciton lifetime is 2 ns and the exciton diffusion length is 25 nm.