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Organic and polymer solar cells 3Y280

Organic and polymer solar cells 3Y280 Department of Chemical Engineering and Chemistry Department of Applied Physics

Department of Chemical Engineering and Chemistry Department of Applied Physics r.a.j.janssen@tue.nl

René Janssen

of Applied Physics r.a.j.janssen@tue.nl René Janssen Website: http://user.chem.tue.nl/janssen/solarcells3Y280.htm

Website:

http://user.chem.tue.nl/janssen/solarcells3Y280.htm

Website: http://user.chem.tue.nl/janssen/solarcells3Y280.htm transcripts of the slides text several review papers on the

transcripts of the slides

text

several review papers on the subject

old exam questions

Maximum photovoltaic solar cell efficiencies (%) and costs (€)

photovoltaic solar cell efficiencies (%) and costs (€) Status of 2005 40 35 30 25 20

Status of 2005

40

35

30

25

20

15

10

5

0

38 crystalline materials € € € € € € thin film materials € € €
38
crystalline materials € € € € € €
thin film materials € € €
organics €
24
increasing
19
19
13
10
5
3J
sc-Si
mc-Si
CIS
a-Si
dye polymer

Photosynthesis : or how coal, oil, gas and biomass are made today

N N O Mg N N O O O O
N
N
O
Mg
N
N
O O
O
O
CIS a-Si dye polymer Photosynthesis : or how coal, o il, gas and biomass are made
CIS a-Si dye polymer Photosynthesis : or how coal, o il, gas and biomass are made

How can we reach 20 TW PV-energy in 2050?

Required power:

20 TW

Sunlight:

1000 W/m 2 12 h a day

Efficiency:

10%

Required area:

400,000 km 2 = 20×10 12 /(1000 × 10% × 12/24)

Compare:

500,000 km 2 = Spain

How can we reach this area in ~30 years?

Required 36.5 km 2 solar cells a day

this is a strip of 365 km by 100 m every day for 30 years

The (only?) solution : plastic solar cells

Roll-to-roll production Lightweight Low cost Source: Konarka
Roll-to-roll production
Lightweight
Low cost
Source: Konarka

Organic and Polymer semiconductors

what is that?

or what happens if a molecule absorbs light and how can we make charges from there?

carbon

Ethene: C 2 H 4

H H

hydrogencarbon Ethene: C 2 H 4 H H C C H H double bond single bond

C C H H double bond
C
C
H
H
double bond

single bond

120
120

Counting electrons:

Every bond (

Ethylene has 12 electrons involved in bonding

) has 2 electrons

Wave functions and molecular orbitals

H H

C
C

H

C H
C
H
120
120
π orbital z H H C C H H x σ orbital σ orbital
π orbital
z
H
H
C
C
H
H
x
σ orbital
σ orbital

y

Molecular orbitals of the ethene molecule

-10 -5 0 5 10
-10
-5
0
5
10

r/a

orbitals of the ethene molecule -10 -5 0 5 10 r/a -10 -5 0 5 10
-10 -5 0 5 10
-10
-5
0
5
10

r/a

antibonding

molecular π∗ atomic p z atomic p z
molecular π∗
atomic p z
atomic p z

molecular π

bonding

Molecular orbital interpretation of UV-Vis absorption

π 6 ∗ π ∗ 4 π 5 ∗ π∗ π 3 ∗ π 4
π
6 ∗
π
4
π
5 ∗
π∗
π
3 ∗
π
4 ∗
251 nm
162 nm
217 nm
π
3
π
2
π
π
2
π
1
π
1

Representative absorption maxima for ultraviolet-absorbing compounds

Compound λ max (nm) Compound λ max (nm) 171 286 182 217 373 263 O
Compound
λ max (nm)
Compound
λ max (nm)
171
286
182
217
373
263
O
279
nπ*
188
ππ*
290
O
315
nπ*
210
ππ*
256
N
N
~350
188 ππ* 290 O 315 nπ* 210 ππ* 256 N N ~350 Extended π conjugation β-Carotene

Extended π conjugation

β-Carotene
β-Carotene
188 ππ* 290 O 315 nπ* 210 ππ* 256 N N ~350 Extended π conjugation β-Carotene

wavelength (nm)

188 ππ* 290 O 315 nπ* 210 ππ* 256 N N ~350 Extended π conjugation β-Carotene

Lycopene

Polymerization of acetylene to polyacetylene

H

H
H

C

H

H
H

C

H

H
H

C

H

C C
C
C
C
C
C
C
C
C

monomer

acetylene

H H C H H C H H C H C C C C C monomer
H C
H
C
H H C C C C C H H H
H H
C
C
C
C
C
H H
H
H C C H
H
C
C
H

polymer

polyacetylene

H

Molecular orbital interpretation construction of bands

π 6 ∗ π ∗ 4 π π∗ 5 ∗ π 3 ∗ π 4
π
6 ∗
π
4
π
π∗
5 ∗
π
3 ∗
π
4 ∗
π
3
π
2
π
π
2
π
1
π
1

molecules

5 ∗ π 3 ∗ π 4 ∗ π 3 π 2 π π 2 π
5 ∗ π 3 ∗ π 4 ∗ π 3 π 2 π π 2 π
5 ∗ π 3 ∗ π 4 ∗ π 3 π 2 π π 2 π

band gap

n
n

semiconductor

1977: Conducting π-conjugated polymers (polyacetylene)

Alternating single and double bonds Delocalized π-electrons

H H H H H H H H H H H H H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H

Conductivity up to 220 S/cm ! (AsF 5 dopant)

Nobel Prize in Chemistry 2000

π* band gap π
π*
band gap
π

E

Poly-paraphenylene: another conjugated polymer

2000 π* band gap π E Poly-paraphenylene: another conjugated polymer Aromatic structure H H C C

Aromatic structure

H H C C C C C C H H
H H C C C C C C
H H
C
C
C
C
C
C

H H

Molecular orbitals of benzene F E D B C A
Molecular orbitals of benzene
F
E
D
B
C
A

F

D E C B
D
E
C
B

A

orbitals of benzene F E D B C A F D E C B A D
D E
D
E
orbitals of benzene F E D B C A F D E C B A D

nodes at para position no interaction

antinodes at para position strong interaction

C B
C
B
a p o s i t i o n n o i n t e r

Benzene to poly-p-phenylene

F

D E

C B A
C
B
A

F

D
D

interaction

C
C

A

E band gap B
E
band gap
B

π-π* Band gaps of selected conjugated polymers

S n n
S
n
n
R S n
R
S
n

poly(isothionaphthalene)

poly(acetylene)

poly(3-alkylthiophene poly(3

E g = 1.0 eV

E g = 1.5 eV

E g = 1.9 eV

OCH 3 n CH 3 O poly(dimethoxyphenylene vinylene)
OCH 3
n
CH 3 O
poly(dimethoxyphenylene vinylene)

E g = 2.1 eV

n
n

poly(phenylene)

E g = 3.0 eV

vinylene) E g = 2.1 eV n poly(phenylene) E g = 3.0 eV O S R

O

S

R

= oxygen

= sulfur

= C 6 H 13

π-Conjugated polymers

π* LUMO
π*
LUMO
optical transition π HOMO
optical transition
π
HOMO

Conduction band

π* LUMO optical transition π HOMO Conduction band band gap Valence band resemble molecules and traditional

band gap

LUMO optical transition π HOMO Conduction band band gap Valence band resemble molecules and traditional

Valence band

resemble molecules and traditional semiconductors

A very important difference !

π* LUMO π HOMO
π*
LUMO
π
HOMO

Organic

semiconductors

light + - + -
light
+
-
+
-

Coulombically bound electron-hole pair

Conduction band

Inorganic

semiconductors

light - + - - + + Free charge carriers
light
-
+
-
-
+
+
Free charge carriers

Valence band

Charge generation ?

If excitation results in bound electron-hole pair how can we ever make a solar cell ?

Have a look at nature

Photosynthetic apparatus
Photosynthetic apparatus

The photosynthetic apparatus of purple bacteria consists of two types of pigment-protein complexes: the reaction centers and the light-harvesting complexes. The main function of the light-harvesting complexes is to gather light energy and to transfer this energy to the reaction centers for the photo- induced redox processes. In most purple bacteria, the photosynthetic membranes contain two types of light-harvesting complexes: light harvesting complex I (LH-I) and light harvesting complex II (LH-II). While LH-I is tightly bound to the photosynthetic reaction centers, LH-II is not directly associated with the reaction centers, but transfers energy to the reaction centers via LH-I.

Photosynthesis : or how coal, oil, gas and biomass are made today Reaction center sequential
Photosynthesis : or how coal, oil, gas and biomass are made today
Reaction center
sequential electron transfer
3 ps
1ps
200 ps
10 µs
1s
P*
Q A →
P
B A
H A
Q B

Photoinduced electron transfer

An organic or polymer solar cell contains two active components

the electron donor and electron acceptor

recombination
recombination

LUMO

absorption

electron transfer

LUMO

HOMO

acceptor recombination LUMO absorption electron transfer LUMO HOMO HOMO electron donor p-type electron acceptor n-type

HOMO

electron donor p-type

electron acceptor n-type

Organic solar cells : three types

Dye sensitized solar cells: Electrochemical cells Electrochemical cells

Small molecule organic solar cells: Made by vacuum deposition Made by vacuum deposition

Polymer solar cells: Made by solution, low temperature processing Made by solution, low temperature processing

Each of these cells face more or less the same challenges:

1. Increase power conversion efficiency

2. Increase stability

3. Develop a technology for large areas

Dye-sensitized TiO 2 solar cell operation principle

_ + Load SnO 2 Glass TiO 2 nanoparticles Redox electrolyte 3I - COOH I
_
+
Load
SnO 2 Glass
TiO 2 nanoparticles
Redox electrolyte
3I -
COOH
I
3 -
HOOC
N
N
SC
N
Ru
N
SC N
N
Light
HOOC
Counter electrode
COOH
Ruthenium Dye

M. Grätzel, Nature 1991, 353, 737.

Materials in DSSCs

Nc-TiO 2 covered with a Ru dye immersed in a liquid electrolyte containing 3I - /I 3

immersed in a liquid electrolyte containing 3I - /I 3 •Nanocrystalline TiO 2 , (10-30 nm)

•Nanocrystalline TiO 2, (10-30 nm) •High surface roughness

HOOC

HOOC

COOH

N N SC N Ru N SC N N
N
N
SC
N
Ru
N
SC N
N

COOH

• Ruthenium(II) + organic ligands

• Carboxylic acid surface groups

• Iodine/Iodide redox pair

-

Photoelectrochemical dye solar cell

(S*/S + ) e- Pt/TCO DV nanocrystalline TiO 2 film (ox/red) hν e- (S/S +
(S*/S + )
e-
Pt/TCO
DV
nanocrystalline
TiO 2 film
(ox/red)
e-
(S/S + )
redox electrolyte
solvent/gel
dye
e -
e -
Load

Efficiencies photoelectrochemical DSC/modules

• 11 % on < 1 cm 2 cells ;

• 7 % on 120 cm 2 module (12 devices)

5-8 % on 1-5 cm 2 cells

Best performance for a single cell so far

-15 -10 -5 AM1.5 (1000 W/mcm 2 ) J sc = 16.9 mA/cm 2 V
-15
-10
-5
AM1.5 (1000 W/mcm 2 )
J sc = 16.9 mA/cm 2
V oc = 0.87 V
FF = 0.75
η = 11.04%
0
0.0
0.2
0.4
0.6
0.8
Current Density mA/cm 2

Potential [V]

80

60

40

20

0

EQE = 83% 400 500 600 700 800
EQE = 83%
400
500
600
700
800

Wavelength [nm]

Photocurrent action spectrum obtained with the N719 dye attached to 16 + 4 µm nanocrystalline TiO2 film

Source: M Grätzel, EPFL

Towards a technology

attached to 16 + 4 µm nanocrystalline TiO2 film Source: M Grätzel, EPFL Towards a technology

Source: M Grätzel, EPFL

attached to 16 + 4 µm nanocrystalline TiO2 film Source: M Grätzel, EPFL Towards a technology
attached to 16 + 4 µm nanocrystalline TiO2 film Source: M Grätzel, EPFL Towards a technology

Organic double layer p/n cell

electron + transfer - absorption donor acceptor exciton dissociation into + and – charge carriers
electron
+
transfer
-
absorption
donor
acceptor
exciton dissociation into
+ and – charge carriers

ITO

Glass p-type Au light
Glass
p-type
Au
light

n-type

C. W. Tang, Appl. Phys. Lett. 1985, 48, 183.

light n-type C. W. Tang, Appl. Phys. Lett. 1985, 48 , 183. Organic photovoltaic cell LUMO

Organic photovoltaic cell

Appl. Phys. Lett. 1985, 48 , 183. Organic photovoltaic cell LUMO recombination absorption electron transfer LUMO

LUMO

recombination
recombination

absorption

electron transfer

cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor
cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor
cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor

LUMO

HOMO

electron donor p-type

cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor n-type

HOMO

electron acceptor n-type

cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor n-type
cell LUMO recombination absorption electron transfer LUMO HOMO electron donor p-type HOMO electron acceptor n-type

Donor and acceptor molecules

N N N N M N N N N
N
N
N
N M
N
N N
N

Phthalocyanin

N N M N N
N
N
M
N
N

Porphyrin

N O N N N O
N
O
N
N
N
O

Perylene derivatives

o r p h y r i n N O N N N O Perylene derivatives

Fullerene C 60

Organic double layer p/n cell is limited by the exciton diffusion length excitons created here
Organic double layer p/n cell is limited by the exciton diffusion length
excitons created here
are lost
active part
of the cell
excitons created here
are lost
+
+
-
-
20
nm
+
-

Bulk-heterojunction solar cells

light glass transparent electrode - - 100 nm metal electrode +
light
glass
transparent electrode
-
-
100 nm
metal electrode
+

nanoscopic mixing of donor and acceptor to overcome ~10 nm exciton diffusion length

R. H. Friend et al., Nature 1995, 376, 498

A. J. Heeger et al., Science 1995, 270, 1789

The actual plastic solar cell consists of several layers

metal electrode active polymer layer: two components conducting polymer transparent electrode + glass or plastic
metal electrode
active polymer layer:
two components
conducting polymer
transparent
electrode
+
glass or plastic
support
TEM graph
sun light
is absorbed by the active layer and
charges are formed that are transported
to the electrodes
-
-

Polymer solution processed cells come in three 'flavors'

Polymer fullerene

come in three 'flavors' Polymer – fullerene Polymer – polymer Polymer – inorganic metal interface

Polymer polymer

Polymer – fullerene Polymer – polymer Polymer – inorganic metal interface layer active layer

Polymer – inorganic

– fullerene Polymer – polymer Polymer – inorganic metal interface layer active layer transparent conductive
– fullerene Polymer – polymer Polymer – inorganic metal interface layer active layer transparent conductive
– fullerene Polymer – polymer Polymer – inorganic metal interface layer active layer transparent conductive
– fullerene Polymer – polymer Polymer – inorganic metal interface layer active layer transparent conductive

metal

interface layer

active layer

transparent

conductive

polymer

transparent

conductive

oxide

glass

20 nm

conductive polymer transparent conductive oxide glass 20 nm Sub-picosecond hole and elect ron transfer in the

Sub-picosecond hole and electron transfer in the blend

Pump 510 nm O ) n h+ ( e- O MDMO-PPV
Pump 510 nm
O
) n
h+
(
e-
O
MDMO-PPV
in the blend Pump 510 nm O ) n h+ ( e- O MDMO-PPV O OMe

O

in the blend Pump 510 nm O ) n h+ ( e- O MDMO-PPV O OMe

OMe

PCBM

blend Pump 510 nm O ) n h+ ( e- O MDMO-PPV O OMe PCBM Pump

Pump 670 nm

-0.8 -0.4 0.0 0.4 970 nm 0.8 488 nm 1.2 630 nm 0.5 1.0 1.5
-0.8
-0.4
0.0
0.4
970 nm
0.8
488 nm
1.2
630 nm
0.5
1.0
1.5
2.0
2.5
-∆T/T

Energy (eV)

-0.2

-0.1

0.0

0.1

0.2

0.3

510 nm 670 nm Probe 970 nm -5 0 5 10 15 ∆T/T
510 nm
670 nm
Probe 970 nm
-5
0
5
10
15
∆T/T

Time delay (ps)

Paul van Hal, Appl. Phys. A. 2004 , 79, 41.

Electron transfer reactions

A molecule in the excited state has lower oxidation potential and a higher electron affinity.

D* A
D*
A
D + A - D A*
D
+ A
-
D
A*

Recombination : monitor photoinduced bleaching in time

MDMO-PPV/PCBM blend (1:4)

80 K 0.1 -α t 0.01 1E-3 Laser power (mW): α: 0.13 0.46 1E-4 1.2
80 K
0.1
t
0.01
1E-3
Laser power (mW):
α:
0.13
0.46
1E-4
1.2
0.50
0.6
0.54
1E-5
10
100
1000
10000
100000
∆T/T

Time delay (ns)

Ton Offermans J. Chem. Phys, 2003, 119, 10924

Plastic solar cell contains two active components the electron donor and electron acceptor

O ) n metal ( interface layer O MDMO-PPV semiconducting polymer
O
)
n
metal
(
interface layer
O
MDMO-PPV
semiconducting polymer

transparent

conductive polymer

semiconducting polymer transparent conductive polymer O PCBM transparent conductive oxide glass OMe Sean
O PCBM
O
PCBM
transparent conductive oxide glass
transparent
conductive oxide
glass

OMe

Sean Shaheen et al., Appl. Phys. Lett. 2001, 78, 841 Jeroen van Duren, Adv. Funct. Mater. 2002, 12, 665.

2.5% efficient organic plastic solar cells

O ) n OMe OMe O O ( O
O
) n
OMe
OMe
O
O
(
O
MDMO-PPV PCBM 0.6 0.5 0.4 0.3 0.2 0.1 0.0 EQE
MDMO-PPV
PCBM
0.6
0.5
0.4
0.3
0.2
0.1
0.0
EQE

400 500 600 700 800 Wavelength [nm]

V OC = 0.87 V

0 -2 FF = 0.60 -4 J SC = 4.9 mA/cm 2 -6 0.0 0.2
0
-2
FF = 0.60
-4
J SC = 4.9 mA/cm 2
-6
0.0
0.2
0.4
0.6
0.8
1.0
Voltage (V)
( V × I
) max ≤
FF =
1
× I
V oc
sc
J
(mA/cm 2 )

Sean Shaheen et al., Appl. Phys. Lett. 2001, 78, 841 Martijn Wienk (ECN) and Jeroen van Duren (TU/e)

Importance of processing and morphology

Importance of processing and morphology O O ) n ( O Chlorobenzene η > 2.5 %

O

Importance of processing and morphology O O ) n ( O Chlorobenzene η > 2.5 %
Importance of processing and morphology O O ) n ( O Chlorobenzene η > 2.5 %
O ) n ( O
O
)
n
(
O

Chlorobenzene η > 2.5 %

5µm 200 nm
5µm
200 nm
O O ) n ( O Chlorobenzene η > 2.5 % 5µm 200 nm OMe Toluene

OMe

Toluene η < 1%

5µm 200 nm
5µm
200 nm

see also: T. Martens et al., Synth. Met. 2003, 138, 243

Joachim Loos and Xiaoniu Yang (TU/e)

Postproduction treatment (annealing) of P3HT:PCBM solar cells

treatment (annealing) of P3HT:PCBM solar cells Pavel Schilinsky, Appl. Phys. Lett. 2002, 81 , 3885 Franz

Pavel Schilinsky, Appl. Phys. Lett. 2002, 81, 3885 Franz Padinger, Adv. Funct. Mater 2003, 13, 85

C 6 H 13 n S O O
C
6 H 13
n
S
O
O

Me

I sc = 8.7 mA/cm 2 V oc = 580 mV FF = 0.55 η e = 2.8%.

P3HT:PCBM solar cells

annealing at 120 °C for 60 min on complete devices

cells annealing at 120 °C for 60 min on complete devices regioregular P3HT M w =

regioregular P3HT M w = 100000 g mol -1 M w /M n = 2.14

Xiaoniu Yang, TU/e

g mol - 1 M w / M n = 2.14 Xiaoniu Yang, TU/e V o

V oc = 0.615 V FF = 0.61 J sc = 7.2 mA cm -2 η e = 2.7 % AM1.5 1000 W/m 2

= 7.2 mA cm - 2 η e = 2.7 % AM1.5 1000 W/m 2 after

after spin coating from chlorobenzene

P3HT

0.39 nm*

W/m 2 after spin coating from chlorobenzene P3HT 0.39 nm* PCBM 0.46 nm after annealing at

PCBM

0.46 nm

spin coating from chlorobenzene P3HT 0.39 nm* PCBM 0.46 nm after annealing at 110 °C for

after annealing at 110 °C for 60 min

P3HT

0.39 nm*

nm after annealing at 110 °C for 60 min P3HT 0.39 nm* PCBM 0.46 nm *

PCBM

0.46 nm

annealing at 110 °C for 60 min P3HT 0.39 nm* PCBM 0.46 nm * P3HT whiskers:

* P3HT whiskers: K.J. Ihn, J. Moulton, P. Smith, J. Polym. Sci. Part B: Polym. Phys. 1993, 31, 735.

Stability : encouraging but needs improvement

Stability : encouraging but needs improvement Sjoerd Veenstra, Wiljan Ve rhees & Jan Kroon (ECN) P3HT:PCBM

Sjoerd Veenstra, Wiljan Verhees & Jan Kroon (ECN)

P3HT:PCBM solar cells via slow drying process

O O
O
O

Me

C 6 H 13 n S
C
6 H 13
n
S
V FF EQE η J SC OC 12.50 0.604 0.594 66 4.5% 10 5 0
V
FF
EQE
η
J SC
OC
12.50
0.604
0.594
66
4.5%
10
5
0
-5
-10
-15
-0.5
0.0
0.5
1.0
current density (mA/cm 2 )

Bias (V)

0.7 J(SR) = 9.27 mA/cm 2 0.6 0.5 0.4 0.3 0.2 0.1 0.0 400 500
0.7
J(SR) = 9.27 mA/cm 2
0.6
0.5
0.4
0.3
0.2
0.1
0.0
400
500
600
700
800
EQE (%)

Wavelength (nm)

G. Li et al.,Nature Mater. 2005, 4, 864.

Jan Gilot (TU/e)

Polymer (donor) : PCBM (acceptor) solar cells

Polymer (donor) : PCBM (acceptor) solar cells Efficiency   2.5% MDMO-PPV 0.87 V 4.2% S N

Efficiency

 

2.5%

MDMO-PPV

0.87 V

4.2%

S N N S S C 10 C 10
S
N
N
S
S
C 10
C 10

C

6 H 13

n

1.00 V

4.4%

S n
S
n

P3HT

0.61 V

 

C 8 H 17

C 8 H 17

C 8 H 17

5.5%

0.65 V

S

S

n

PCPDTBT

N N
N
N

S

PF10TBT

O O
O
O

Me

PCBM

S.

E. Shaheen, Appl. Phys. Lett. 2001, 78, 841.

L.

H. Slooff, Appl. Phys. Lett. 2007, 90, 143506.

Y.

Kim, Nature Mater. 2006, 5, 197.

J.

Peet, Nature Mater. 2007, 6, 497.

Polymer:polymer solar cells using PF1CVTP

OC 10 H 21 n MeO
OC 10 H 21
n
MeO
CN MeO S S n NC OC 10 H 21 H 17 C 8 C
CN
MeO
S
S
n
NC
OC 10 H 21
H 17 C 8
C 8 H 17

MDMO-PPV

PF1CVTP

AM1.5G conditions:

J sc = 3.0 mA/cm 2 V oc =1.40 V FF = 0.37 η = 1.5% EQE = 52% at 530nm

V o c =1.40 V FF = 0.37 η = 1.5% EQE = 52% at 530nm

Marc Koetse et al., Appl. Phys. Lett. 2006, 88, 083504

O n O
O
n
O
O n O MDMO-PPV:ZnO hybrid solar cells vacuum 3.0 - hν + 5.3 4.4 4.3 Al

MDMO-PPV:ZnO hybrid solar cells

vacuum

3.0 - hν + 5.3
3.0
-
+
5.3

4.4

hybrid solar cells vacuum 3.0 - hν + 5.3 4.4 4.3 Al 5.0 7.6 ZnO PEDOT:
hybrid solar cells vacuum 3.0 - hν + 5.3 4.4 4.3 Al 5.0 7.6 ZnO PEDOT:

4.3

Al

5.0

hybrid solar cells vacuum 3.0 - hν + 5.3 4.4 4.3 Al 5.0 7.6 ZnO PEDOT:

7.6

solar cells vacuum 3.0 - hν + 5.3 4.4 4.3 Al 5.0 7.6 ZnO PEDOT:  

ZnO

PEDOT:

 

PSS

MDMO-

PPV

20 nm.
20 nm.
MDMO-PPV:nc-ZnO PEDOT: Al blend PSS ITO Glass
MDMO-PPV:nc-ZnO
PEDOT:
Al
blend
PSS
ITO
Glass

Waldo Beek (TU/e)

Choice of acceptors in bulk heterojunctions

Polymer fullerene

of acceptors in bulk heterojunctions Polymer – fullerene 5.5% Polymer – polymer 1.8% Polymer – inorganic

5.5%

Polymer polymer

1.8%
1.8%

Polymer – inorganic

5.5% Polymer – polymer 1.8% Polymer – inorganic 2.8% Examples: [60]PCBM and [70]PCBM ☺ Good

2.8%

Examples: [60]PCBM and [70]PCBM

Good performance, high e-mobility, easy processing

Morphologically not very stable, low light absorption

Examples: F8BT, PCNEPV,

High light absorption, easy processing

Low mobility (traps), large phase separation

Examples: CdSe, TiO 2 , ZnO

Stable morphologies (?), high e-mobility

Low light absorption, difficult processing

Towards a technology source: Siemens/Konarka
Towards a technology
source: Siemens/Konarka
Towards a technology source: Siemens/Konarka Roll-to-roll on its way source : Konarka, March 2008

Roll-to-roll on its way

source : Konarka, March 2008

Status and challenges

Efficiencies of 4-5% have been reached

The performance is an intricate combination of:

photophysics charge transport nanoscale morphology electrodes and device architecture

What remains to be done:

new materials to increase voltage and spectral overlap increase transport and collection establish long lifetimes develop a real technology

State-of-the-art solar P3HT cells

O Me O n S PCBM P3HT
O
Me
O
n
S
PCBM
P3HT

photon energy > 1.9 eV !!!!!

FF = 0.65

V oc = 0.62 V

energy > 1.9 eV !!!!! FF = 0.65 V o c = 0.62 V 6 14.3%
6 14.3% 4 2 0 500 1000 1500 2000 2500 3000 3500 Photons In (x
6
14.3%
4
2
0
500
1000
1500
2000
2500
3000
3500
Photons In (x 10 -18 )
Electrons Out
Power In

0.20

0.15

0.10

0.05

0.00

4.0% 500 1000 1500 2000 2500 3000 3500 Power Out
4.0%
500
1000
1500
2000
2500
3000
3500
Power Out

Wavenlength (nm)

Wavelength (nm)

Voltage Loss: 1.9 0.6 eV

1.9 eV

P3HT

PCBM

3.3 5.2
3.3
5.2

driving force for charge separation = 0.9 eV

4.2

HOMO D -LUMO A = 1.0 eV

loss at electrodes 2 x ~0.2 = 0.4 V

V oc 0.62 V

J. Halls et al., Phys Rev B. 1999, 60, 5721 V. Mihailetchi et al., J. Appl. Phys. 2003, 94, 6849 M. C. Scharber et al., Adv. Mater. 2006, 18, 789

Low band gap materials

must be carefully designed

loss of voltage electron transfer voltage voltage donor acceptor donor acceptor
loss of voltage
electron
transfer
voltage
voltage
donor
acceptor
donor
acceptor
electron transfer voltage voltage donor acceptor donor acceptor loss of electron transfer voltage donor acceptor

loss of electron transfer

voltage donor acceptor
voltage
donor
acceptor

Theoretical efficiencies

Wavelength (nm)

20 ∆E CS = 0.2 eV 15 10 5 ∆E CS = 0.9 eV 0
20
∆E CS = 0.2 eV
15
10
5
∆E CS = 0.9 eV
0
2.0
1.5
1.0
Theroretical Efficiency (%)
600
800
1000
1200
1400
1600
1800
2000

Band gap energy (eV)

assuming: FF = 0.7, EQE = 0.9 and 0.2 V loss at each electrode

H

O O O O S N O S C 12 H 25 S O N
O
O
O
O
S N
O
S
C 12 H 25
S
O N
S
n
pBBTDPP2
[60]PCBM
[70]PCBM

25 C 12

Improved solar cell performance PBBTDPP2 :PCBM (1:2)

0.5 0.4 0.3 0.2 0.1 0.0 400 500 600 700 800 900 EQE
0.5
0.4
0.3
0.2
0.1
0.0
400
500
600
700
800
900
EQE

wavelength (nm)

10 5 0 -5 -10 -15 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 current
10
5
0
-5
-10
-15
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
current density (mA/cm 2 )

voltage (V)

 

J

SC

(mA/cm 2 )

FF

V

OC

(V)

η

(%)

PBBTDPP2:[60]PCBM

9.4

0.54

0.63

3.2

PBBTDPP2:[70]PCBM

11.3

0.58

0.61

4.0

M. Wienk, M. Turbiez, J. Gilot

Multi-junction polymer solar cells

wide band low band metal gap BHJ gap BHJ e - e - h +
wide band
low band
metal
gap BHJ
gap BHJ
e
-
e
-
h
+
h
+
n
p

AM1.5 1000 W/m 2

recombination junction

30% for a single band gap cell 42% for a tandem cell, 49% for a triple junction device 68% for an infinite stack

Organic tandem cell with interstitial Au contact

metal-free phthalocyanine N,N'-diemethylperylenediimide
metal-free phthalocyanine
N,N'-diemethylperylenediimide

M. Yokoyama, Chem. Lett. 1990, 327

Aim: create transparent electron and hole transporting layers that enable efficient recombination of charges

e - h + e - h +
e
-
h
+
e
-
h
+

Back cell

Recombination layer

Front cell

I,V
I,V

ZnO in

acetone

Light

Hole transporting layer

Contact layer

Electron transporting layer

20 nm.
20 nm.

Solution-processed double junction solar cell with hole and electron transporting layers

- + LiF/Al P3HT:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT:PSS ITO Glass
-
+
LiF/Al
P3HT:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT:PSS
ITO
Glass

V oc = 1.34 V I sc = 2.7 mA/cm 2 FF = 0.37 MPP = 1.3 mW/cm 2

1 0 -1 -2 front cell -3 back cell tandem -4 0.0 0.5 1.0 1.5
1
0
-1
-2
front cell
-3
back cell
tandem
-4
0.0 0.5
1.0
1.5
2.0
Current Density (mA/cm 2 )

Voltage (V)

5 solution processed layers on top of each other

PEDOT: Orgacon from Agfa

Few seconds exposure to UV irradiation

- + LiF/Al P3HT:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT:PSS ITO Glass
-
+
LiF/Al
P3HT:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT:PSS
ITO
Glass

V oc = 1.34 V I sc = 2.7 mA/cm 2 FF = 0.37 MPP = 1.3 mW/cm 2

1 0.75 V 0.82 V 0 1.53 V -1 -2 -3 front cell back cell
1
0.75 V
0.82 V
0
1.53 V
-1
-2
-3
front cell
back cell
tandem
tandem + UV
-4
0.0 0.5
1.0
1.5
2.0
Current Density (mA/cm 2 )
+ UV -4 0.0 0.5 1.0 1.5 2.0 Current Density (mA/cm 2 ) Voltage (V) V

Voltage (V)

V oc = 1.53 V I sc = 3.0 mA/cm 2 FF = 0.40 MPP = 1.8 mW/cm 2

J. Gilot, Appl. Phys. Lett. 2007, 90, 143512

Solution-processed triple junction solar cell with hole and electron transporting layers

- + LiF/Al P3HT:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT:PSS ITO Glass
-
+
LiF/Al
P3HT:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT:PSS
ITO
Glass
1 0.75 V 2 x 0.82 V 0 -1 2.19 V -2 -3 front cell
1
0.75 V
2 x 0.82 V
0
-1
2.19 V
-2
-3
front cell
back cell
triple junction
-4
0.0
0.5
1.0
1.5
2.0
2.5
Current Density (mA/cm 2 )

Voltage (V)

8 solution processed layers on top of each other processing time ~10 min.

V oc = 2.19 V I sc = 2.6 mA/cm 2 FF = 0.37 MPP = 2.1 mW/cm 2

Appl. Phys. Lett. 2007, 90, 143512

- + LiF/Al P3HT:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT ZnO MDMO-PPV:PCBM PEDOT ZnO
-
+
LiF/Al
P3HT:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT
ZnO
MDMO-PPV:PCBM
PEDOT:PSS
ITO

Glass V oc = 3.46 V I sc = 1.6 mA/cm 2 FF = 0.32 MPP = 1.7 mW/cm 2

I s c = 1.6 mA/cm 2 FF = 0.32 MPP = 1.7 mW/cm 2 Six-fold

Six-fold Junction

Large stacks: six-fold junction

17 solution processed layers on top of each other

1 0 -1 -2 Single junction Double junction Triple junction Six fold junction -3 Current
1
0
-1
-2
Single junction
Double junction
Triple junction
Six fold junction
-3
Current Density (mA/cm 2 )

01234

Voltage (V)

junction -3 Current Density (mA/cm 2 ) 01234 Voltage (V) V o c = 1.53 V

V oc = 1.53 V I sc = 3.0 mA/cm 2 FF = 0.40 MPP = 1.8 mW/cm 2

Double Junction

mA/cm 2 FF = 0.40 MPP = 1.8 mW/cm 2 Double Junction V o c =

V oc = 0.75 V I sc = 3.5 mA/cm 2 FF = 0.48 MPP = 1.3 mW/cm 2

Single Junction

V oc = 2.19 V I sc = 2.6 mA/cm 2 FF = 0.37 MPP = 2.1 mW/cm 2

Triple Junction

Preliminary results from solar simulator

- + LiF/Al PBBTDPP2:PCBM n PEDOT ZnO PF10TBT:PCBM PEDOT:PSS ITO Glass
-
+
LiF/Al
PBBTDPP2:PCBM
n PEDOT
ZnO
PF10TBT:PCBM
PEDOT:PSS
ITO
Glass

78 nm

155 nm

1 0 -1 -2 -3 -4 -5 -6 0.0 0.5 1.0 1.5 2.0 Current Density
1
0
-1
-2
-3
-4
-5
-6
0.0
0.5
1.0
1.5
2.0
Current Density (mA/cm 2 )

Voltage (V)

Predicted current

5.3 mA/cm 2

TU/e

J SC (SR) = 5.3 mA/cm 2 V OC = 1.57 V FF = 0.47 η est = 3.9 %

Solar simulator (ECN)

J SC (SS) = 5.0 mA/cm 2

V OC = 1.54 V FF = 0.46 η = 3.6 %

one

month

later

after UV illumination

Preliminary spectral response measurement

- + LiF/Al PBBTDPP2:PC 60 BM PEDOT ZnO PF10TBT:PC 60 BM PEDOT:PSS ITO Glass
-
+
LiF/Al
PBBTDPP2:PC 60 BM
PEDOT
ZnO
PF10TBT:PC 60 BM
PEDOT:PSS
ITO
Glass

Red Bias

6.58 mA/cm 2

Green Bias

6.40 mA/cm 2

Predicted value

I sc = 6.56 mA/cm 2

100 nm 245 nm 0.5 Red Bias 0.4 Green Bias 0.3 0.2 0.1 0.0 400
100
nm
245
nm
0.5
Red Bias
0.4
Green Bias
0.3
0.2
0.1
0.0
400
500
600
700
800
900
1000
Spectral Response

Wavelength (nm)

Summary

Dye sensitized solar cells reach ~11% efficiency Organic / polymer solar cells reach ~5% efficiency Both types are being developed at academia and industry

Important future developments:

a. Increase efficiency

b. Increase lifetime

c. Develop low cost technology based on a and b

Results will depend on

a. New improved materials

b. New device architectures

c. Simple technologies

based on a and b Results will depend on a. New improved materials b. New device
based on a and b Results will depend on a. New improved materials b. New device
based on a and b Results will depend on a. New improved materials b. New device
based on a and b Results will depend on a. New improved materials b. New device