Organic,

Organic, “Plastic”
“Plastic” Photovoltaics
Photovoltaics

Niyazi
NiyaziSerdar
SerdarSARICIFTCI
SARICIFTCI
Linz
LinzInstitute
Institutefor
forOrganic
OrganicSolar
SolarCells
Cells(LIOS),
(LIOS),
Physical
PhysicalChemistry,
Chemistry,Johannes
JohannesKepler
KeplerUniversity
UniversityLinz
Linz
Austria
Austria
 CONTENTS

Part 1: Introduction to plastic solar cells

Photoinduced electron transfer from conjugated
polymers onto fullerenes
Part 2: Nanomorphology of the donor-acceptor composites
Transport of charge carriers
“Double Cable” materials
Part 3: Photon harvesting
Optical absorption of conjugated polymers
Low band gap polymers
 Device Geometries

BILAYER BULK HETEROJUNCTION

- + - +
Aluminum Aluminum

PEDOT-PSS P EDOT-PSS
ITO ITO
Plastic foil Plastic foil

Light Light

MDMO-PPV MDMO-PPV
PCBM PCBM
 Small Molecular
Organic Solar Cells

“Tang- Cell“

C. W. Tang
Appl.Phys. Lett. 48(86)183
 e-
WORKING PRINCIPLE RO
OR O
OMe

OR

Photoexcitation in conjugated polymers

RO

OR

RO
n

Conjugated Polymer

LUMO

Exciton
Diffusion
≈ 5-15 nm

HOMO
 e-
WORKING PRINCIPLE RO
OR O
OMe

OR

Photoexcitation in conjugated polymers

RO

OR

RO
n

Conjugated Polymer

nanosecond range
LUMO

Non radiative
recombination

Radiative
recombination
Heat

HOMO
 e-
WORKING PRINCIPLE RO
OR O
OMe

OR

Ultra-fast charge transfer

RO

OR

RO
n

Conjugated Polymer

LUMO

Exciton
Diffusion Need to dissociate
≈ 5-15 nm the exciton...

HOMO
 e-
WORKING PRINCIPLE RO
OR O
OMe

OR

Bi-layer polymer solar cells

RO

OR

RO
n

[eV] vs vacuum

-3 LUMO

-3.5

-4 LUMO

-4.5
DONOR ACCEPTOR
“P" “N"
-5
HOMO

-5.5 ITO PEDOT Al

PSS
-6
HOMO
 Schematic Band Diagram
π∗ MEH-PPV
π∗ MEH-PPV
2.8 eV

LUMO C60 Eg LUMO C60

3.7 eV
Eg
4.7 eV 4.3 eV
EF
5 eV π MEH-PPV
Al
ITO
ITO π MEH-PPV Al

HOMO
6.1 eV C60
HOMO C60

Metal-Insulator-Metal (MIM) picture

implies the field of assymetric metal electrodes
(All interface effects neglected!)
 Band Models

vacuum level vacuum level

Ip χS
- + φM2 CB φM2
CB - + hν
- +

W
φM1 φM1
Eg
metal 2
+ P+
hν -
Eg
P- low workfunction
VB high workfunction
metal metal
metal 1
VB
conjugated polymer

conjugated polymer

Schottky Contacts for MIM Picture for

high Impurities low Impurities
n >> 1017cm-3 n << 1017cm-3
 e-
WORKING PRINCIPLE RO
OR O
OMe

OR

Bulk-heterojunction
RO

OR

RO
n

"Bulk Heterojunction " MDMO-PPV / PCBM 1:4

5
4
Current Density (mA/cm )
2

3
2
1
Isc = 5.25 mA/cm²
0 Voc = 820 mV
-1 FF = 0.61
-2 η = 2.5%
-3
-4
-5
-6
0.0 0.2 0.4 0.6 0.8 1.0
Voltage (V)
 Intensity Dependence of Photocurrent

Scaling Coefficient α ~ 0.92

AM 1.5 Intensity Scaling of New Generation Device
Photocurrent [A/10 mm ]
2

1E-4 B
C
D
0 V; α = 0.915
-1 V; α = 0.916
-2 V; α = 0.912

1E-5
1 10 100
2
Am 1.5 Intensity [mW/cm ]
 Voc vs LUMO of Acceptor

0,85
PCBM
0,80 (a)
S1 = 0.95
0,75
Voltage [V]

0,70
azafulleroid 5 C60
0,65

0,60

0,55 ketolactam 6

-0,70 -0,65 -0,60 -0,55

1
E Red
[V]
Brabec et al., Advanced Functional Materials (2001), 11, No.5, 374-380
.
 Voc vs HOMO of the Polymer Donor

Δ : Ip – LUMO level of C60

2.8 eV 3.08 eV
3.31 eV
C60 LUMO
3.9 eV
Δ 1
2 3
4.9 eV
5.42 eV
5.44 eV
MEH-PPV p-DMOP-PPV
p-DMOP-co-
MEH-PPV (7:3)

•High PL Quantum Efficiency Materials 1 2 3

•High Ionization Potential Materials Q.E. 10% 40% 23%

Kwanghee Lee et al, Pusan Univ. Korea

Plastic
Plastic Solar
Solar Cells
Cells

Production
Production Scheme
Scheme
 Plastic Solar Cells - SUBSTRATES
Substrates are available in any scale. They are flexible and transparent

Polyester
Insulating String
ITO 6 cm
We use Indium Tin
Oxide (ITO)
6 cm coated polyester
foils or glasses.
R ~ 10-100 Ω/cm2

Substrates are cut

in the desired size
and cleaned in
common organic
solvents in a
ultrasonic bath.
 WHY Plastic Solar Cells - MATERIALS
The electroactive compounds can be already bought from
companies. Prices are appr. 300 - 500 US$/gram for the
polymers, fullerenes are appr. 20 - 50 US$/gram.

Polymers and Fullerenes are

dissolved in common organic
solvents. 1 gram yields appr.~
200 ml solution

Different colors of the solutions correspond

to different spectral sensitivities - Band Gap Tuning
 Plastic Solar Cells - FILM PREPARATION

Spin Casting is a easy coating

technique for small areas. Material
loss is very high. Doctor Blade Technique
was developed for large
area coating

Doctor Blade Technique

has no material loss

FILM THICKNESS IS ~ 100 nm

 Production - Large Area

Large Area Thin Film Production using Doctor/Wire Blading

1 2

a)

b)
 Production - Large Area

Large Area Thin Film Production Using Screen Printing

Squeegee
Screen

Polymer Film
Substrate

1000

100

Current Density (mA/cm )

2
10

0,1

0,01

1E-3

1E-4

1E-5

1E-6
-2,0 -1,5 -1,0 -0,5 0,0 0,5 1,0 1,5 2,0
Voltage (V)

S. Shaheen, R. Radspinner, N. Peygambarian, G. Jabbour, Appl. Phys. Lett. 79, 2996 (2001)
Plastic Solar Cells - SUMMARY
 Anomalous Temperature Dependence
0,248
0,88
0,244
0,87

Isc, mA
Voc, V

0,86 0,24

0,85
0,236
0,84

0,83 0,232
30 35 40 45 50 55 60 30 35 40 45 50 55 60
0
temperature, 0C temperature, C

1,96

1,92
efficiency, %

Eugene Katz,
1,88
David Faiman, et al
Journal of Applied Physics,
1,84 Vol 90, (2001), 5343-5350

1,8
30 35 40 45 50 55 60
temperature, 0C
Outdoor Experiment in
Negev Desert Israel
 Photoinduced Electron Transfer
From Conjugated Polymers onto Fullerenes
 Intermediate Steps in Photoinduced Electron Transfer

D + A + hυ → 1,3D* + A π- π* excitation of the donor

1,3D* + A → 1,3 (D…A)* Excitation delocalised on D-A

complex, (exciplex formation)

1,3 (D…A)* → 1,3 (Dδ+…Aδ-)* Formation of charge transfer

complex (Mulliken type)

1,3 (Dδ+…Aδ-)* → 1,3 (D+…A-)* Radical pair formation

1,3 (D+…A-)* → D+ + A- Complete charge separation

 Photoinduced Charge Generation

An ultrafast e- transfer occurs between Conjugated Polymer / Fullerene composites upon

illumination. The transition time is less than 40 fs. The Internal Quantum efficiency of
charge generation is therefore ~100%.

DONOR ACCEPTOR

O n

MDMO PPV PCBM

3,7 - dimethyloctyloxy methyloxy 1-(3-methoxycarbonyl) propyl-1-phenyl [6,6]C61
PPV

N. S. Sariciftci, L. Smilowitz, A. J. Heeger and F. Wudl., Science 258, 1474 (1992)

 Photoinduced Charge Generation

Energy

CB

LUMO

VB
HOMO

Semiconducting Polymer
Acceptor

N. S. Sariciftci, L. Smilowitz, A. J. Heeger and F. Wudl., Science 258, 1474 (1992)

 Photoinduced Charge Generation

×10-2

×10-4
N. S. Sariciftci, L. Smilowitz, A. J. Heeger and F. Wudl., Science 258, 1474 (1992)
 Photoinduced Charge Generation

1/τPL = 1/τo + 1/τet

1/τPL ≈ 1/τo,
and the PL intensity is correspondingly reduced;
(IPL) / (IPL)o ∼ τet/τo
(IPL) / (IPL)o ≈ 10-3. τPL ≈ 600 ps for MEH-PPV,
τet << 1 ps.

Lemmer et al, 1995

Transient Photoconductivity

Peak Photocurrent as well as the

lifetime of the charge carriers are
enhanced upon increasing the C60
content in the composite.

Changhee Lee et al.,

Phys. Rev. B 48, 15425 (1993)
 Enhanced Photoconductivity

Steady state photoconductivity of conjugated polymer is enhanced by several orders of

magnitude upon adding C60. Changhee Lee et al., Phys. Rev. B 48, 15425 (1993)
 Light Induced Electron Spin Resonance

LESR of Poly(3-octylthiophene) + C60

(1:1 weight %), Ar+ Laser 488nm 100mW/cm2, 80 K
N. S. Sariciftci, et al., Int. J. Mod. Phys. B8, 237 (1994)

Integrated LESR
Intensities
 Subpicosecond Photoinduced Absorption

P3OT

• Photoinduced absorption changes

within one picosecond.

• Dichroic ratio (polarization

memory) is lost within 500 fs.
P3OT+ 1% C60

B. Kraabel, et al., Phys. Rev. B 50, 18, (1994)

 Ultrafast Femtosecond Studies

Photoinduced electron transfer quenches the coherent excitation of vibrations.

Fourier Transform of the ∆T oscillations results in Raman spectrum

15

10
Polymer

Raman Intensity [a. u.]

5
∆T [a. u.]

0
Polymer/C60
-5

-10 800 1000 1200 1400 1600 1800 2000

0,0 0,2 0,4 0,6 0,8 1,0
−1
Time [ps] Energy [cm ]

Pump: 10 fs pulses peaking at 540 nm

Probe: same pulse with filter at 650 nm C. J. Brabec et al.,
Chem. Phys. Lett. 340, 232 (2001)
 Nanomorphology of the
donor-acceptor composites
 Bulk Heterojunction Device Structure

A B C
AFM 200 nm TEM 200 nm
metal

interface layer

active layer

transparent
conductive
polymer
transparent
conductive
oxide

glass

Rene Janssen et al, 2004

 Bulk Heterojunctions

e-
Al Electrode
Al Electrode
e- e- e-
P+
e-
e-
e-
e-
P+
ITO on Glass / Plastic

PCBM hν Alkoxy-PPV
 3-D Percolation

Strong luminescence quenching occurs at appr. 1 mol% of PCBM in alkoxy-PPV.

Photocurrent onset at appr. 17 mol% PCBM, in accordance with percolation theory.

1,0 1,0

Lum Intensity [a. u.]

Luminescence
Isc
0,8 0,8
Isc [a. u.]

0,5 0,5

0,3 0,3

0,0 0,0
0,1 1 10 100

Concentration of PCBM [mol%]

 Property Optimization
Molecular Structure
Molecular Engineering

Structure Property

Interchain
Self Organization (Intermolecular)
Interactions

Nanomorphology
 Nanomorphology: Solvent Effects
a

Toluene cast film

Surface Height (nm)

(a)
8

-4
0.0 0.5 1.0 1.5 2.0 2.5
0.5 µm Distance ( µ m)

b
Surface Height (nm)

(b)
8
Cholorobenzene cast film
4

-4
0.0 0.5 1.0 1.5 2.0 2.5
Distance ( µ m)
0.5 µm
 Morphology: Solvent effects

100 0
Transmission (%)

90

Current Density (mA/cm )

-1

2
80
70
60 -2
50
-3
60
50 -4
IPCE (%)

40
30
-5
20 from toluene
10 from chlorobenzene
0 -6
400 450 500 550 600 650 700 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Wavelength (nm) Voltage (V)

A 2-3 fold increase of the IPCE and short circuit current was observed by S.E.
Shaheen et al.* due to the change from toluene to chlorobenzene as solvent, while
by AFM measurements a decrease in the surface roughness was detected.

*S.E. Shaheen, C.J. Brabec, N.S. Sariciftci, F. Padinger, T. Fromherz, J.C. Hummelen, Appl. Phys. Lett. 78, 841 (2001)
 Nanomorphology: Solvent Effects
Improved performance: higher mobility
Au contacts
( drain and source) VG = 0
Organic semiconducting 0.0
layer O -7
-2.0x10
-7
SiO2 n -4.0x10
-7
MDMO-PPV -6.0x10
-7
O -8.0x10
-6

IDS
Al contact (gate) -1.0x10
-6
-1.2x10
O
-6
-1.4x10
OMe
-6
-1.6x10 VG = -60
µ FEWCox
(V − Vt )
-6

I dssat = gs
2
PCBM
-1.8x10
-6
Toluene
2L -2.0x10
-80 -60 -40 -20 0
VG = 0
VDS
µ FEWCox
(V − Vt )Vds
0.0
I dslin = gs
L -2.0x10
-6

-6
-4.0x10
Field Effect Transistors with
-6
-6.0x10

IDS
Conjugated Polymer as
-6
-8.0x10
Active Layer
-1.0x10
-5
VG = -60
Mobility calculated from linear and saturation regime using
long integration times -1.2x10
-5
Chlorobenzene
-80 -60 -40 -20 0
Wim Geens et al, Organic Electronics 3, 105 (2002)
VDS
Toluene concentration series –
MDMO-PPV:PCBM

1:4 1:2

1:3 1:1
 Nanomorphology Effects-SEM Studies

Harald Hoppe et al. Adv. Func. Mater. 14, (2004) 1005,

 ...and from Chlorobenzene?

1:4

Harald Hoppe et al. Adv. Func. Mater. 14, (2004) 1005,

Nanomorphology Effects-SEM Studies

Chlorobenzene cast films

have
much smoother and
more homogenous
nanostrcuture

Harald Hoppe, et al. Adv. Func. Mater. 14, 1005 (2004)

 Wessling Nanospheres

4
Vs = π rs3
3

⇒ Diameter of MDMO-PPV Nanospheres ≈ 15-20 nm

Harald Hoppe, PhD Thesis (2004)

Bulk Heterojunctions: Revised
 Transport in Conjugated Polymers

-3.5

-4
log µ / (cm V s )
-1

RR-MDMOPPV
-1

-4.5
versus
2

-5 RRa-MDMOPPV

-5.5

-6

-6.5
210 420 630 840 1050
E1/2 / (V cm-1)1/2

Attila Mozer et al, J. Phys. Chem. B 108, (2004) 5235

 Transport in Conjugated Polymers

Negative Field
Dependence in
RR-P3HT

Attila Mozer et al, Chem. Phys. Lett., 389 (2004) 438

 Transport in Conjugated Polymers
⎧ ⎛ ε − εi ⎞
⎛ ∆Rij ⎞⎪exp⎜ − j ⎟ ε j > εi
ν ij = ν 0 exp⎜⎜ − 2γa ⎟⎟⎨ ⎜ kT ⎟
⎝ ⎠
Bässler formalism, using ⎝ a ⎠⎪
⎩ 1; εj <ε
Miller Abrahams hopping rate and
a Gaussian density of localized states

⎡ 2 2⎤
[ (
µ (T , E ) = µ 0 exp ⎢− σˆ ⎥ exp − C σˆ 2 − Σ 2 E 1 / 2 ) ]
⎣ 3 ⎦
σ= σ/(kBT) and Σ are parameters characterizing
energetic disorder and positional disorder,
σ [eV] is the width of the Gaussian density of states,
µ0 [cm2V-1s-1] is a prefactor mobility in the disorder-free system,
E [Vcm-1] is the electric field, and C is a fit parameter.

H. Bässler; Phys. Stat. Sol (b) 175 (1993) 15

 Photo-CELIV Method

2d 2
µ=
2 ⎡ ∆j ⎤
3 At max ⎢1 + 0 .36 ⎥
⎣ j (0 ) ⎦

Attila Mozer et al, Phys. Rev. B 71, (2005) 35214

 Photo-CELIV Method

Attila Mozer et al, Phys. Rev. B 71, (2005) 35214

 ToF-Photo-CELIV Comparisons

Attila Mozer et al, Phys. Rev. B 71, (2005) 35214

 ToF-Photo-CELIV Comparisons

Attila Mozer et al, Phys. Rev. B 71, (2005) 35214

 Percolation Problem in Composites

Metal Metal
Electrode Electrode

Fullerene (acceptor)
Conjugated Polymer (donor)
Both donor and acceptor phases have to be percolated !!!
 “Double Cable” Polymers

Metal Metal
Electrode Electrode

Fullerene (acceptor)
Conjugated Polymer (donor)
Both donor and acceptor phases will be percolated simultaneously
A. Cravino and N. S. Sariciftci, J. Mater. Chem. 12, 1931 (2002)
 „Double Cable“ Polymers

H
S S

H S S
S S
H
n
S S
H

O
O O
O
O
O O

electropolymerization O
O
O O
O
O
O

N
N

A. Cravino, G. Zerza, M. Maggini, S. Bucella, M. Svensson, M.R. Andersson,

H. Neugebauer, N.S. Sariciftci, Chem. Commun. 2487 (2000)
Supramolecular Ordering

Di-block copolymer
miscelle formation
encapsulating
fullerenes.

S. Jenekhe, & Chen,

Science 279, 1903 (1998)
Solar photon harvesting
Spectral Mismatch to Solar Emission
 Photon Harvesting

18 photon flux AM 1.5

6x10
integrated photon flux [%]
18 absorbed photons [%]
5x10
100
photons [n m s nm ]
-1

MDMO-PPV/PCBM 1/4
18
4x10
-1
-2

18

[%]
3x10
50
18
2x10

18
1x10

0 0
400 600 800 1000 1200
Wavelength [nm]
 OR
e- O
OMe
RO

Color Variations: Band Gap Engineering

OR

RO

OR

RO
n
 PTPTB Photovoltaic Devices

S S N
N
N N
R R
S S
N n
O
C12H25
OMe
n = 1- 4
PTPTB R = H, Br

Al / Ca (80 nm)
PCBM
LiF(0.6 nm)

Active layer (~100 nm) ITO

PEDOT (~80 nm)
Glass
C. B. Brabec, C. Winder, N. S. Sariciftci, J. C. Hummelen,
A. Dhanabalan, P. A. van Hal, R. A. J. Janssen, Adv. Func. Mater. 12 (2002) 709
 MDMO-PPV/PTPTB

luminescence
absorption
MDMO-PPV
PTPTB
PTPTB

luminescence [a.u.]
energy transfer 1,0
absorption [a.u.]

1,0

0,5 0,5

0,0 0,0
600 800

wavelength [nm]
 PTPTB Sensitization

PTPTB in PPV
70
0%
1%
60
5%
Electroluminescence [a.u.]

50 % (*10)
50 100 % (*20)

40

30

20

10

0
500 600 700 800 900
Wavelength [nm]
Pc-C60
C(CH3)3

N N
N
CH3

(CH3)3C N Zn N
N

N
N N

C(CH3)3

Pc-C60

M. A. Loi, P. Denk, H. Hoppe, H. Neugebauer,

C. Winder, D. Meissner, C. Brabec, N. S.
Sariciftci, A. Gouloumis, P. Vazquey, T. Torres,
Journal of Materials Chemistry 13 (2003) 700
 Functioning Principle of Hybrid Solar Cells

Θ Θ
Θ

ITO p-type n-type Al

„Interpenetreting Network“
 Quantization
E. Arici, D. Meissner, N. S. Sariciftci, Adv. Func. Mater. 13, (2003) 1

⎛ h ⎞ ⎛⎜ 1 1 ⎞
2

Eg = Eg (Bulk)
*
+ ⎟
2
+⎜ ⎟⎜ - 1 . 8 e
⎝ 8R ⎠ ⎝ m e m h ⎟⎠ 4πε 0ε R
2

Particle-in-the-box-Term Coulomb-Term

R CIS < R WM
Wannier Mott Exciton Radius
Rwm = (εoo/µ). αB
= 8.1 nm
εoo = Dielectric const.
µ = Reduced Mass
αB = Bohr Radius of H-Atom
2.3 eV 1.5 eV
*L.E. Brus, J. Chem. Phys. 80, 4403 (1984)
 Device and Materials

PEDOT active
glass ITO :PSS layer
Al

Blend with weight ratio

1 : 4

O n

MDMO PPV PCBM

3,7 - dimethyloctyloxy 1-(3-methoxycarbonyl)
methyloxy propyl-1-phenyl [6,6]C61
Energy Scheme Poly(paraphenylenevinyle
ne)
 Charge Generation Profil

100nm 180nm

40nm 240nm

H. Hoppe, N. Arnold, N.S. Sariciftci, D. Meissner

Solar Energy Materials & Solar Cells Vol 80 (2003), 105-113
 Photocurrent for IQE=1

H. Hoppe, N. Arnold, N.S. Sariciftci, D. Meissner

Solar Energy Materials & Solar Cells Vol 80 (2003), 105-113
Stability
 OUTLOOK - Stability
1,0

0,8
- Exponentional Decay Fit

Voc [ a. u.]
0,6 Lifetime : 2.6 hours
UNPROTECTED 0,4

0,2

0,0
0 3 7 10
Time [Hours]
1,0

0,8
Voc [a. u.]

PROTECTED
0,7

0,5
0 30 60 90 120 150
Time [days]
 OUTLOOK - Stability

C60 slows down degradation of the Conj. Polymer

C60 1182 cm-1

MDMO-PPV/ C60 1182 cm-1

Rel. Peak Area

MDMO-PPV/ C60 1506 cm-1

MDMO-PPV 1506 cm-1

Time [Hours]
 LIOS
Linz Institute for Organic Solar Cells
Physics of Organic Semiconductors:
1.) Photoexcited spectroscopy
2.) Photoconductivity
3.) Thin film characterization
4.) Nanoscale engineering
5.) Nanoscale microscopy (AFM, STM...)
6.) In situ spectro-electrochemistry

Organic
Plastic Solar Cells Field Effect
CD-Labor Organic/Inorganic
Small Molecular Transistors
Hybrid
Solar Cells
Solar Cells

„Incubator“ for small high tech spin-off companies:

Konarka Austria (former QSEL), NanoIdent AG, …