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Addis Abeba Lecture 1, May 3rd, 2010

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Organic,
Organic, Photovoltaic
Photovoltaic Energy
Energy Conversion:
Conversion:
From
From Photovoltaic
Photovoltaic Electricity
Electricity to
to Synthetic
Synthetic Fuels
Fuels using
using
CO
CO22 Recycling
Recycling

Niyazi
NiyaziSerdar
SerdarSARICIFTCI
SARICIFTCI
Linz
LinzInstitute
Institutefor
forOrganic
OrganicSolar
SolarCells
Cells(LIOS),
(LIOS),
Institute
Institutefor
forPhysical
PhysicalChemistry,
Chemistry,Johannes
JohannesKepler
KeplerUniversity
UniversityLinz,
Linz, Austria
Austria
www.lios.at
Happy Life RO

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Scope RO
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 e-

Scope
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 Photovoltaics
Required Land Areas
using 10 % efficient photovoltaic modules
Percentage of
total Sahara area:
1 0.12 %

2 0.7 %

3 5.4 %

4 7.6 %

1 40 % of present annual end energy consumption of FRG (3*1018 J)

2 50% of present end energy use of Western Europe (1.8 * 10 19 J)
3 50 % of present annual world energy consumption (1020 J)
4 50 % of extrapolated annual world energy consumption in 2030 (2* 10 19 J)
Arbeitskreis Alternativenergie Tübingen (Herausg.): "Energiepolitik vonunten", Fischer, Frankfurt/Main, 1982
 e-

Solar Energy Distribution in Europe

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Payback Time of Photovoltaic Investment

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Source: Alsema E.A., Nieuwlaar E (2000). Energy viability of photovoltaic systems. Energy Policy 28, 999-1010
Solar Energy Passively Used in Architecture
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 e-

Solar Stirling Engines

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McDonnell Douglas/Southern of California

California Edison 25 kW dish/Stirling system.
The 944 square foot concentrator consists of 82 spherically curved glass mirrors each 3 foot by 4 foot.
The United Stirling 4-95 Mark II engine
(4 cylinders of 95 cc displacement) uses hydrogen as the working pressure at a maximum gas pressure of 2900psi..
This engine delivered 25kW output at 1000W/m2 insolation.
First press release, 1954
 Nobelprize for Chemistry 2000

Alan Heeger, Alan MacDiarmid (†) and Hideki Shirakawa

1974: Discovery of metallic conductivity in
iodine doped trans-polyacetylene (CH)x
Semiconducting Polymer “Inks”
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Color Variations: Band Gap Engineering

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 e-

Full Color OLED Flat Panel Displays

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 RO
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Organic Solar Cell Device Geometries

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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 RO
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Organic Solar Cells

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“Tang- Cell“

C. W. Tang
Appl.Phys. Lett. 48(86)183
 e-
WORKING PRINCIPLE RO
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Photoexcitation in conjugated polymers

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Conjugated Polymer

LUMO

Exciton
Diffusion
 5-15 nm

HOMO
 e-
WORKING PRINCIPLE RO
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Photoexcitation in conjugated polymers

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Conjugated Polymer

nanosecond range
LUMO

Non radiative
recombination

Radiative
recombination
Heat

HOMO
 e-
WORKING PRINCIPLE RO
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Ultra-fast charge transfer

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Conjugated Polymer

LUMO

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

HOMO
 e-
WORKING PRINCIPLE RO
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Bi-layer polymer solar cells

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[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
 Photoinduced Electron Transfer
From Conjugated Polymers onto Fullerenes
 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)

C60
TOF Mass. Spec

C70
Molecular Orbital Energy Diagram
 Electrochemical Properties

Xie, Q.; Pérez-Cordero, E.; Echegoyen, L. j. Am. Chem. Soc. 1992, 114, 3978
 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)

 Intensity Dependence of Photocurrent RO
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Scaling Coefficient  ~ 0.92

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

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

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

 Voc vs HOMO of the Polymer Donor RO
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Markus Scharber et al, Adv. Mater. 18 (2006) 789

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Production
Production Scheme
Scheme
 e-

THIN FILM PREPARATION

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Spin Casting is an easy coating

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

Doctor Blade Technique

has no material loss

FILM THICKNESS IS ~ 100 nm

 Production - Large Area RO
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Large Area Thin Film Production using Doctor/Wire Blading

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)
 Production – Roll to Roll

Konarka Technologies Inc., www.konarka.com

Outdoor Demonstrations
Solar cell integrated textiles
A commercial solar jacket
and bag

(www.scottevest.com, www.neubers.de )
Fiber based solar cell

Direct photovoltaic textile fibers

Great chance for textile industry

 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

 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%]

 Nanomorphology Effects-SEM Studies

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

 Nanomorphology: Solvent Effects
a

Surface Height (nm)

8
(a)
Toluene cast film
4

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

b
Surface Height (nm)

(b)
8

4
Cholorobenzene cast film
0

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

100 0
90
Transmission (%)

Current Density (mA/cm )

80 -1

2
70
60 -2
50
-3
60
50 -4
40
IPCE (%)

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)
Bulk Heterojunctions: Revised
 Property Optimization
Molecular Structure
Molecular Engineering

Structure Property

Interchain
Self Organization (Intermolecular)
Interactions

Nanomorphology
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„Optimum“ Geometry for

Organic and Hybrid Solar Cells
High workfunction
electrode

Organic p-type
conductor (donor)

Organic n-type
conductor
(acceptor)

Low workfunction
electrode
 OR
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CIS Nanoparticles
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E. Arici, D. Meissner, N. S. Sariciftci, Adv. Func. Mater. 13, (2003) 1

 h   1 1  1.8e 2
2

*E g E g (Bulk ) +    -
4 0R
 8 R   me mh 
2

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

R CIS < R WM
Wannier Mott Exciton Radius
Rwm = (oo/). B
= 8.1 nm
oo = Dielectric const.
=Reduced Mass
B = Bohr Radius of H-Atom
2.3 eV 1.5 eV
*L.E. Brus, J. Chem. Phys. 80, 4403
(1984)
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Organic/Inorganic
OR

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Hybrid Solar Cells

Serap Günes et al., Adv. Func. Mat. 2006

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Photon Harvesting
n

18 photon flux AM 1.5

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

MDMO-PPV/PCBM 1/4
-1

18
4x10
-1

18
-2

3x10

[%]
50
18
2x10

18
1x10

0 0
400 600 800 1000 1200
Wavelength [nm]
 e-

Photon Harvesting Problem

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Incident Photon to Electron Conversion efficiency:

40

30
IPCE(%)

20

10

0
400 500 600 700 800
Wavelength (nm)

By low band gap materials we are loosing the green-blue region

 e-

Energy Transfer Cascades

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2 Förster resonant
energy transfer
cascade

1 Light
absorption 3 charge transfer
+ transport

- R. Koeppe, O. Bossart, G. Calzaferri, and N.S. Sariciftci, Sol. Energ. Inspired by

Mater. Sol. Cells. 91(11); 986-995 (2007)
photosynthesis
 e-

Tandem Solar Cells

OR O
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Organic tandem solar cells:

Aluminium
electrode

ZnPc:C60 solar cell

noncontinuous recombination
Polymer:PCBM layer
solar cell transparent ITO electrode
Glass G. Dennler, H.-J. Prall, R. Koeppe, M. Egginger,
R. Autengruber, N.S. Sariciftci, APL 89 (2006), 073502-1
Stability
 Encapsulation

Novaplasma Inc.,
Montreal, Canada

G. Dennler et al, 2005

 Encapsulation

NOVAPLASMA Encapsulation Foils

G. Dennler et al, 2005

Can we get rid of ITO
As Substrate?
 OR
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NANOTUBE ELECTRODE ?
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Rowell et al, Appl. Phys. Lett. 88 (2006) 233506

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NANOTUBE ELECTRODE ?
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It works !!!

Rowell et al, Appl. Phys. Lett. 88 (2006) 233506

 Storage-Transport Problem
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Space
Consumption Consumption
Somewhere else later and somewhere else
Transport
Energy
Energy
Conversion Consumption
later

Time

Storage of Energy

Transportable fuel created by solar energy conversion !!!

 Interfacing two R&D worlds
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INTERFACE BETWEEN CO2 REDUCTION AND

RENEWABLE ENERGY CREATION

CO2 EMISSIONS RENEWABLE

CLIMATE CHANGES ENERGIES

RECYCLE CO2 !!!

CREATE FUEL

Future recycling of CO2 as important mission of renewable energies

 Interfacing two R&D worlds
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INTERFACE BETWEEN CO2 REDUCTION AND

RENEWABLE ENERGY CREATION
Renewable energies such as solar photovoltaic or wind energy have
instabilities that can not be controlled in time domain.
► creating synthetic fuels will solve this problem

10-20 billion tons of CO2 is coming from burning fossil fuels

including coal for making electricity.
► Local high sources of CO2
► Can be combined with renewable energy for recycling
► CO2 can be much easier transported in gas pipelines than H2

Binding CO2 away from emissions will bring increasingly more

macroeceonomic load (Kyoto, Seweso etc, payments)
► Recycling CO2 will be ecenomically attractive
 e-

Natural Photosynthesis
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Recycling of CO2
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Over 90 % of emitted CO2 is

generated by energy
products.
To convert back CO2 to
fuels hydrogen or energy is
required.
One promising field
in this direction is
the photochemical
Or electrochemical
reduction of
carbon dioxide
using solar light
IS IT POSSIBLE TO RECYCLE CO2? RO
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The answer is yes!

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 RECYCLING CO2
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Methanol as carrier and storage of energy

a.) Methanol can be mixed to gasoline

b.) Methanol is used in fuel cells

c.) Methanol is starting chemical for

Many other derivatives

George Olah, Nobel Prize 1994

Univ. of Southern California, USA
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Electrochemical reduction of CO2

• Excess electric energy can be conveniently used for the

catalysed reduction of CO2 in water to afford alcohols
and/or Cn-hydrocarbons :
storage of electricity!
• Such use of excess electric energy can play a key role in the
short term for the conversion of CO2 into fuels
implementing a significant recycling of carbon.
• The use of solar energy for CO2 reduction in water is a key
issue for the medium term: a substantial recycling of carbon
could be performed.
 e-

Photocatalytic reduction of CO2

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1.Ru(bpy)32+ (bpy = 2,2’-bipyridine) as both photosensitizer and catalyst

2. Ru(bpy)32+ as the photosensitizer and another metal complex as the

catalyst

3. ReX(CO)3(bpy) (X = halide or phosphine-type ligand) or a similar

complex as both photosensitizer and catalyst

4. Ru(bpy)32+ or Ru(bpy)32+-type complex as the photosensitizer in

micro-heterogeneous systems

5. A metalloporphyrin as both the photosensitizer and the catalyst

6. Organic photosensitizers with transition-metal complexes as catalysts

1.“Photochemical carbon dioxide reduction with metal complexes” E. Fujita, Coord. Chem. Rev. 1999
 O RO
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NH2
OR

C NH
RO

H2N 2
RO
n
OR

ONa/K HO H3COH
COONa/K A
HCOOH

O O RNH2
O
+
O O HCONHR
O
n
D
O CnH2n+2

O O
H2 CnH2n
O O

CO
O CO
ROH
RO C OR
CO 22 COOH
COOH

O2 O O H2C=CH2
B HOOC
O
COOH
COOR Br COOH

R R
RC CR
C
O
COOH
O e- , H+ HOOC

O +
RNH2 + R’X RNHC
OR’
O
C
N O OH
H O H
N C N C N
H O O
n
n
 Coupling Chemistry and Biotechnology:
From CO 2 and H 2 O to CH 3 OH at rt
• CO 2 aq  HCOO - Formate dehydrogenase

• HCOO -  H2 CO Formaldehydedehydrogenase

• H2 CO  CH 3 OH Methanoldehydrogenase

• NAD+/NADH is the source of energy .

• Key issue : how to reverse the NAD +/NADH couple after
oxidation ?
• Use of chemical
or systems for
r solar light harvesting
and conversion
 e-

Interdisciplinary R & D
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Photochemistry
Photophysics Biocatalysis
Photocatalysis

System
Electrocatalysis Recycling CO2 Integration
Engineering

Prototyping
testing
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The SOLAR FUEL

OR

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Concept
Air
O2
(w/o CO2)

air
O2
(no CO2)
H2O CH4
Renewable Electrical
H2O
Energy Power

Sun
H2O MeOH

Water
H2O H2O
Waves
TECHNOLOGY
H2O Gasoline

Wind
Air
H2O
… (with CO2)
H2O Diesel
 Prototype @ JKU OR
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Worlds 1st Solar Fuel Station

Development & Demonstration Plant
10 kW electrical input
Product: Methane
Completion: Ende 2009
Total Investment: 1.5 Mio. €

Air
O2
(w/o CO2)

air
O2
(no CO2)
H2O CH4
Renewable Electrical
H2O
Energy Power

H2O

H2O H2O

TECHNOLOGY
H2O

Air
H2O
(with CO2)
H2O
www.solar-fuel.com

93
 Unstability in Wind Energy Supply
MW

Needs Buffering
 LIOS
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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

Plastic Solar Cells CO2 Recycling

(CD-Labor) Organic/Inorganic
Small Molecular
Hybrid
Solar Cells
Solar Cells

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

Konarka Austria (former QSEL), NanoIdent (insolv.), Botest, Isiqiri,
Plastic Electronic GesmbH, Prelonic GesmbH , Solar Fuel GesmbH …
 Acknowledgements
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Members of LIOS:
Helmut Neugebauer, Elif Arici, Anita Fuchsbauer,
Martin Egginger, RobertKöppe, Philipp Stadler,
Alberto Montaign, Jacek Gasiorovski, Patchanita
Thamyongkit, (Sandro Lattante), Almantas Pivrikas,
Gebi Matt, Martin Kruijen, Peter Trefflinger, Gerda
Kalab, Edina Mujcinovic, Ercan Avci, Beatrice Esteban-
Meana, Kerstin Oppelt, Daniel Egbe, Serpil Tekoglu,
Stefan Schaur, Doris Sinwel, Sandra Kogler, Christoph
Ulbricht
Uni. Linz, Collaborators.: Helmut Sitter, Thomas
Spin-off companies: Fromherz, Siegfried Bauer, Reinhard Schwödiauer,
Günther Knör

Konarka Austria (plastic solar cells)

(NanoIdent) (Insolv.)
Botest
Funded by: Plastic Electronic
Solar Fuel Company Prelonic (printed batteries)
Austrian Foundation of Science (FWF) Isiqiri (inelligent display boards)
European Commission Solar Fuel (artificial fuels)
 e-

Most Cited Paper in Solar Cells in 10 Years

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 Short CV
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1st April 1996-

Ordinarius Professor (Chair) and Director (Vorstand) of the Institute for
Physical Chemistry at the Johannes Kepler University in Linz/Austria.
Founding Director (Vorstand) of the Linzer Institut für organische
Solarzellen (LIOS)
1st January 1992 -1st April 1996
Senior research associate at the Institute for Polymers & Organic Solids at
the University of California, Santa Barbara
(Prof. Alan J. HEEGER, Nobel Prize for Chemistry 2000)
1st September 1989 - 31st December 1991:
Postdoctoral research associate at the 2nd. Physics Institute, of University
of Stuttgart, Fed. Rep. (Prof. Dr. Michael MEHRING)
1986 - 1989:
PhD study at the University of Vienna, Prof. Dr. Hans KUZMANY, at the
Institute of Solid State Physics , second supervisor Prof. Dr. Adolf
NECKEL at the Institute of Physical Chemistry.
1980-1986:
Study of Physics (Diplom) at the University of Vienna
Born in Konya, Turkey, 19th March,1961