Daniel Ayuk Mbi EGBE

Linz Institute for Organic Solar Cells, Johannes Kepler University Linz,

Altenbergerstr. 69, 4040 Linz, Austria

ANSOLE e.V., Ebertstr.14, 07743 Jena, Germany

daniel.egbe@ansole.org/daniel_ayuk_mbi.egbe@jku.at

Skype: danielegbe1

Designing Organic Materials for Optoelectronics and Low Cost

Solar Cell Applications - Benefits for Africa

Inaugural Brian O´ Connell Visiting Fellows Lecture, 30 March 2016

University of the Western Cape, Cape Town, South Africa

CONTENT

• JKU Linz, Austria

• African Network for Solar Energy

• Generalities on Organic Semiconducting Materials

• Materials Design Principles• Case Study on Arylene-Ethynylene/Arylene-Vinylene Hybrid Systems

• Acknowledgements

Johannes Kepler University Linz, Austria

JKU was created in 1966, celebrates its 50th anniversary this year,

has 22 000 students studying in 4 faculties

-Faculty of Social Sciences

-Faculty of Law

-Faculty of Technical and Natural Sciences

-Faculty of Medicine (since 2014)

Linz Institute of Technology (LIT)

(since 2016)

UWC is the only African University in bilateral cooperation with JKU

Linz Institute for Organic Solar Cells (LIOS)Physics (and Chemistry) of Organic Semiconductors:

1.) Photoexcited spectroscopy

2.) Photoconductivity + Magnetoconductivity

3.) Thin film characterization

4.) Nanoscale engineering

5.) Nanoscale microscopy (AFM, STM...)

6.) In situ spectro-electrochemistry

7.) Materials synthesis

Organic/Hybrid

Solar Cells

CO2 Recycling into

Synthetic Fuels

Spectroscopy

and

Electrochemistry

(Bio)-Organic

Electronic Devices

OR

RO

OR

RO

OR

ROn

O

OMe

e-

Headed by Prof. Serdar Sariciftci

CONTENT

• JKU Linz, Austria

• African Network for Solar Energy

• Generalities on Organic Semiconducting Materials

• Materials Design Principles• Case Study on Arylene-Ethynylene/Arylene-Vinylene Hybrid Systems

• Acknowledgements

• Less than 40% of sub-Saharan Africans have access to electricity

• The present yearly economic growth of Africa is ~5.5%, despite of lack

of sufficient energy and infrastructure.

• However, Africa cannot embark on the same path as Europe, USA and

China for its development by relying only or strongly on non

environment-friendly energy sources. This is imperative in order to

achieve the Sustainable Development Goals (SDGs) (2016-2030) and

the resolution of COP 21 of maintaining the world temperature rise

not above 1.5 °C .

• The appropriate use of the abundant solar energy can be regarded as a

solution to the African energy problem. This requires highly qualified

human resources at all levels.

The Sun as Energy Source

The Sun is the primary

source of energy on Earth.

It transforms hydrogen into

helium thru nuclear fusion,

whereby energy is released

as electromagnetic rays

(photons)

The Sun as Energy Source

Every hour the Sun bathes

the Earth with enough

energy to satisfy global

energy needs for a year

Solar energy currently

accounts for about 0.1% of

the global energy demand

Solar energy is the primary

source of power for today's

space missions

Source: National Geographic/Nasa

„Within 6 hours deserts receive more energy

from the Sun than Mankind consumes within a

year“

Dr. Gerhard Knies, Desertec Initiative

Solar Panels to ring the Moon

How the moon could provide for our energyNews and Trends, January 8, 2014

11000 Km solar panels around the moon equator and transmission of energy to Earth

via microwave (Japanese project 2035)

Renewable Energies

Hydropower

Geothermal energy

Solar energy• Solarthermics• Photovoltaics

Ocean tides

Wind energy

Bioenergy (biomass)

Photovoltaics

First Generation:

Monocrystralline Si: >14%

Polycrystalline Si: >12%

Second Generation

Amorphous Si: > 6%

CdTe: > 8 %

GaAs: >18-20 %

CIGS: >10-12 %

Third Generation (New Technologies)

Grätzel-Cells: = 11 %

Organic Solar Cells: >10 %

• Perovskites: >18 %

10

Annual solar radiation -© Meteotest, Berne, Switzerland

Batteries, inverter, cables, etc

Electricity

PV panels

Solar thermalcollector Heat exchangers,

storage tank, controllers, etc

Heat Electricity

ANSOLE is a platform of exchange among various stakeholders (non-experts,

scientists, researchers, industrial experts, public and private institutions, NGO´s, etc)

who are all devoted to promote in A CONCERTED WAY the use of sustainable energy

to address the (acute) energy problem in Africa while preserving and protecting the

environment.

http://light2015blog.org/2015/06/22/the-african-network-for-solar-energy-ansole/

http://www.bbc.com/news/science-environment-34987467

www.ansole.org

Human capacity buildingis our main focus!

Participants at the Launching of ANSOLE on the 4th of February 2011

ANSOLE was initiated on the 4th of November 2010 in Sousse Tunisia and launched on the 4th of February 2011 at LIOS, JKU, Linz Austria.It celebrated its 5th anniversary this year (2016) in Cairo, Egypt.

www.ansole.org

ANSOLE members at the 5th anniversary celebration on the 4th of February 2016

Fosters technical and vocational education and training(TVET) inrenewable energies at various skill levels (capacity building)

Fosters research activities in renewable energy among Africanscientists and non African scientists who are directly involved inthe education of African students and experts (capacitybuilding)

Promotes and encourages the use of renewable energy in Africa(substainable development, environmental protection, businessmediation, etc)

Goals of ANSOLE

ANSOLE has more than 850 members based in:

42 African Countries: Algeria, Benin, Botswana, Burkina Faso, Burundi, Cameroon, Chad,

Central African Republic, Congo-Brazzaville, Democratic Republic of Congo, Cote d´Ivoire,

Djibouti, Egypt, Ethiopia, Gambia, Ghana, Guinée Conakry, Kenya, Liberia, Lesotho, Malawi, Mali,

Mauritania, Mauritius, Morocco, Mozambique, Namibia, Niger, Nigeria, Rwanda, Senegal, Sierra

Leone, Somalia, South Africa, Sudan, South Sudan, Tanzania, Togo, Tunisia, Uganda, Zambia,

Zimbabwe.

28 non African Countries: Albania, Austria, Belgium, Britain, Canada, China, Denmark, Estonia,

Finland, France, Germany, India, Ireland, Italy, Luxembourg, Jordan, Malaysia, Holland, Palestine,

Portugal, Russian Federation, Scotland, Spain, Sweden, Switzerland,Taiwan,Turkey and USA

Logos of Institutional Members

Stand 30 March 2016

1) (Co)Organisation of RE conferences, symposia, workshops & summer schools

Cameroon 2011& 2012, Morocco 2013, Tunisia 2013, Kenya 2013, South Africa 2013, Ghana 2014,

Algeria 2015, Tanzania 2015, Egypt 2016

Upcoming: (Kenya 2016), Cameroon 2016, Burkina Faso 2016, Tanzania 2016,

Tunisia 2017, Algeria 2017,Cameroon 2017

2)Assisting in organization of non-ANSOLE RE related events worldwide

Hamburg 2011, Giessen 2012, Brussels 2012, Istanbul 2013, Berlin 2014, Dresden 2014, etc

3) Training, Education & Research

• „Sur-Place“ scholarships to selected 3rd year Bachelor, Masters and PhD students

• Mobility scholarships to Masters & PhD students (Intra-African Exchange, INEX,

Africa-North Exchange, ANEX, & Africa-Latin America Exchange, ALAMEX)

• Mediation of students & researchers from Africa, Europe, USA with own funding

to African & non-African RE laboratories

• Implementation of vocational training and education programs in RE at existing

training institutions (First initiative planned 2016 in Cameroon)

• Facilitation of building of research consortia within Africa and between Africa and

Europe

Activities

4) RE public education & awareness raising in Africa:

• radio & TV, print media, open-air events, popular theater („No Bill with the Sun“)

ANSOLE website, ANSOLE News (ANSOLE e-Magazine)

5) Business mediation

6) ANSOLE websites

information about RE events, job, training, funding opportunities, e-learning

( upcoming: ansole.com with French content!)

7) ANSOLE e-Magazine (ANSOLE News)

country specific detailed RE information; ANSOLE reports, RE events reports,

events calendar, life stories, etc (4 issues + 1 supplement published since 2014)

8) ANSOLE mailing list

• Rapid information dissemination to members, who forward the information thru

own mailing lists

9) Bridging Africa, Latin America and Europe on Water and Renewable Energies

Applications (BALEWARE)-www.baleware.org

will be launched in December 2016 in Arusha Tanzania (11-13.12.2016)

Students Exchange & Fellowship Programs

ANSOLE Sur-Place Fellowships (ANSUP)

Intra-Africa Exchange (INEX)

Africa-North Exchange (ANEX)• Africa-Latin America Exchange (ALAMEX): Upcoming

Mainly funded by the ICTP, Trieste, Italy:

And partly (~5%) by ANSOLE e.V.

Meriem Guesmi (Tunisia)Serge Izzedine (Benin/Senegal)

Alain Tossa (Benin/ Burkina Faso)

Suru Vivian John (Nigeria/South Africa)

Araba Amo Aidoo (Ghana)

Fellows 2015 & 2016

Moudarinan Aimadji (Chad/Morocco)

A. Lutgarde (South Africas Czech Rep) T. Chickri (Algeria Austria)

S. Nhi Huynh (ANEX, Sweden Namibia) M. Abdi ( ANEX, USA Cameroon)

S. Tombe (South Africa Austria)

D. Abdelrhman (Egypt France)

Some mediated students to African or European Labs

Email of Thanks

Email of Thanks

African PhD students trained at JKU through the mediation of ANSOLE since 2012

Many young African female scientists have been empowered !

Our motivation is based on the promises of God, which

are in line with The Second Law of Thermodynamics

I will bless you… and you shall be a blessing…Genesis 12:2

…I have placed before you an open door that no one can shut… Revelation 3:8

The First Law

The internal energy U of an isolated system is constant

The Second LawThe entropy S of an isolated system = universe (system+ surroundings) tends to increase

Source: Physical Chemistry for the Life Sciences, Second Edition, Peter Atkins, Julio de Paula, Oxford University Press

Level of Positive Entropy = Level of Joy and Happiness

Individual Heat = Temperature=

Level of

wealth

Entropy =

Level of joy

Amadji 3000 J 0 °C (273 K) 10.99 J/K

Daniel 3000 J 100°C (373 K) 8.04 J/K

With the same amount of energy (money/wealth/etc) more

positive entropy (= joy and happiness) is created in Amadji´s

life than in Daniel´s

Going from The First Law mindset to

The Second Law mindset

Stotal = S +Ssur

SSur = -H/T

G = -T (Stotal) = -T(S +Ssur)

G = -T(S -H/T)

G = H -TS G is the maximum non-expansion energy

G is the useful energy

Source: Physical Chemistry for the Life Sciences, Second Edition, Peter Atkins, Julio de Paula, Oxford University Press

CONTENT

• JKU Linz, Austria

• African Network for Solar Energy

• Generalities on Organic Semiconducting Materials

• Materials Design Principles• Case Study on Arylene-Ethynylene/Arylene-Vinylene Hybrid Systems

• Acknowledgements

Band Gaps in Materials

A. J. Heeger A. G. MacDiarmid H. Shirakawa

Nobel Prize 2000 in Chemistry„For the discovery and developmentof conductive polymers“

R. F. Heck E.-I. Negishi A. Suzuki

Nobel Prize 2010 in Chemistry„ for palladium-catalyzed cross couplings in organic synthesis“

A. Geim K. Novoselov

Nobel Prize 2010 in Physics"for groundbreaking experiments regarding the two-dimensional material graphene"

1977: Discovery of metallic conductivity in

iodine doped trans-polyacetylene (CH)x

**

n

1.Wessling und Gilch-Reaction (Synthesis of PPVs)

2. Horner-Wadsworth-Emmons / Knoevenagel Reactions

(synthesis of PPVs / CN-PPVs)

3. Transition Metal (Ni, Pd, Cu, Ag)-catalyzed Reactions

(Suzuki, Heck, Sonogashira, Stille, Yamamoto, etc) for the

Synthesis of PPP, LPPP, PPV, PPE, PT, PF, DA- Copolymers.

4. Metathesis –Reactions (Alkene- und Alkine-Metatheses):

PPV (Grubbs, Bazan, Thorn-Csanyi), PPE (Bunz, Moore),

PA (Feast: Durham Route)

5. Grignard-Metathesis (GRIM) Reactions for the Synthesis

of rr-P3HT and Block-Copolymers

(living chain growth polymerisation)

SSSBr

n m

P3HT: n:m = 100:0P3HT-b-P3EHT: n:m = 50:50 or 75:25 (block copolymers)P(3HT-co-3EHT): n:m = 50:50 or 75:25 (random copolymers)P3EHT: n:m = 0:100

J. Am. Chem. Soc. 2008, 130, 7812-7813.

Macromol. Rapid Commun. 2009, 30, 1059-1065.

Synthetic Methods of Conjugated Polymers

www.photonicswiki.org

Organic Semiconductors

Images source: Karl Leo, TU-Dresden

35

Organic Light-Emitting Diodes (OLEDs)

3mm thickReaction time: 0.001 mscontrast: 107:1Wide viewing angleVery low energy consumption

Source: Mitsubishi Chemicals

(www.scottevest.com, www.neubers.de )

•Active layer: blend of conj. polymer and fullerene (OPV)

•Active layer: conj. Polymer (OLED)

•Contacts:

Electrons: Al/LiF

Holes: ITO/ PEDOT:PSS

(Poly[3,4-(ethylenedioxy) thiophene] : Poly(styrene- sulfonate))

PEDOT:PSS

Active layer

eventually LiF (6 Å)

Aluminium

ITO

Glass

Vaporisation

Spin coating,doctor blading,Printing techniques

Etching, laser-etching

Also flexiblesubstrate (PET)

38

Design of Organic Solar Cells (OSC) and Organic Light-

Emitting Diodes (OLEDS)

-3

-3.5

-4

-4.5

-5

-5.5

[eV] vs vacuum

-6

HOMO

HOMO

LUMO

LUMO

ITO PEDOT

PSS

Al

DONOR

“P"

ACCEPTOR

“N"

1.Light absorption creates bound electron-hole pair (Exciton) (EB=0.1-1eV)

2. exciton diffusion (for conj. polymers ca 5-20 nm)

3. exciton dissociation (charge separation at the interface)

4. Charge transport to the electrodes

Working Principle

39

Cathode

Anode

Substrate (PET Foil)

Cathode (ITO)

Anode (Al)

D-A-Blend

O

O

P3HTexcitation

P3HT*

PCBM(0)

P3HT+

PCBM(-I)

electron transfer

S

Working Principle of OPV

PCBM:[6,6]-phenyl-C61-butyric acid methyl ester

Efficiency = JscVocFFPin

-0.75 -0.50 -0.25 0.00 0.25 0.50 0.75-12

-8

-4

0

4

8

Curr

en

t density (

mA

/cm

2)

Voltage (V)

= 2.9 %

P3HT:PCBM

Short circuit current Jsc

(Light absorption,)

Fill factor FF(transport, charge collection)

Open circuit voltage Voc

(HOMO-LUMO offset,)

Organic Solar Cells Parameters

CONTENT

• JKU Linz, Austria

• African Network for Solar Energy

• Generalities on Organic Semiconducting Materials

• Materials Design Principles• Case Study on Arylene-Ethynylene/Arylene-Vinylene Hybrid Systems

• Acknowledgements

Low band gap (Eg < 2.0 eV)

Suitable HOMO/LUMO-energy-levels

(LUMODonor ca. 3.3-3.5 eV with PCBM as acceptor)

High absorption coefficient

Broad absorption spectrum

Sufficient charge carrier mobility(10-4-10-2 cm-2/V.s)

Optimized „ bulk heterojunction“ layer

Soluble and good film forming

Lowering the band gap

increases light absorption

but decreases VOC

LUMO

HOMO

LUMO

HOMO

Donor Acceptor

VOC

H. Hoppe et al. J. Mater. 2006, 16, 45.

S. Günes et al. Chem. Rev. 2007, 107, 1324.

G. G. Malliaras et al. Materials Today 2007,10, 34.

M. D. McGehee et al. Materials Today 2007,10, 28.

Requirements on Materials

Eg = Er + ERes + E + ESub + Eint

Er= bond length alternation BLA.

ERes = resonance energy

E= inter ring torsion angle

ESub= Substituent effects

Eint = interchain coupling

J. Roncalli Chem. Rev. 1997, 97, 173. Eg

44

Band Gap Engineering

C. L. Chochos, S. A. Choulis, Progress in Polymer Science 2011, 36, 1326-1414

Decrea

sing b

on

d len

gth

altern

atio

n (B

LA

)

O

CH3O

O

CH3O n

MEH-PPV MDMO-PPV

Eg = 2.1 eV

O

CH3O

O

CH3O

NC

CN

CN-MEH-PPV

n

n

Aromatic form ↔ Quinoid form Influence of side groups

O O

SS

nn

rr-P3HT PEDOT

Eg = 1.9 eV Eg = 1.5 eV

NH2H2N

S

O2N NO2

S

n

Eg = 1.1 eV

45

Band Gap Engineering

O

CH3O

O

CH3O

n

O

CH3O

O

CH3O n

O

CH3O

O

CH3O

O

CH3O n

Eg = 2.20 eV Eg = 2.10 eV Eg = 1.90 eV

J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 2243

Chem. Rev. 2009,109, 5868.

Se

n

rr-P3HS

Eg = 1.6eV

S

n

rr-P3HT

Eg = 1.9 eV46

Coplanarity

N N

R R

N N

S

R R

NS

N

S

NS

NNSe

NN

SN

NS

N

Ph Ph

Si

R R

N

NN

S

S

N

S

S

O

OS

S

COOR

F

S

S

COR

F

S S

R R

S

Si

S

R R

S

S

OR

OR

N

RR

R

S

S

S

S

S

SS

D A

n

Electron rich ( „Donor“) building units

Electron deficient („Acceptor“) building units

Y.-J. Cheng et al. Chem. Rev. 2009, 109, 5868.47

Donor-Acceptor (Push-Pull) Concept

CONTENT

• JKU Linz, Austria

• African Network for Solar Energy

• Generalities on Organic Semiconducting Materials

• Materials Design Principles• Case Study on Arylene-Ethynylene/Arylene-Vinylene Hybrid Systems

• Acknowledgements

R

R

CH CH

I: R = H (gelb)II: R = CH3 ( gelb)

III: R = CH3O (rot)

n

H.-H. Hörhold et al. Makromol. Chem. 1970, 131,

105.

49

PPV in OLED: Burroughes, J. H. et al. Nature 1990,347,539

PPV in OPV: Sariciftci, N. S. et al. Science 1992, 258, 1474.

insoluble

n

O

On

O

On

O

On

O

On

PPV DB-PPV DO-PPV MEH-PPV MDMO-PPV

increase of solubility in common organic solvents F. Wudl et al. ACS Symp. Ser.

1991, 455, 683

J. Mater. Chem. 2011, 21, 1338-1349

R

R

n

Ar

R

R

Ar

R

R

Arn

n

poly(arylene)s poly(arylene-vinylene)s poly(arylene-ethynylene)s

PAs PAVs PAEs

R

R

R

R

Ar Ar

n

PAE-PAVs

Poly(arylene-ethynylene)-alt-poly(arylene-vinylene)s

50Prog. Polym. Sci. 2009, 34, 1023-1067

Ask, and it will be given to you; seek and you will find, knock and it will be opened to you. For everyone who asks receives, and he who seeks finds, and to him who knocks it will be opened.

Matthew 7: 7-8

Story Behind the Scene

„ You should always try to solve a problem as far as it is possible. You must be patient; that is very important“

Gerhard Erl : Nobel Prize in Chemistry 2007

N N

CH2 diurethan-spacer

n

N NCHOOHC

N N

CH2OHHOCH2

+ diisocyanate

Aldehyde + phosphonate alkene (-CH=CH-) : The birth of PPE-PPV

Story Behind the Scene

Sonogashira ReactionDrawbacks: Longer reaction time.Lower molecular weights.1 to 3% diyne defect structures.Difficulty to remove the catalyst from the end polymeric product.Advantage:Polydispersity always around 2

X =PO(OEt)2 Horner-Wadsworth-Emmons ReactionX = CN: Knoevenagel ReactionAdvantages:Shorter reaction time.

Higher molecular weight

No defect structure

Pure products after work up.

Macromol. Chem. Phys. 2001, 202, 2712-2726

OR

RO

OR1

R1O

Y

Y

n

Br

Br

OR1

R1O

Y

Y

OR

RO

OHC CHO

OR

RO+

CH2XXCH2

OR1

R1O

+

Y = HY= CN

Retrosynthetic Approach

OHC CHO

OR

RO

The rejection of the first publication led to the study of side chains effects

~40 polymers of this type have been synthesized till date

O(CH2)7CH3

CH3(CH2)7O

CH2PO(OEt)2(EtO)2POCH2

O(CH2)17CH3

CH3(CH2)17O

O(CH2)7CH3

CH3(CH2)7O

DE11= P18/8

OHC CHO

O(CH2)17CH3

CH3(CH2)17O

+

n

Story Behind the Scene

D. A. M. Egbe et al. Prog. Polym. Sci. 2009, 34, 1023 (review article)

N. Bouguerra et al. Macromolecules 2016, 49, 455-464

N. Bouguerra et al. Macromolecules 2016, 49, 455-464

Nassima Bouguerra, a Berber PhD student from Algeria

Role of side chains1. Solubilising agents

2. The donating effect contribute in lowering the band gap of polymers

3. Influence the thin film supramolecular ordering

4. Dilute the amount of photoactive species

5. Can lead to discrepancy between optical and electrochemical Eg

6. Insulating nature is good for electroluminescence

7. Can be used to tune the (nano)morphology of solar cell active layers

Macromolecules 2004, 37, 6124. Macromol. Rapid. Commun. 2005, 26, 1389.

J. Polym. Sci. Part A: Polym. Chem. 2007, 45, 1631.

Prog. Polym. Sci. 2009, 34, 1023 (review article)

Macromolecules 2010, 43, 1261.J. Mater. Chem. 2010, 20, 9726.

J. Mater. Chem. 2011, 21, 1338 (feature article)

OR1

R1O

OR2

R2On

OR1

R1O

Ooctyl

octylO

OR2

R2O

Ooctyl

octylOn

6:a =450 nm, f = 490nm, f =60-70%

8:a =470 nm, f = 520nm, f =60-80%

Increase of the

number of side

chains leads

to red shift

Photophysics in Solution

Photophysics in Thin Film

OR1

R1O

OR2

R2On

OR1

R1O

Ooctyl

octylO

OR2

R2O

Ooctyl

octylOn

Solid state properties depend on the number, position, length and

geometry of the grafted alkoxy side chains

Four-fold substitution

Eight-fold substitution

0

20

40

60

80

100

120

300 400 500 600 700 800 900 1000Wavelength / nm

Int.

(a.u

.)

DE36

DE11

Dependence of the solid state absorption and emission on the position of the side chains

DE11: a = 465 nm, Egopt = 2.39 eV, e = 602 nm, f = 19%

DE36:, a = 455, 482 nm, Egopt = 2.41 eV, e = 510, 544 nm, f = 29%

OR1

R1O

OR2

R2On

DE11=P18/8: R1 = octadecyl, R2 = octyl, orange

DE36= P8/18: R1 = octyl, R2 = octadecyl, yellow

1. P8/18: R1 = octyl, R2 = octadecyl

2. P18/8: R1 = octadecyl, R2 = octyl

3. P18/7: R1 = octadecyl, R2=heptyl

4. P18/16: R1 = octadecyl, R2 = hexadecyl

5. P18/12: R1 = octadecyl, R2=dodecyl

6. P12/12: R1 = R2 = dodecyl

1

2

3

4

5

6

a b c d e f

OR1

R1O

OR2

R2On

E. Tekin et al. J. Mater. Chem. 2006,

16, 4275-4280

Decreasing film thickness

125 100 75 65 60 50 nm

Inkjet Printed Films: Combinatorial Effects

of Side Chains and Film Thickness

Emine Tekin

Intensity increase of the PL 0-2 transition due to superposition with excimer-like emission

P8/18 P18/16 P18/8

J. Mater. Chem. 2006, 16, 4275-4280

Inkjet Printed Films: Combinatorial Effects

of Side Chains and Film Thickness

63

Tuning of solar cells active layer nanomorphology

O

O

S

O

On

O

O

S

O

On

O

O

S

O

On

VOC = 900 mV

FF= 54 %

JSC= 2.50 mA/cm2

= 1.20%

VOC = 900 mV

FF= 53 %

JSC= 3.70 mA/cm2

= 1.74%

VOC = 800 mV

FF= 44 %

JSC= 5.15 mA/cm2

= 1.80%

3: PCBM (1:3 wt)

Variation of Side Chains Volume Fraction

S

O

O

O

On

DO-PThE1-PPV2

(D1)

S

O

O

O

On

MEH-PThE1-PPV2

(D2)

2.521.510.50

2.5

2

1.5

1

0.5

0

X[µm]

Y[µ

m]

2.521.510.50

2.5

2

1.5

1

0.5

0

X[µm]

Y[µ

m]

2.521.510.50

2.5

2

1.5

1

0.5

0

X[µm]

Y[µ

m]

VOC = 840 mV

FF= 41 %

JSC= 4.5 mA/cm2

= 1.58%

VOC = 860 mV

FF= 40 %

JSC= 6.02 mA/cm2

= 2.0%

VOC = 742 mV

FF= 36 %

JSC= 4.95 mA/cm2

= 1.35%

Material (cm2.V-1.s-1)

D1 1.8 10-5

D2 2 10-6

D1:D2 2.6 10-4

Ternary Blend

G. Adam et al. J. Mater. Chem. 2011, 21, 2594

J. Mater. Chem. 2011, 21, 2594.

Getachew Adam

Phys. Status Solidi A. 2009, 12, 2695; Macromolecules 2010, 43, 1261;

Macromolecules 2010, 43, 306, J. Mater. Chem. 2010, 20, 9726

Effect of -Stacking Distance

400 500 600 700 8000,0

0,2

0,4

0,6

0,8

1,0A

bso

rptio

n O

.D.

Wavelength [nm]

AnE-PV

P3HT

Page 68

OR1

R2O

OR1

R2O

OR3

R4On

J. Mater. Chem. 14, 3462 (2004)28.03.

HL 58.7

AnE-PV

LUMO: -3.3 eV

HOMO: -5.4 eV

P3HT

LUMO: -3.0 eV

HOMO: -5.1 eV

OHC CHO

OR1

R2O

OR2

R1O6

+ (EtO)2OPCH2 CH2PO(OEt)2

OR3

R4O 14

t-BuOK

toluene

OR1

R2O

OR2

R1O

OR3

R4O

n

AnE-PV

Code R1 R2 R3 R4

AnE-PVaa octyl octyl octyl octyl

AnE-PVab octyl octyl 2-ethylhexyl 2-ethylhexyl

AnE-PVac octyl octyl methyl 2-ethylhexyl

AnE-PVad octyl octyl decyl decyl

AnE-PVae octyl octyl dodecyl dodecyl

AnE-PVba 2-ethylhexyl 2-ethylhexyl octyl octyl

AnE-PVbb 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl 2-ethylhexyl

AnE-PVcc methyl 2-ethylhexyl methyl 2-ethylhexyl

d / nm

0.380 0.002

0.386 0.002

0.381 0.002

0.380 0.002

0.380 0.002

-

-

0.3790.002

Synthesis + X-Ray Data

Macromolecules 2010, 43, 306. Macromolecules 2010, 43, 1261.

O

O

O

O

O

On

O

O

O

O

O

On

AnE-PVab

AnE-PVba

Comparison between AnE-PVab and AnE-PVba

300 400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

0

5

10

15

20

25

Abs

orba

nce

O.D

.

Wavelength (nm)

ab

ab:PCBM

Nor

mal

ised

PL

[a.u

.]

0

10

20

30

40

50

60

70

80

300 400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

Abs

orpt

ion

O.D

.

Wavelength [nm]

ba

ba:PCBM

Nor

mal

ised

PL

[a.u

.]

O

O

O

O

O

On

O

O

O

O

O

On

Macromolecules 2010, 43, 1261.

Macromolecules 2010, 43, 306.

Comparison between AnE-PVab and AnE-PVba

d = 0.386 nm

AnE-PVab:PCBM (1:1) AnE-PVba:PCBM (1:1)

O

O

O

O

O

On

O

O

O

O

O

On

Comparison between AnE-PVab and AnE-PVba

Macromolecules 2010, 43, 1261.

-0,2 0,2 0,4 0,6 0,8 1,0 1,2

-10

-5

5

10

15

20

Cur

rent

den

sity

[mA

/cm

²]

AnE-PV ab

AnE-PV ba

Voltage [V]

3.1%

1.1%

AnE-PVab AnE-PVba

JSC : 7.14 3.44 mA

VOC: 0.79 0.93 V

FF: 55.65 34.67 %

: 3.1 1.1 %

Comparison between AnE-PVab and AnE-PVba

O

O

O

O

O

On

O

O

O

O

O

On

Macromolecules 2010, 43, 1261.

O

O

O

O

O

On

0

10

20

30

40

50

60

70

80

300 400 500 600 700 800 900

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

Abs

orpt

ion

O.D

.

Wavelength [nm]

ba

ba:PCBM

Nor

mal

ised

PL

[a.u

.]

Vivian Suru John, ANEX,

UWC, SA JKU, Austria

OHC CHO

OC8H17

H17C8O

OC8H17

H17C8O

1a: C8H17 = octyl (1)

+ (EtO)2OPCH2 CH2PO(OEt)2

OC8H17

H17C8O

t-BuOK

toluene

OC8H17

H17C8O

OC8H17

H17C8O

OC8H17

H17C8O

AnE-PVstat

n

+1b: C8H17 = 2-ethylhexyl (1)

2a: C8H17 = octyl (1)

+2b: C8H17 = 2-ethylhexyl (1)

Statistical distribution of sequences of C8H17 = octyl and of C8H17 = 2-ethylhexyl

Side Chain Based Random Copolymer

d = 0.393 nm

J. Mater. Chem. 2010, 20, 9726

µ = 5.43 ×10-4 cm2/Vs

Mn = 27,000 g/molMw = 54,000 g/mol

-0.2 0.2 0.4 0.6 0.8 1.0

-10

-8

-6

-4

-2

2

4

6

8current

density

[mA/cm2]

illumination

non

before annealing

after annealing

potential [V]

Stat:2PCBM before after

Voc [mV] 810 830

JSC [mA/cm2] 7.82 7.83

FF [%] 56 58

[%] 3.6 3.8

-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

1E-4

1E-3

0.01

0.1

1

10

100

Photovoltaic Properties: stat

J. Mater. Chem. 2010, 20, 9726

Mn = 27,000 g/molMw = 54,000 g/mol

0.34

0.35

0.36

0.37

0.38

0.39

0.40

statccacabaead

d [n

m]

AnE-PVaa

2%

3.0% 3.8%

amorphes Polymer 1%

µ= 2.57 ×10-5 cm2/Vs

~10-5 cm2/Vs

µ = 4.52 ×10-4 cm2/Vs

µ = 5.43 ×

10-4 cm2/Vs

Possible Polymer Alignment on a Substrate (Electrode)

Edge-on alignmentFace-on alignment Vertical alignment

S. Rathgeber et al. Polymer 2011, 52, 3819-3826

• well ordered lamellar domains,

also in the presence of the fullerene,

• "face-on" domains close to the

electrodes,

• enhanced isotropic domain orientation

throughout the active layer.

This leads to the best solar cell performance!

AnE-PVstat leads to active layers with:

•Polymers with solely linear side chains align edge-on the substrate

•Polymers bearing branched side chains align face-on on the substrate

•Face-on alignment is favorable for better charge transport andconsequently for better performance

Effect of Fullerene Derivatives

P. Troshin et al. Adv. Funct. Mater. 2009, 19, 779.

0,0 0,2 0,4 0,6 0,8

-12

-10

-8

-6

-4

-2

0

2

4C

urr

en

t de

nsity, m

A/c

m2

Voltage, V

AnE-PVstat: PC61

BM

AnE-PVstat: F11

P3HT: F11

S

P3HT

OC8H17

H17C8O

OC8H17

H17C8O

OC8H17

H17C8O

AnE-PVstat

n

= 4.8-5%

Mn = 5000 g/mol

Mw= 18000 g/mol

Adv. Energy Mater. 2013, 3, 161-166

Nature Photonics 2013, 7, 811-816

Nature Photonics 2013, 7, 811-816

S. AAZOU (ANEX, Morocco-Austria)

OHC

OR

RO

S

S

S

C12H25

BrBr+Pd(PPh3)4 /CuI

iPr2NH, toluene, N2

OHC

OR

RO

SCHO

S

S

C12H25

OR

RO

OR

RO

S

S

S

C12H25

OR

RO

OR1

R1O n

OR1

R1O

CH2PO(OEt)2(EtO)2OPCH2

t-BuOK, toluene, reflux, N2

BTE-PVaa: R = R1 = octyl; BTE-PVab: R =octyl, R1 = 2-ethylhexyl; BTE-PVbb: R = R1 = 2-ethylhexyl; BTE-PVba: R =2-ethylhexyl, R1 = octyl

BTE-PV

1 2 3

4

1a, 3a, 4a: R = R1 = octyl 1b, 3b, 4b: R = R1 = 2-ethylhexyl

Two-dimensional Conjugated PAE-PAV Systems

300 400 500 600 700 8000.0

0.2

0.4

0.6

0.8

1.0

0.0

0.2

0.4

0.6

0.8

1.0 BTE-PVab

BTE-PVbb

BTE-PVba

BTE-PVaa

(b)

A

Wavelength (nm)

I em (

a.u

.)

104

105

10-5

10-4

10-3

10-2

104

105

10-5

10-4

10-3

E 1/2

(V cm-1

)1/2

h

(c

m2 V

-1 s

-1)

e (c

m2 V

-1 s

-1)

E 1/2

(V cm-1

)1/2

BTE-PVab

BTE-PVbb

BTE-PVba

BTE-PVaa

(b)

(a)

R Jadhav et al. RSC Advances,

under revision

Pune University

Journal Polym. Sci: Polym. Phys

2014, 52, 338-346

Sameh BOUDIBA, Tebessa

(ANEX, Algeria-Austria)

Shaimaa Ali MOHAMED

Zewail City of Science/

Benha University, Cairo,

(ANEX, Egypt-Austria)

CuI as versatile hole-selective contact

For organic solar cells

Solar Energy Materials & Solar Cells 2015,

143, 369-374

Colloidal PbS Quantum Dots:

Thin Film Application in Photovoltaics

Adv. Mater. 2015, 27, 1533-1539

Some Cooperation partnersDr. Harald Hoppe, University of Jena, Germany

Prof. Vera Cimrova, IMC, Prague, Czech Republic

Dr. Nadia Camaioni, CNR Bologna, Italy

Prof. Silke Rathgeber, University of Koblenz-Landau, Germany

Dr. Pavel Troshin, Russian Academic of Sciences, Moscow

Prof. Emmanuel Iwuoha, UWC, Cape Town, South Africa

Profs Samir and Amel Romdhane, University of Tunis-Elmanar, Tunisia

Dr.Kathy Schmidtke

Dr. Andreas Wild

Dr. Emine Tekin

Stefan Türk

Rupali Jadhav

Dr. Getachew Adam

Dr. Özlem Usluer

Dr. Christoph Ulbricht

Nassima Bouguerra

Sameh Boudibah

Vivian Suru John

Dr. Samuel Inack Ngi

ACKNOWLEDGEMENTS

http://jahr-der-dankbarkeit.net/

In everything give thanks; for this is the will of God in

Christ Jesus for you. 1 Thessalonians 5:18

Oct.2015 – Oct. 2016: Year of Thanfulness!

Prof. Brian O´Connell

and UWC are thanked!