Presentacion Polimeros Conjugados

Makromolekulare Chemie
Synthesis of Conjugated Polymers
Ullrich Scherf
Macromolecular Chemistry Group

Dept. of Chemistry and
Institute for Polymer Technology (IfP)
Bergische Universität Wuppertal
Gauss-Str. 20, D-42097 Wuppertal, Germany
scherf@uni-wuppertal.de
http://www2.uni-wuppertal.de/FB9/poly/
Kristina Schottler 1/43
Scherf Group
Prof. Ullrich Scherf

Chair Macromolecular Chemistry
Director Institute for Polymer Technology
ca. 560 publications

H-index: 61 (2011)
Total number of citations: > 16,000
#26 of highest impact materials scientists (Thomson Reuters 2011)
http://sciencewatch.com/dr/sci/misc/Top100MatSci2000-10/
Kristina Schottler
Conjugated Polymers – Nobel Prize in Chemistry 2000
Polyacetylene
+e-

Organic and Polymer semiconductors what is that?

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

















Semiconducting (Conjugated) Polymers

Kovacic, Wegner, Wessling, Hörhold, Swager, Bunz, Inbasekaran et al. (DOW),
Schlüter, Rehahn Gilch, Rehahn Moore, Weder Scherf, Leclerc, Holmes
R R R
R R
n n n n
R R R
poly(p-phenylene) poly(p-phenylvinylene) poly(p-phenylethynyle) poly(fluorene)

(PPP) ( PPV) ( PPE) ( PF)
Scherf, Müllen McCullough, Schlüter Shirakawa, Feast,

R1 R2
Rieke, McCulloch Naarmann, Grubbs
R3
R
n
S N
n n
R1 R2 R3 R n
ladder-poly(p-phenylene) polythiophene polypyrrole polyacetylene

( LPPP) ( PT) ( PPy ) (PA)


Requirements:
- High Molecular Weight (> 10,000)
- Solution Processing
Synthesis of Conjugated Polymers
1. Wessling/Zimmermann and Gilch procedure (PPVs)

(chain growth polymerization of arylenebismethide intermediates)
2. Transition metal (Pd, Ni, Cu) catalyzed aryl-aryl, aryl-ethenyl, aryl-ethynyl couplings
(Suzuki, Heck, Sonogashira, Stille, Yamamoto etc.)
for PPP, PPV, PPE, PT, PF, LPPP, PPy, DA-type alternating copolymers
First example: PPP synthesis (Schlüter, Wegner, Rehahn)
(step growth or chain growth polycondensation/catalyt transfer polycondensation)
3. Metathesis reactions (alkene & alkyne metathesis)

PPV (Grubbs, Bazan, Thorn-Csanyi), PPE (Bunz, Moore), PA (Feast: Durham route)
Kristina Schottler
Transition metal catalyzed couplings
Kristina Schottler
StilleMakromolekulare
coupling Chemie
Kristina Schottler
Other couplings
Kristina Schottler
Other couplings
Kristina Schottler
Requirements
Hairy-rod concept
(developed by Ballauf & Wegner for polyesters)

Solubilization of (conjugated) polymers
Problem: Substitution can cause steric hindrance
PPP: out-of-plane distortion ca. 15-20°
2.5-dialkyl-PPP: out-of-plane distortion ca. 80°
Kristina Schottler
Requirements PPP: out-of-plane distortion ca. 15-20°

Hairy-rod concept 2.5-dialkyl-PPP: out-of-plane distortion ca. 80°
(developed by Ballauf & Wegner for polyesters)

Solubilization of (conjugated) polymers
Problem: Substitution can cause steric hindrance
Solution
R R
Polyfluorenes Ladder-PPP (LPPP)

Kristina Schottler
Poly(para-phenylene vinylene)s
Kristina Schottler
Kristina Schottler
Kristina Schottler
Poly(para-phenylene
Makromolekulare Chemie vinylene)s

Formation of TBB defects in GILCH PPV derivatives

Kristina Schottler
Kristina Schottler
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Poly(fluorene)s (PF)
Kristina Schottler
– Synthesis after Yoshino and Pei/Yang
Poly(fluorene)s
Kristina Schottler
Poly(9,9-dialkylfluorene) – Synthesis after Yamamoto
Kristina Schottler
Poly(9,9-dialkylfluorene) – Synthesis after Suzuki
Kristina Schottler
Poly(9,9-dioctylfluorene) (PFO or PF8)
Kristina Schottler
Poly(9,9-dihexylfluorene) - Oligomers
Kristina Schottler
Conjugated Polymers
Progress in Synthesis - Poly(9,9-dialkylfluorene)s
(RO)2 B B(OR)2
R R
Br B(OR)2
Pd[0] n Pd[0]
R R R R
Br Br
PF (PFO, PF2/6 etc.) AB-type monomer
R R
AA/BB-type monomers
SUZUKI route (Mike Inbasekaran et al., DOW)
Mn: up to 250.000
Dp > 900
Br Br
Ni(COD) 2
n
R R R R
YAMAMOTO route (Ulli Scherf et al.)
Kristina Schottler
Poly(9,9-dialkylfluorene) – Thermal Formation of Keto
Defects
Kristina Schottler
Poly(9,9-dialkylfluorene) – Formation of Keto Defects
Kristina Schottler
Poly(9,9-dialkylfluorene) – Keto defects by
Photooxidation
Kristina Schottler
Poly(9,9-dialkylfluorene amine)
Kristina Schottler
Synthesis of Conjugated Polymers:
Isotactic Poly(9.9-dialkylfluorene)s
H3 C C 12H 25 H 3C C 12 H25
Atactic
n
C12H 25 CH 3 C12H 25 CH 3
H3 C C 12 H 25 H 3C C12 H25
Isotactic
n
C 12 H 25 CH3 C 12H 25 CH3
H3 C C 12 H 25 H 3C C12 H25
Syndiotactic
n
C 12 H 25 CH3 C 12H 25 CH3
C. Kudla, N. Koenen, U. Scherf (BUW), W. Pisula (MPIP Mainz) et al.

Macromolecules 2009, 42, 3483
Isotactic Poly(9.9-dialkylfluorene)
Makromolekulare Chemie via Directed Suzuki
Polycondensation of Chiral AB-type Monomers
Br Br
C. Kudla, N. Koenen, U. Scherf (BUW), W. Pisula (MPIP Mainz) et al.
C 12H 25 CH 3 Macromolecules 2009, 42, 3483
O
racemic F1-12 Br B
O
O C 12 H25 CH3
Br B
O
C 12 H25 CH3
O
Br B
F1-12
O
H3 C C 12 H25
(+)-F1-12/(-)-F1-12
n
C12H 25 CH 3
a-PF1-12
Enantiomeric separation
n by preparative scale chiral HPLC
C 12 H25 CH3
Br Br
i-PF1-12
Kristina Schottler
C12H 25 CH 3 50/43
Isotactic Poly(9.9-dialkylfluorene)s – 13C NMR Spectroscopy
C12H 25 CH 3
C9 C10 C1
C7
C2 C13
C8 C9 n
C12H 25 CH 3 C1/8
C2/7
atactic a-PF1/12: 2 signals,

RR/SS and RS dyads
isotactic i-PF1/12: 1 signal,

RR/SS dyads
n R1: -CH3
R1 R2
R2: -C12H25

Poly(9.9-dialkylfluorene)s –
Isotactic
Solid State Characterization
a) b)
c) 2D-WAXS1images: i-PF1-12 a-PF1-12

0
a) atactic a-PF1-12
0
a-PF1-12
b) isotactic i-PF1-12 (recorded at 30 °C)

Intensity / a.u.
1
H3 C C 12 H 25 1 H 3C C12H25
0
100 i-PF1-12
n
C 12 H 25 CH3 C 12H 25 CH3
Polarizing Microscopy images:

Kristina Schottler 1 2 3
a-PF1-12 forms nematic LC mesophases, i-PF1-12 not !!
52/43
LPPP -Makromolekulare
a Conjugated Chemie
Polymer Material of Highest Definition
Ladder Poly(para-phenylene)
Photoluminescence (a. u.)

0-0
R1 R Rx R’
R 2 R3 0-1
1
Extinction (a. u.)

0-1
n 0-2
R1
x R’
R2 R3
R1
n
R2 R3
R
R1: -hexyl 0-2

x R= -CH3
2: -4-decylphenyl
R R=3: -C 6H13
-methyl
R‘ = -1.4-C6H4-C10H21 350 400 450 500 550 600
Wavelength (nm)
„A soluble ladder polymer via bridging of functionalized poly(p-phenylene)-precursors”

U. Scherf, K. Müllen; Makromol. Chem., Rapid Commun. 1991, 12, 489–497
Synthesis of Conjugated Polymers: Spiro-LPPP
Q. L. Zhou et al., Org. Lett. 2004, 6, 2381
C.-T. Chen et al., Org. Lett. 2005, 7, 3717
Generation ofKristina
spirobifluorenes
Schottler in an one-step (cascade) reaction starting from bis(biphen-2-yl)ketones 54/43
Conjugated Polymers
Progress in Synthesis – Ladder PPP (LPPP) Synthesis
R
C 10 H21 C 10 H21 C10 H21
O O
B B
O O O R O R O
R
Br Br
O n
R O R O
C10H 21 C10 H21 C10H 21
C 10 H21 C10H 21
R R
CH3 SO3 H
n
R
R
C 10 H 21 C 10H 21
Spiro-LPPP (Scherf 2009, alternative route by Z. Bo 2008)

Polythiophenes
Kristina Schottler
Conjugated Polymers
Progress in Synthesis - Regioregular Poly(3-alkylthiophene)s
R R R R
LDA MgX2 Ni[0]
Br Li S Br XMg S Br S
S n
McCULLOUGH route I (Rick McCullough et al.)

Mn: up to 40.000
Dp up to 250
R „Chain-growth polycondensation“
(McCullough et al.; Yokozawa et al.)
XMg S Br
R R
CH3 MgX Ni[0]
R
Br S Br S n
Br S MgX
P3AT (P3HT etc.)
McCULLOUGH route II ("GRIM metathesis"; Rick McCullough et al.)

commercialized by PLEXTRONICS, MERCK
Kristina Schottler
Conjugated Polymers
Progress in Synthesis - Regioregular Poly(3-alkylthiophene)s
P3AT (P3HT etc.)

R
XZn S Br
R R
"Rieke-Zn" Ni[0]
R
Br S Br S n
Br S ZnX
Mn: up to 30.000
Rieke route (Rieke et al.)
Commercialized by BASF
Kristina Schottler
Applications for p-Conjugated Organic Materials
Organic Solar Cells (OSC)
Organic Light Emitting Diodes (OLED)
Organic Field-Effect Transistors (OFET)
Organic Lasers,
Photodetectors,
Sensors etc.
Kristina Schottler
Materials: Polymers versus Small Molecules
Kristina Schottler
Organic Lasers,
Photodetectors,
Sensors etc.
Kristina Schottler
Light Emitting Diodes (OLEDs) –
Organic
„Adressing Two Markets“ (Novaled)
Kristina Schottler
Organic Light Emitting Diodes (OLEDs) for Displays
OLED Display Volume:
2010: 892 Mio. Dollar

2015: 3600 Mio. Dollar
SAMSUNG 40´´ TV OLED Display
Kristina Schottler
Organic Light Emitting Diodes (OLEDs) for Displays
Transparent Display from TDK
Kristina Schottler
Organic Light Emitting Diodes (OLEDs) for Lighting
Universal Displays
OLED Lighting Volume:
Philips: Design Objects, 2015: 1500 Mio. Dollar Novaled
Specialities
Kristina Schottler
Organic Light Emitting Diodes (OLEDs) –
Sophisticated Device Structures
Kristina Schottler
Novel, High Molecular Weight PhoLED Matrix Polymers
O F F
O + CH2Cl2, TFSA
N -H2O Polyhydroxymethylation in a
CH3 F F Superelectrophilic Solvent System
H3C CH3 H3C CH3
F F
PME 124
(Mn 114,000, Mw 216,000)
O F F
N H3C CH3 H3C CH3
n
CH3
PME 124
Mikhail Zolotukhin, UNAM Mexico-City

Andy Monkman, Durham University
Klaus Meerholz, Cologne University
Ullrich Scherf, BU Wuppertal
and co-workers
Kristina Schottler Macromolecules 2009, 42, 9225 67/43

Friedel-Crafts-Polycondensation
Bifunctional Aromatic
Bulding Block Carbonyl Component
O O
O O
N N
H
F
F F F
F
F F
F F3C O
F H O
S
N N O O
Mikhail Zolotukhin, UNAM Mexico-City

PME 124 Toluene Sol.
Novel PhoLED
Makromolekulare
1,0 Matrix Polymers - Optical Properties
Chemie
F
F N
0,5 O
PME 124
(Mn 114,000, Mw 216,000)
F
F
n
0,0
1,0 Ir(mppy)3 Phosphorescence
2.4 eV
Intensity / a. u.
Fluorescence
Absorption
PME 124 Film
0,5
0,0
2,0 2,5 3,0 3,5 4,0 4,5
Mikhail Zolotukhin, UNAM Mexico-City Energy / eV
Andy Monkman, Durham University
Klaus Meerholz, Cologne University
Ullrich Scherf, BU Wuppertal Solid state optical spectra of PME 124
and co-workers
Macromolecules 2009, 42, 9225

Novel PhoLED Matrix Polymers - OLED experiments
Mikhail Zolotukhin, UNAM
PME 124 Andy Monkman, Durham
100nm Al Klaus Meerholz, Cologne Univ.
2nm CsF F
F N Ullrich Scherf, Wuppertal
60 nm PME + O and co-workers
3, 7, 10% dye Macromolecules 2009, 42, 9225
F
10nm HTL 2 F
n
40nm HTL 1
35nm PEDOT
N
ITO 1,0
N
Ir 2.37 eV 40-3 10V
Glas 40-3 8V
N 40-7 7V
0,8 40-7 9V
Configuration of the 40-10 6V
Normalized Intensity
40-10 8V
investigated PhoLEDs
Ir(mppy)3 0,6
0,4
Similar EL spectra
at different voltages (6-10 V) 0,2
and Ir(mppy)3 loadings (3, 7, 10 %)

0,0
Maximum PhoLED efficiency: 400 450 500 550 600 650 700 750 800
17.5 Schottler
Kristina Cd/A @ 5 V and 7 % dye loading Wavelength, nm 70/43
Other Applications for p-Conjugated Organic Materials
• Large area & flexible substrates possible

• Large variety of materials
• Low cost
Kristina Schottler
Organic Lasers,
Photodetectors,
Sensors etc.
Kristina Schottler





Inorganic Solar Cells (Indium free!)
Liquid-based, thin film deposition:

Todorov et al.; Adv. Mater. 22 (2010) E156
Kristina Schottler


Solar Panels based on Inorganic Materials
OSCs
2nd generation 1st generation

Kristina Schottler (thin films) (bulk silicon)






























Bulk Heterojunction Polymer Solar Cells
Efficiency Limits
Servaites et al.; Appl. Phys. Lett. 95 (2009) 163302.
Kristina Schottler
BulkMakromolekulare
HeterojunctionChemie
Solar Cells - Efficiency Limits
R1 R 2 R3 R
1
MeLPPP
R1 R1 n
R2 R 3
high and medium
bandgap homopolymers
R
P3HT
S
n
low bandgap
S donor-acceptor
N N
copolymers
P3HT: 4.9 %
S S n PCPDTBT
S
N N PCPDTTBTT
S S S S n
MeLPPP: 1.25 %
Chart: from Scharber et al.; Adv. Mater. 2006, 18, 789;
N
S
N
PCPDTTTDT data points for MeLPPP, P3HT added
S S
S S S n
A D
Kristina Schottler n
Bulk Heterojunction Polymer Solar Cells (BHSCs)
State-of-the-Art:
ca. 8.2 % Power Conversion Efficiency published (PCE) (2011: 9.3 % press release)
(current record value: Luping Yu, Univ. Chicago; Standard: AM 1,5)
Donors: P3HT, PCPDTBT (KONARKA), other polythiophenes PBT1-7 (L. Yu) and polycarbazoles
Acceptors: PC61BM, PC71BM etc.
Efficiency Target:
>10% predicted (Scharber et al., KONARKA, Adv. Mater. 2006, 18, 789)
Needs for PCE Improvement:

1.) HOMO/LUMO alignment (LUMO donor ca. 3.3 - 3.5 eV with PC61BM acceptor)
2.) High absorption coeffcients
3.) Sufficient charge carrier mobility
4.) Optimized „Bulk Heterojunction“ morphology
5.) Processing improvements
Kristina Schottler

DA-type Alternating Copolymers
Luping Yu (U Chicago)
Mario Leclerc (U Laval)
Mats Andersson (U Gothenburg)
René Janssen (TU Eindhoven)
Gui Bazan (UCSB)
Yong Cao (CAS)
Electron-poor („acceptor“) moieties John Reynolds (UF Gainesville)
Zhenan Bao (Stanford U)
A + D A D Seth Marder (GeorgiaTech)
n Russell Gaudiana (KONARKA)
Electron-rich („donor“) moieties Wei You (U North Carolina)
Alex Jen (U Washington)
Samson Jenekhe (U Washington)
Iain McCulloch (Imperial)
Steven Tierney (MERCK)
David Ginley, Dana Olsen (NREL)
Thuc-Quyen Nguyen (UCSB)
Mark Watson (U Kentucky)
Zhishuan Bo (CAS)
Ullrich Scherf (BU Wuppertal)
Review: X. Zhan, D. Zhu; „Conjugated polymers
for high-efficiency organic photovoltaics“,
…. and many others
Polymer Chem. 1 (2010), 409-419
Kristina Schottler
Improved Match with the Solar Spectrum
in Polymer/PCBM-based BHSCs
P3HT PCBM
P3HT/PCBM
PCE: ca. 5.0 %
PCPDTBT
PCPDTBT (KONARKA)
PCE: 5.5 %, Heeger et al. 2007
Kristina Schottler
Polymer/PCBM-based BHSCs
Role of Processing Additives (a,w-alkane dithiols)
HS SH
n
Peet et al.; Acc. Chem. Res. 42 (2009) 1700.

Kristina Schottler
Donor Acceptor
DA-type Alternating Copolymers – Structure
n
D D A D
S S n
N
R R
R R R
René Janssen (TU Eindhoven)
A Electron-rich
B („donor“)
C moieties Mats Andersson (U Gothenburg)
Mario Leclerc (U Laval)
S
S
S
S
S
S
Russell Gaudiana (KONARKA)
S
Luping Yu (U Chicago)
D E F
Gui Bazan(UCSB)
Yong Cao (CAS)
A A Zhishuan Bo (CAS)
R R R R S S
Ullrich Scherf (BU Wuppertal)
N N
N N N N
N N
John Reynolds (UF Gainesville)
Klaus Müllen (MPIP Mainz)
S N
S
N Mark Watson (U Kentucky)
a b c d Zhenan Bao (Stanford U)
Electron-poor („acceptor“) moieties
Ph Ph O …. and many others
N N
S S
Si N S
N S
R R
O Review: X. Zhan, D. Zhu; „Conjugated polymers
e f g h for high-efficiency organic photovoltaics“,
Polymer Chem. 1 (2010), DOI 10.1039/b9py00325h
Kristina Schottler
of Aromatic and Quinoid Resonance Structures –
Interplay
Decreasing Arrgyomatic Resonance Energy and
HOMO/LUMO Bandgap
S OR1
F S S OR1
F S
S
ROOH2C S
S
R1O ROOC
S
R1O
Ground State Excited State
S S
N N N N
S S
N N N N
S S
Kristina Schottler
DA-type Alternating Copolymers – Synthesis Example
A D
n Moule, Tsami, Scherf, Brabec et al.; Chem. Mater. 20 (2008) 4045
S
S
R1
N N R1 n
R2 R2 PCPDTQ
S S
N N S
S
PCPDTTBTT R1
R1 n
Mn: 13,200/13,500
Mw: 20,000/20,000
R1: -2-ethylhexyl; R2: -n-octyl
Kristina Schottler

Moule, Tsami, Scherf, Brabec et al.; Chem. Mater. 20 (2008) 4045
A D
n Absorption PCPDTBTT
1,5 Absorption PCPDTQ 1,5
S Emission PCPDTBTT
Photoluminescence (a.u.)
S Emission PCPDTQ
Absorbance (a.u.)
R1
N N R1 n
1,0 1,0
R2 R2 PCPDTQ
S
0,5 0,5
S S
N N S
S
PCPDTTBTT R1
R1 n
0,0 0,0
Mn: 13,200/13,500 400 600 800
Mw: 20,000/20,000
R1: -2-ethylhexyl; R2: -n-octyl Wavelength (nm)
PCE (AM 1.5) PCPDTTBTT/PC61BM: 2.1 % (Adam Moulé, UC Davis)
Kristina Schottler PCE (AM 1.5) PCPDTTBTT/PC71BM: 2.7 % (V. Dyakonov et al., Univ. Würzburg)
A D
n
R3
N O
O S
S
S
R1
R1 n
PTPD8CPDT
PCE (AM 1.5) PTPD8CPDT/PC71BM: 4.65 %

(V. Dyakonov et al., Univ. Würzburg)
Kristina Schottler

Cyclopentadithiazole (CPDTz)-based
DA-type Alternating Copolymers – Monomer Synthesis
C. Kudla, U. Scherf et al.; Macromolecules 43 (2010), 7864.

Cyclopentadithiazole (CPDTz)-based Alternating Copolymers
C. Kudla, U. Scherf et al.;

Macromolecules 43 (2010), 7864.
1,0
PCPDTzN
PCPDTN
0,8
lmax: 641 nm/1.93 eV for PCPDTzN Absorbance /a.u.

0,6
764 nm/1.62 eV for PCPDTN
DEabs: 0.31 eV
0,4
HOMO energy values (ionization potential IP)

Riken Keiki AC-2
0,2
- 5.95 eV for PCPDTzN
- 5.68 eV for PCPDTN
DEIP: 0.27 eV downshift 0,0
(in BHJ SCs: Voc increase expected) 300 400 500 600 700 800 900
Kristina Schottler Wavelength /nm 126/43

A D
1132 1237
n 1,0
Absorbance [a.u.]
S
N N S
S
R 0,5
N N R n
S
*
Solution (1,2-Dichlorobenzene)
Film
* solvent
0,0
What influences the HOMO/LUMO energy 500 1000 1500 E = 0.75 eV
opt
levels in these alternating copolymers? Wavelength [nm]
Complex interplay of:

- Donor and acceptor strength
- Donor-acceptor distance
- Aromatic resonance energy in the ground and excited state
(especially for the incorporation of „non-classical“ aromatic building blocks)
Kristina Schottler

Record Power Conversion Efficiency of
Polymer/PCBM-based BHSCs (Yu et al.; Adv. Mater., Jan. 2010)
solvents:
chlorobenzene (CB)
dichlorobenzene (DCB)
processing additive:
1,8-diiodooctane (DIO)
Kristina Schottler






Solar Panels based on Polymer/PCBM-based BHSCs
Non-spin coating method

Total area: 202 cm2
Efficiency:
- Active area: 4.56%
- Module: 3.87%
Plastic Solar Panels from Solarmer
Kristina Schottler

Conjugated Polymers - Semiconducting Polymers
polythiophene-b-
polyfluorene

All-Conjugated Block Copolymers - Active Layers
of „Bulk Heterojunction“-Type Organic Solar Cells ?
Solid State Morphologies

of Diblock Copolymers
Spheres Cylinders Lamellae
Concept: Formation of Lamellar Nanostructures (via the Block Copolymer

Approach) based
Kristina on all-Conjugated Semiconducting Copolymers
Schottler 139/43
Synthesis and Microstructure Investigation of the
Donor/Acceptor Block Copolymer P3HT-b-PPerAcr
2
10
P3HT-b-PPerAcr
T=210° C
• independent crystallization
T=210° C T=210° C
1
10
intensity [a.u.]
of both blocks
• formation of nanoscale
0
10
-1
10 phases by crystallization
-2
10
T=90° C T=90° C T=90° C
-3
10 -1 0 1 -1 0 -1
10 10 10 10 scattering 10
vector q [nm10] 1 10
-1
10
0
10
1
-1 -1
scattering vector q [nm ] scattering vector q [nm ]
M. Thelakkat et al.
200 nm Angew. Chem. Int. Ed. 47 (2008) 7901.
J. Mater. Chem. 19 (2009) 4126.
Kristina Schottler
Amphiphilic P3AT-b-PF
Makromolekulare Chemie Diblock Polymers –
Synthesis („grafting from“-Approach)
A. Gutacker, U. Scherf et al.;
Macromol. Rapid Commun. 30 (2009) 1059;
Acc. Chem. Res. 41 (2008) 1086.
O Pd[0], 8 hours
B Br
O C 6 H12Br
C8 H 17 C 8H 17 H Br
S n Br-P3BrHT
C 6H 12Br C6 H12 N(CH 3) 3+ Br-

N(CH3 )3
S n S
m n m
C8 H 17 C 8H 17 C8 H 17 C 8H 17
PF2/6-P3BrHT PF2/6-P3TMAHT (methanol and water-soluble !!)
PF2/6-b-P3TMAHT used as electron injection layer in PCDTBT/PCBM BHJ-type solar cells - PCE up to 6.3%
collaboration with Gui Bazan/Alan Heeger, UCSB; Yong Cao, Guangzhou – JACS, asap DOI 10.1021/ja2037673
Kristina Schottler
Amphiphilic P3AT-b-PF Diblock Copolymers –
Self Assembly into Vesicles
Topography Phase
R. Advincula, U. Scherf et al.,

Transfer of the LB films at a Macromolecules 41 (2008) 6169.
Surface Pressure of 50 mN/m
Kristina Schottler
Amphiphilic P3AT-b-PF Block Copolymers:
Mechanism of Vesicle („Polymersome“) Formation
THF/Water (10 – 60 %)
THF/Water (> 70 %)
THF (non-selective solvent) vesicle formation,
vesicle formation,
almost isolated chains aggregation of the hydrophobic
aggregation of the hydrophilic
PF blocks (1st step)
PT blocks (2nd step)
„polymersomes“
Polyfluorene Block
Polythiophene Block C 6 H12PO(OC 2H 5 )2
S
n m
C 8H 17 C 8 H17
1.) Water is a non-solvent for the hydrophobic (non-polar) PF block

2.) PT aggregation (2nd step) induces the distinct color change
Amphiphilic
Makromolekulare P3AT-b-PF
Chemie Block Copolymers:
Model for the Aggregation of the Polar PT Blocks
increasing
water content
1,2 a Solvents:THF/Water
Water 0%
Water 50%
Water 60%
0,8 Water 70%
Intensity Water 80%
Water 90%
0% 50% 60% 70% 80% 90%

0,4
water
0,0
300 400 500 600 700
1st step 2nd step
Kristina Schottler Wavelength (nm) 144/43
Amphiphilic P3AT-b-PF Block Copolymers:
Vesicle („Polymersome“) Size
20 - 40 nm
ca. 140 nm ca. 125 nm
increasing water content

Amphiphilic P3AT/PF Diblock Copolymers:
Aggregation in THF/Water Mixtures
a THF: non-selective solvent
1,2 Solvents:THF/Water
PF (dissolves both blocks)
Water 0%
water: non-solvent for the non-polar PF block
Water 50%
Water 60%
0,8 Water 70%
Intensity
Water 80% G. Tu, H. Li, L. Balk, U. Scherf et al.

Water 90%
PT SMALL 2007, 3, 1001
0,4 Very similar optical properties of PF-b-PT

diblock copolymers reported by:
A. E. Javier, S. R. Varshney, R. D. McCullough,
Macromolecules, 2010, 43, 3233
0,0
300 400 500 600 700
0% 50% 60% 70% 80% 90%
Wavelength (nm)
water
C 6 H12PO(OC 2H 5 )2
S
n m
C 8H 17 C 8 H17
AFM: a: 30 %; b: 80 %, c: 90 % water
Particle size: ca. 140 nm (a, b), 125 nm (c)
400
a Solvents:THF/Water
Water 0% C 6 H12PO(OC 2H 5 )2
Water 10%
300 Water 20%
Water 30% S
n m
Water 40%
PF
Intensity
Water 50% C 8H 17 C 8 H17

200 PT Water 60%
Water 70%
Water 80%
1 Water 90% In the emission spectra and in the AFM images –
100 2 two aggregation steps (1 and 2) are observed
G. Tu, H. Li, L. Balk, U. Scherf et al.

0 SMALL 2007, 3, 1001
400 500 600 700
Wavelength
Kristina Schottler (nm) 147/43
1,2 a Solvents:THF/Water
PF
Water 0%
Water 50% In the absorption spectra only the second
Water 60% aggregation step of the P3AT blocks is
0,8 Water 70%
observed
Intensity
Water 80%
Water 90%
PT G. Tu, H. Li, L. Balk, U. Scherf et al.
SMALL 2007, 3, 1001
0,4
2
0,0
300 400 500 600 700
0% 50% 60% 70% 80% 90%
Wavelength (nm) water
C 6 H12PO(OC 2H 5 )2
S
n m
C 8H 17 C 8 H17
Ionic P3AT-b-PF Diblock Polymers – Synthesis
(„grafting from“-Approach)
A. Gutacker, U. Scherf et al.;

Macromol. Rapid Commun. 30 (2009) 1059;
Acc. Chem. Res. 41 (2008) 1086.
O Pd[0], 8 hours
B Br
O C 6 H12Br
C8 H 17 C 8H 17 H Br
S n Br-P3BrHT
C 6H 12Br C6 H12 N(CH 3) 3+ Br-

N(CH3 )3
S n S
m n m
C8 H 17 C 8H 17 C8 H 17 C 8H 17
PF2/6-P3BrHT PF2/6-P3TMAHT (methanol and water-soluble !!)
Kristina Schottler
Amphiphilic P3AT-b-PF: Vesicle Formation
C6 H 12 NC 5H 5 + Br-
U. Scherf, A. Gutacker, N. Koenen, S. Adamczyk,
Macromol. Rapid Commun. 2009, 30, 1059 S
n m
C 8H 17 C 8 H17
AFM: Tapping Mode (Topography – left; and phase image – right), on mica,
drop casting
Kristina from methanolic solution with c = 0.08 mg/mL
Schottler 150/43
Amphiphilic P3AT/PF Diblock Polyelectrolytes:
Crystallisation of the P3DMAHT Vesicle Shell
C6 H12 N(CH 3) 3+ Br-
S
n m
C8 H 17 C 8H 17
drop casting from methanolic solution with c = 0.1 mg/mL
Amphiphilic P3AT/PF Diblock Polyelectrolytes: Bu
Crystallisation
C6 H12 N(CH 3) 3+ Br-
S
n m
C8 H 17 C 8H 17
drop casting from methanolic solution with c = 0.1 mg/mL
Amphiphilic P3AT-b-PF
Makromolekulare Chemie Diblock Polyelectrolytes:
Confocal PL Microscopy (in Methanol) - Sectional Images
C6 H 12 NC 5H 5 + Br-
Vesicle size: ca. 3.5 mm, c = 10 mg/mL

S
n m
C 8H 17 C 8 H17
Kristina Schottler Done in collaboration with Gui Bazan‘s group, UCSB153/43

Ionic P3AT-b-PF Diblock Polymers as Electron Extraction
Layers of BHJ-type Organic Solar Cells
Al
CPE PF2/6-b-P3TMAHT and P3TMAHT as ionic electron
extraction layers (EEL) in PCDTBT/PCBM BHJ-type
PCDTBT:PC71BM solar cells leads to PCE improvements up to 6.5%
PEDOT:PSS J.. H. Seo, A. Gutacker, G. Bazan, A. Heeger, Y. Cao,

ITO U. Scherf et al., J. Am. Chem. Soc. 2011,133, 8416
Kristina Schottler
Energy vs. Charge Transfer Systems
CT
LUMO LUMO LUMO
LUMO
LUMO hn LUMO
FRET
hn or: CT hn
HOMO HOMO HOMO

HOMO HOMO
HOMO
High Low Bandgap Charge Charge Charge Charge

Bandgap Component Donor Acceptor Donor Acceptor
Component (e.g. P3HT) (e.g. P3HT) (e.g. PCBM)
(e.g. PF2/6)
Energy vs. Charge Transfer Systems
CT
LUMO LUMO LUMO
LUMO
LUMO hn LUMO
FRET
hn or: CT hn
HOMO HOMO HOMO

HOMO HOMO
HOMO
High Low Bandgap Charge Charge Charge Charge

Bandgap Component Donor Acceptor Donor Acceptor
Component (e.g. P3HT) (e.g. P3HT) (e.g. PCBM
(e.g. PF2/6) or PFTBTT)
Donor-Acceptor-Type, All-Conjugated Block Copolymers:
P3HT-b-PFTBTT Synthesis
C 6H 13
H S Br
S S n
R' 3Sn
N
N
S R
R Br Stille-type coupling
R. Mulherrin, N. Greenham, S. Jung,

C 6H 13
U. Scherf et al..
S S Nano Letters 2011, 11, 4846.
S
n
N
N
S R
R
m
P3HT-b-PFTBTT (APFO-type)
Br-Endcapped Br-P3HT: Mn: 11,300 (PDI: 1.06)

Block Copolymer P3HT-b-PFTBTT : Mn: 19,000 (PDI: 1.30) (R: 2-octyldodecyl)
Absorption Spectra of P3HT-b-PFTBTT (Solution and Film)
C 6H 13
H S Br
S n
N
S R
R Br
C 6H 13
S S
S
n
N
N
S R
R
m
P3HT-b-PFTBTT
PL and PL Excitation Spectra of P3HT-b-PFTBTT (Solution)
C 6H 13
H S Br Diblock PL
S n
Excitation: 500 nm
N
S R
R Br
C 6H 13
S S
S
n
N Excitation spectrum taken @ 575 nm: P3HT
N
S R
R Excitation spectrum taken @ 710 nm: PFTBTT
m
P3HT-b-PFTBTT only little (intrachain) energy transfer in solution:
Kristina Schottler in isolated chains both blocks act „independent“ 159/43
C 6H 13
H S Br
S n
N
Donor-Acceptor-Type,
N All-Conjugated Block Copolymers:
S R
Solid State Structure Formation
R Br
C 6H 13
S S
S
n
N
N
S R
R
P3HT-b-PFTBTT m
Formation of lamaellar morphology obeserved
Sectional TEM images point for

standing lamellae throughout the film
(A) AFM height (image height 4 nm) and
(B) phase image of the ternary mixture
after annealing (2 h at 220°C)
R. Mulherrin, N. Greenham, S. Jung, U. Scherf et al.

Nano Letters 2011, 11, 4846.
C 6H 13
H S Br
S n
N
Donor-Acceptor-Type,
N All-Conjugated Block Copolymers:
S R
Bulk Heterojunction-Type All-Polymer Solar Cells
R Br
C 6H 13
S S
S
n
N
N
S R
R
P3HT-b-PFTBTT m
BHJ-type solar cells with a ternary blend

P3HT / PFTBTT / P3HT-b-PFTBTT (ca. 40-50% diblock) as
active material showed maximum PCE’s of up to 1.0%.
More interestingly, the active layers show a

high morphological stability up to temperatures of > 200°C.

Nano Letters 2011, 11, 4846.

Morphological Stability of Ternary Blends
C 6H 13
H S Br
S n
N
N
S R
R Br
P3HT-b-PFTBTT
C 6H 13
S S
S
n
N
N
S R
R
m

Nano Letters 2011, 11, 4846.
Microporous Polymer Networks (MPNs) – State-of-the-Art
Yamamoto-type coupling
Record BET surface area: 5500 m²/g (now improved up to 6000 m²/g)
Ben et al., Angew. Chem. 2009, 121, 9621
(most other examples: BET surface area up to 2000 m²/g)

Microporous Polymer Networks – Our Approach
O
HOAc/HCl/H20 Truxene/Truxenone Synthesis
3 98%
16h / 100°C
O O
H2SO4 conc. O
3
90%
3h / 100°C
O
O
E. V. Dehmlow, T. Kelle, Synth. Commun. 1997, 27, 2021

Microporous Ladder Polymer Networks
R R
R
R
R R R R R
R R
O R R R R
R
R
R R
R R R
O TiCl4 R R R R R R
A R R R R R R
R R R
O R R
R
R R R
R R R R R
R R R R R R
O
R R R
B R R R
R R
R R
R R R R R
R
R R R
R R R
R
R R R
S. Sprick, A. Thomas, U.Scherf,

Polym. Chem. 2010, 1, 283. R: H (A) or Me (B)


O O
O O O
O O
MSA
C
O O O
O
O O O
O
O
O
O O
O O O O
O
Entry Monomer Reagent/ Temp. Time Yield SBET O O
Solvent (°C) (h) (%) (m2/g) O
O
1 A TiCl4/ODCB 180 72 quant. 1165
O
2 B PTSA/ODCB 105 72 31.7 -
3 B PPA 160 72 70.6 -
4 B molten ZnCl2 400 72 10.3 173
5 B TiCl4/ODCB 180 72 84.5 395
6 C H2SO4 100 24 quant. 49 S. Sprick, A. Thomas, U.Scherf,

(20% aqueous) Polym. Chem. 2010, 1, 283.
7 C MSA/ODCB 180 3 quant. 1650
R R
R
R
R R R R R
R R
R R R R
R
R
R R
R R R
R R R R R R
R R R R R R
R R R
R R R
R R R
R R R R R
R R R R R R
R R R
SSB R R R
R R
R R
R R R R R
R
R R R
300 200 100 0 R R
[ppm] R
R
R R R
13C {1H}
CP/MAS NMR spectrum (10 kHz MAS) of the cyclotrimerization product
of monomer B (R=CH3; entry 5); SSB: spinning side bands.

Microporous Polymer
Makromolekulare Chemie Networks in Simple
Polycondensations after Friedel-Crafts
N N N
N N
O O
O
A C
B
N N N N N
O O O
D E F
N N
N N
O
O
H
G
N N N N
E. Preis, A. Thomas, U.Scherf,

Polym. Chem. 2011, 2, published online asap. O O
Kristina Schottler I J 168/43

Microporous Polymer
N R R N
N R N
R
N N N N
N R N
R R R R R
O
A/B N N
N N
R R
R R
N N N N R
R R R
OH
E. Preis, A. Thomas, U.Scherf,

Polym. Chem. 2011, 2, published online asap.
Microporous Polymer
Entry Monomer(s) Yield SBET surface SBET after Total pore
area supercritical volume
(m2/g)[1] CO2 washing (cm3/g)[2]
(m2/g) [after SC CO2
washing]
1 A quant. 1420 1243 1.31 [0.90]
1260[3] - 0.60[3]
2 B quant. 57 - 0.06
3 A/B (1:1 w/w) quant. 716 924 0.47 [0.53]
4 C quant. 228 - 0.16
5 A/C (1:1 w/w) quant. 718 1775 0.43 [1.26]
6 B/C (1:1 w/w) quant. 9 - 0.009
E. Preis, A. Thomas, 7 D quant. 1161 1394 0.80 [0.85]
8 E quant. 12 - 0.01
U.Scherf,
9 F quant. 16 - 0.02
Polym. Chem. 2011, 2, 10 D/E (1:1 w/w) quant. 9 - 0.01
published online asap. 11 D/F (1:1 w/w) quant. 372 - 0.28
12 E/F (1:1 w/w) quant. 14 - 0.02
13 G quant. 9 - 0.01
14 H quant. 18 - 0.02
15 G/H (1:1 w/w) quant. 3 - 0.01
16 I quant. 17 - 0.02
17 J quant. 163 - 0.30
18 I/J (1:1 w/w) quant. 947 1447 0.67 [0.97]
Kristina Schottler 19 A/D (1:1 w/w) quant. 968 1748 0.77 [1.6]
170/43
Acknowledgements
Dr. Michael Forster

Makromolekulare Chemie Dr. Sybille Allard
Sylwia Adamczyk, Anke Helfer,

Eduard Preis
Post docs
PhD students
Master students
Dr. Woijtek Pisula (Müllen group), Dr. Gunther Brunklaus (Spiess group), MPIP Mainz, Germany
Prof. Klaus Meerholz, Cologne Univ., Germany
Prof. Arne Thomas, Berlin Technical Univ., Germany
Prof. Hugh Burrows, Dr. Sophia Fonseca, Coimbra Univ., Portugal
Prof. Gui Bazan, UCSB, US
Prof. Mikhail Zolotukhin, UNAM, Mexico
Prof. Andy Monkman, Durham Univ., UK
Dr. Neil Greenham, Cambridge Univ., UK
Prof. Yuguang Ma, Yilin Univ., Changchun, PR China
Prof. Rigoberto Advincula, Univ. of Texas/Houston, US
Dr. Rachel Evans, Trinity College Dublin, Ireland
Kristina Schottler Funding: EU (ONE-P), BMBF, DFG171/43

Presentacion Polimeros Conjugados

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Presentacion Polimeros Conjugados

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Makromolekulare Chemie

Synthesis of Conjugated Polymers

Macromolecular Chemistry Group

Prof. Ullrich Scherf

ca. 560 publications

Kristina Schottler 3/43

Organic and Polymer semiconductors what is that?

Kristina Schottler 4/43

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Semiconducting (Conjugated) Polymers

poly(p-phenylene) poly(p-phenylvinylene) poly(p-phenylethynyle) poly(fluorene)

Scherf, Müllen McCullough, Schlüter Shirakawa, Feast,

ladder-poly(p-phenylene) polythiophene polypyrrole polyacetylene

Kristina Schottler 21/43

Kristina Schottler 22/43

Synthesis of Conjugated Polymers

1. Wessling/Zimmermann and Gilch procedure (PPVs)

3. Metathesis reactions (alkene & alkyne metathesis)

(developed by Ballauf & Wegner for polyesters)

PPP: out-of-plane distortion ca. 15-20°

2.5-dialkyl-PPP: out-of-plane distortion ca. 80°

- High Molecular Weight (> 10,000)

Hairy-rod concept 2.5-dialkyl-PPP: out-of-plane distortion ca. 80°

(developed by Ballauf & Wegner for polyesters)

Polyfluorenes Ladder-PPP (LPPP)

Kristina Schottler 33/43

Formation of TBB defects in GILCH PPV derivatives

YAMAMOTO route (Ulli Scherf et al.)

C. Kudla, N. Koenen, U. Scherf (BUW), W. Pisula (MPIP Mainz) et al.

atactic a-PF1/12: 2 signals,

isotactic i-PF1/12: 1 signal,

Kristina Schottler 51/43

c) 2D-WAXS1images: i-PF1-12 a-PF1-12

b) isotactic i-PF1-12 (recorded at 30 °C)

Polarizing Microscopy images:

Photoluminescence (a. u.)

Extinction (a. u.)

R1: -hexyl 0-2

„A soluble ladder polymer via bridging of functionalized poly(p-phenylene)-precursors”

Q. L. Zhou et al., Org. Lett. 2004, 6, 2381

C.-T. Chen et al., Org. Lett. 2005, 7, 3717

Progress in Synthesis – Ladder PPP (LPPP) Synthesis

C10H 21 C10 H21 C10H 21

Spiro-LPPP (Scherf 2009, alternative route by Z. Bo 2008)

Kristina Schottler 55/43

McCULLOUGH route I (Rick McCullough et al.)

P3AT (P3HT etc.)