molecular engineering [kompatibilitätsmodus] · molecular engineering. lecture 3b. molecular...
TRANSCRIPT
LINZ LECTURES
Lecture 1. The Development of Organic Conductors: Metals, Superconductors and Semiconductors, p
Lecture 2A. Introduction and Synthesis of Important Conjugated PolymersLecture 2B. Solid State Polymerization
Lecture 3. Fullerene ChemistryLecture 3B. Molecular Engineering
Lecture 3B. Molecular Engineering of Conjugated Polymers for OE
Processing Design
Bandgap Design
N-Dopable Designp g
Self-Dopable and Water Solubility DesignSe opab e a d ate So ub ty es g
The Most Popular Conjugated PolymersHN
n(CH)xPA PANI
n
O O
Y
S nPPPPITN
S nPEDOT
X
XZ
X = S, NH, NR; Y = H, R, Ph, etc
PT, PPy, etc Y PPVs
n
X Y
n
PFs
THE DRIVE TOWARD PROCESSING
O
The Evolution of Processable PPV as an ExampleO
n
O
O
nO
n
n
O O O
O O
Cl
Cl
O
n
O O
MEH-PPV
F. Wudl, P.-M. Alleman, G. Srdanov, Z. Ni, D. McBranch in “Materials for Nonlinear Optics” S. Marder, J.E. Sohn. G.D. Stucky, Eds; American Chemical Society Symposium Series, 1991. pp 683-686.
Designing the Semiconductor Gap
The Bandgaps of Conducting Polymers(π−π∗)
Polymer ΔE Gap, eV
3 0ca. 3.0
S S S ca 2 1S S
ca. 2.1
ca 1 5ca. 1.5
SS
SS
S ca. 1.1
The Concept of Low Bandgap Based on Benzenoid and Quinoid Equivalence
S S S S
Benzenoid and Quinoid Equivalence
SS
SS
SS
SS
TA TB
E E<<EA EB<<
SS
SS
SS
SS
IA IB
EA EBA B
Poly(isothianaphthene). Wudl, F.; Kobayashi, M.; Heeger, A. J. J. Org. Chem. 1984, 49, 3382–3384.The Electronic and Electrochemical Properties of Poly(isothianaphthene). Kobayashi, M.; Colaneri, N.;
l dl h hBoysel, M.; Wudl, F.; Heeger, A. J. J. Chem. Phys. 1985, 82, 5717–5723 Bredas, J.-L.; Heeger, J. A.; Wudl, F. J. Chem. Phys.1985, 85, 4673
Transparent to the Human Eye
Application of the Concept to a PEDOT Analog
S S S S
S
S
SS
S
SS
S
SS
S
S
S S S S
TATB
EA ≅ ΕΒ
B. Lee, V. Seshadri, G. A. Sotzing Langmuir 2005, 21, 10797
B. Lee, V. Seshadri, G. A. Sotzing Langmuir 2005, 21, 10797
The Concept of Low Bandgap Based on Intramolecular Donor-Acceptor Interactions
ON
HON
S
O*N
Hn O
O
SN
C12H25
n
Eg ca 0.5 eV
Havinga, E.E.; Pomp, A.; Ten Hoeve, W.; Wynberg, H. Synthetic Metals, 1995, 69, 581Havinga E E ; Pomp A ; Ten Hoeve W ; Wynberg H Polym Bull 1992 29 119Havinga, E.E.; Pomp, A.; Ten Hoeve, W.; Wynberg, H. Polym. Bull., 1992, 29, 119J. Eldo and A. Ajayaghosh Chem. Mater. 2002, 14, 410-418
J. P. Ferraris and T. L. Lambert J. CHEM. SOC., CHEM. COMMUN., 1991, 1268
J. P. Ferraris and T. L. Lambert J. CHEM. SOC., CHEM. COMMUN., 1991, 1268
J. P. Ferraris and T. L. Lambert J. Chem. Soc., Chem. Commun., 1991, 1268
Said Akoudad and J. Roncali J. C h e m.Soc. Chem. Commun., 1998, 2081
Said Akoudad and J. Roncali J. C h e m.Soc. Chem. Commun., 1998, 2081
I. F. Perepichka, E. Levillain and J. Roncali J. Ma t e r. C h e m., 2004, 14, 1679
I. F. Perepichka, E. Levillain and J. Roncali J. Ma t e r. C h e m., 2004, 14, 1679
The Concept of Low Bandgap Polymer Based on Small Bandgap MonomerBased on Small Bandgap Monomer
If the monomer units have a small HOMO LUMO gap it stands toIf the monomer units have a small HOMO-LUMO gap, it stands to reason the incorporation into a conjugated backbone ought to produce an even smaller bandgap polymer
An Example of a Very Low Bandgap Molecule
O
OO
A New Polymer with a 0.9 eV BandgapS S
nS S
FeCl3
THF
1 8
2.0
Monomer in CHCl
RR
1.4
1.6
1.8 Monomer in CHCl3 Polymer in CHCl3 Polymer Film
u.)
1.0
1.2
orpt
ion
(a.
0 4
0.6
0.8
Abs
o
0.0
0.2
0.4
300 400 500 600 700 800 900 1000 1100 1200
Wavelength (nm)Satish PatilWes Walker
Materials with Spectral Response: 400nm ~ 1400nm
8
9
10
11
12
(L/g
cm
)
O3
4
5
6
7
Abs
orpt
ion
Coe
ffici
ent '
SS
R
0
1
2
3
250 350 450 550 650 750 850 950 1050 1150 1250 1350 1450 1550 1650Wavelength(nm)
A
Rn
R =
Wavelength (nm)
4
10-3
10-2
Photo Current
-4 1eV
-3.9 eV
Electron Donor: FW-D1
10-6
10-5
10-4
J (A
/cm
2 )
-4.1eV
FW-D
1
PCB
M
10-9
10-8
10-7
-1 -0.5 0 0.5 1 1.5
Dark Current
-4.9 eV
-6.3 eV
P Bias (V)
Preliminary Results
Hexyl
S
SNi
S
nS
S
S
Hexyl
Rajeev Kumar/Britt Veldman
The Drive Toward n-Dopable Polymers
The Drive Toward n-Dopable Polymers
OC6H13
C6H13O
*
*
CN
NCn
OC6H13
C6H13O
OC6H13
C6H13O
*
*
CN
NCn
SCH3
C12H25O
OR
O
*
*
CN
NC
OR
O n12 25
CN-PPV1 (Eg = 2.1 eV)
* CNOC6H13
CN-PPV2 (Eg = 2.2 eV)λPL = 710 nm λPL = 610 nm
R = C8H17R = C10H21R = C12H25R = C16H33
Eg = 2.0 eVλPL = 611nmλEL = 603-618 nm
*
*
CN
NCnC6H13O
*
*
CN
NCn
*
*
CN
NCnOCH3
CN-PPV3 (Eg = 2.85 eV)
CN-PPV4 (Eg = 3.2 eV) CN-PPV5 (Eg = 3.05 eV)λPL = 516 nm; λEL = 510 nm
*
*
CN
NC
*S
*
*
CN OC6H13C12H25
*S*
CNC12H25
S
C12H25
( g ) g
n NCC6H13O n NC n
CN-PPV6 (Eg = 2.7 eV) CN-PT-co-PPV (Eg = 1.8 eV) CN-PT (Eg = 1.55 eV)
λPL = 950 nmλPL = 840 nm; λEL = 730 nm
*CN
*CN
CNN
*
nEg = 2.3 eVλEL = 560 nm
CNN
*
nEg = 2.5 eVλPL = 530 nmλEL = 560 nmλEL = 510 nm
N. C. Greenham, S. C. Moratti, D. D. C. Bradley, R. H. Friend, A. B. Holmes Efficient Light-Emitting Diodes Based on Polymers with High Electron Affinities Nature 1993, 365, 628-630
T. Nakagawa, D. Kumaki, J. Nishida, S. Tokito, Y. Yamashita Chem. Mater. 2008, 20, 2615–2617
Self-Doping and Water Solubility
Self-Doping Conducting Polymer/Water Soluble Conducting PolymerConducting Polymer
Ikenoue, Y.; Chiang, J.; Patil, A. O.; Wudl, F.; Heeger, A. J. J. Am. Chem. Soc. 1988, 110, 2983–2985
Ikenoue, Y.; Chiang, J.; Patil, A. O.; Wudl, F.; Heeger, A. J. J. Am. Chem. Soc. 1988, 110, 2983–2985
Ikenoue, Y.; Chiang, J.; Patil, A. O.; Wudl, F.; Heeger, A. J. J. Am. Chem. Soc. 1988, 110, 2983–2985
A Water-Soluble PPV
S. Shi, F. Wudl Macromolecules 1990, 23, 2119
“Superquenching of a Water-Soluble PPV
L. Chen, D. W. McBranch, H.-L. Wang, R. Helgeson§, F. Wudl, G. Whitten PNAS, 1999, 12287
Biosensor Application
L. Chen, D. W. McBranch, H.-L. Wang, R. Helgeson§, F. Wudl, G. Whitten PNAS, 1999, 12287
Summary
By application of simple design conceptsBy application of simple design concepts conjugated poly processable,
t ll bl E d bl d tcontrollable Eg, n-dopable and water-soluble conjugated polymers could be j g p yprepared and applied to organic electronics and biologyelectronics and biology