Conjugated Polymeric Materials: Opportunities in Electronics, Optoelectronics, and Molecular Electronics

590 Pages·1990·21.081 MB·English

by  Robert Silbey (auth.), J. L. Brédas, R. R. Chance (eds.)

Conjugated Polymeric Materials:
Opportunities in Electronics, Optoelectronics,
and Molecular Electronics
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NATO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The Series is pUblished by an international board of publishers in conjunction with the
NATO Scientific Affairs Division
A LBe Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston and London
D Behavioural and Social Sciences
E Applied Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris and Tokyo
Series E: Applied Sciences -Vol. 182
Conjugated Polymeric Materials:
Opportunities in Electronics,
Optoelectronics, and
Molecular Electronics
edited by
J. L. Bredas
University of Mons, Mons, Belgium
and
R. R. Chance
Exxon Research and Engineering Co.,
Annandale, New Jersey, U.S.A.
Kluwer Academic Publishers
Dordrecht / Boston / London
Published in cooperation with NATO Scientific Affairs Division
Proceedings of the NATO Advanced Research Workshop_ on
Conjugated Polymeric Materials: Opportunities in Electronics,
Optoelectronics, and Molecular Electronics
Mons, Belgium
September 3-8, 1989
Library of Congress Cataloging in Publication Data
ISBN-13: 978-94-010-7416-2 e-ISBN-13: 978-94-009-2041-5
DOl: 1O.l007/978-94-009-2041-5
Published by Kluwer Academic Publishers,
P.O. Box 17, 3300 AA Dordrecht, The Netherlands.
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© 1990 by Kluwer Academic Publishers
Softcover reprint of the hardcover 1s t edition 1990
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TABLE OF CONTENTS
Preface IX
Theory of Conjugated Polymers and Molecular Crystals 1
R. Silbey
Survey of Electrically Conducting Organic Materials 11
H. Naannann
New Developments in the Synthesis and Doping of Polyacetylene
and Polyaniline 53
A.G. MacDiarmid and AJ. Epstein
Synthesis, Characterization, and Applications of Substituted Polyacetylenes
Derived from Ring-Opening Metathesis Polymerization of Cyc100ctatetraenes 65
EJ. Ginsburg, c.B. Gorman, R.H. Grubbs, F.L. Klavetter, N.S. Lewis,
S.R. Marder, 1.W. Perry, and M.J. Sailor
Synthesis and Characterization of a Water Soluble Polyparaphenylene
Vinylene Derivative 83
S. Shi and F. Wudl
Molecular Organization and Electrical Properties of Mixed Langmuir-
Blodgett Multilayer Thin Films of Polypyrrole 91
J. Cheung, R.B. Rosner, M.F. Rubner, X.Q. Yang, 1. Chen,
and T.A. Skotheim
The Electronic and Chemical Structure of Poly(3-hexylthiophene) Studied
by Photoelectron Spectroscopy 101
W.R. Salaneck, R. Lazzaroni, N. Sato, M. Logdlund, B. Sjogren,
M.P. Keane, S. Svensson, A. Naves de Brito, N. Correia, and S. Lunell
Poly-l,2-Azepines by the Photopolymerization of Phenyl Azides:
A New Route to Processible Conducting Polymers 115
E.W. Meijer, S. Nijhuis, F.C.B.M. Van Vroonhoven, and E.E. Havinga
Polyheteroarylmethines, Syntheses and Physical Properties 133
R. Becker, G. Blochl, and H. Braunling
Conformation of Conjugated Polymers in Good Solvent 141
J.P. Aime
vi
Electronic Structure of Processable Conducting Polymers 149
R. Lazzaroni, M. Logdlund, S. Stafstrom, W.R. Salaneck, D.D.C. Bradley,
R.H. Friend, N. Sato, E. Ortl, and J.L. Bredas
Bridged Mixed Valence Phthalocyaninato-Metal Compounds 163
A. Hirsch and M. Hanack
Polyaniline Processed From Sulfuric Acid and in Solution in
Sulfuric Acid: Electrical, Optical, and Magnetic Properties 171
Y. Cao, P. Smith, and AJ. Heeger
Polyaniline versus Polyacetylene, or, Rings versus Bonds and the Roles
of Barriers and Crystallinity 195
AJ. Epstein and A.G. MacDiarmid
Linear Polyenes: The Interplay Between Electronic Structure, Geometric
Structure, and Nonlinear Optical Properties 207
lM. Toussaint, F. Meyers, and lL. Bredas
Semiconductor Device Physics in Conjugated Polymers 221
J.H. Burroughes, C.A. Jones, R.A. Lawrence, and R.H. Friend
Chemistry and Physics of Molecular-Based Polymers Exhibiting a
Spontaneous Magnetization 247
O. Kahn
Ion Implanted Polyparaphenylene: Modifications of Lateral and in Depth
Concentration Profiles upon Annealing 263
G. Froyer, Y. Pelous, M. Gauneau, R. Chaplain, A. Moliton, and B. Ratier
The Electroactive Nature of Polyaniline. The Nature of the Chromaphores 273
AP. Monkman
Transport in Oriented Polyacetylene 285
M. Galtier, M. Rolland, A Montaner, and A Alibenamara
Transient Photoconductivity in Poly acetylene and Molecular
Electronic Aspects 293
S. Roth, J. Anders, and J. Reichenbach
Dehydrochlorination of Polyvinylchloride by Phase Transfer Catalysis 299
S. Dhainaut, A Perichaud, P. Bernier, S. Lefrant, and A. le Mehaute
Vinylene-Linked Low-Band-Gap Conducting Polymers: Electronic Structure
and Defects 305
H. Eckhardt, K.Y. Jen, L.W. Shacklette, and S. Lefrant
vii
Organic Conjugated Materials for Optoelectronic and Applications 321
J.e. Dubois
Nonlinear Optics of Conjugated Polymers: Progress in Science and
Prospects for Technology 341
S. Etemad, W-S. Fann, P.D. Townsend, G.L. Baker, and J. Jackel
Transition Dipoles of Polyacetylene Oligomers 353
B.E. Kohler and J.A. Pescatore, Jr.
Linear Optical Properties of a Series of Polyacetylene Oligomers 365
H.E. Schaffer, R.R. Chance, K. Knoll, R.R. Schrock, and R. Silbey
Novel Linear and Nonlinear Optical Effects in Polydiacetylenes 377
D. Bloor, DJ. Ando, P.A. Norman, A.F. Drake, S. Mann, A.R. Oldroyd,
B.S. Wherrett, A.K. Kar, W. Ji , and T. Harvey
Nonlinear Optical Properties of Ultrathin Polymer Films 387
D. Neher, A. Kaltbeitzel, A. Wolf, C. Bubeck, and G. Wegner
Third Harmonic Generation of Poly thiophene Derivatives 399
H. Sasabe, T. Wada, T. Sugiyama, H. Ohkawa, A. Yamada, and A.F. Garito
Third Order Hyperpolarizability of Poly thiophene and Thiophene Oligomers 409
F. Charra and J. Messier
Exciton Relaxation in PDA-4BCMU: from Crystals to Films 421
M.1. Nowak, GJ. Blanchard, GJ. Baker, S. Etemad, and Z.G. Soos
Photoinduced Absorption and Nonlinear Optical Response in
a Polycondensed Thiophene-Based Polymer (PTT) 429
G. Ruani, A.J. Pal, R. Zamboni, C. Taliani, and F. Kajzar
Study of Second Harmonic Generation of a Hemicyanine Dye in Floating
and Deposited Organic Monolayers 443
A. Scheelen, P. Winant, and A. Persoons
Nonlinear Optics in Solid Schiff Bases 451
E. Hadjoudis, 1. Moustakali-Mavridis, and 1. Zyss
Triplet Exciton-Polarons in Polydiacetylene Single Crystals 457
H. Sixl and W. RUhle
Diffraction by Holographic Gratings in Diacetylene Crystals 471
Th. Vogtmann, H-D. Bauer, I. MUller, and M. Schwoerer
viii
Scanning Tunneling Microscopy at the Polymer-Metal Interface 483
J.P. Rabe and S. Buchholz
Nonlinear Optics Coefficients of Polyenes: Size and Alternation Dependence 495
Z.G. Soos, G.W. Hayden, and P.C.M. McWilliams
Electronic Structure and Static Electric Dipole Polarizability of
Acetylenic Analogs of Carbocyanines 509
V.P. Bodart, J. Delhalle, and J.M. Andre
Macrocycles as Molecular Units to Build up Electroresponsive Materials:
A Comparative Theoretical Investigation of the Electronic and Optical
Properties of Phthalocyanine and Related Systems 517
E. Ortf and J.L. Bredas
Control of Intramolecular Interferences Through Benzene and Cyclophane
Using Donor and Acceptor Groups 531
P. Sautet and C. Joachim
Organic Crystals and Quadratic Nonlinear Optics: The Transparency-
Efficiency Trade-off 545
J. Zyss
Conducting Polymer Electromechanical Actuators 559
R.H. Baughman, L.W. Shacklette, R.L. Elsenbaumer, E. Plichta,
and C. Becht
Working Group Reports:
- Prospects in Synthesis and Processibility of Conjugated Polymers 583
- Molecular Electronics Prospects 587
- Theoretical Developments 591
- Optoelectronics Prospects 595
- Electronics Properties 597
Index 599
PREFACE
This book constitutes the Proceedings of the NATO Advanced Research Workshop on
Conjugated Polymers held at the University of Mons, Belgium, during the first week of
September 1989. The Workshop was attended by about fifty scientists representing most of
the leading research groups within NATO countries, that have contributed to the
development of conjugated polymeric materials. The program was focused on applications
related to electrical conductivity and nonlinear optics. The attendance was well balanced
with a blend of researchers from academic, industrial, and government labs, and including
synthetic chemists, physical chemists, physicists, materials scientists, and theoreticians.
The Workshop provided an especially timely opportunity to discuss the important
progress that has taken place in the field of Conjugated Polymers in the late eighties as
well as the enormous potential that lies in front of us.
Among the recent significant developments in the field, we can cite for instance:
(i) The discovery of novel synthetic routes affording conjugated polymers
- that are much better characterized, especially through control of the molecular weight;
- that can be processed from solution or the melt; the early promise that conducting
polymcrs would constitute materials combining the electrical conductivities of metals with
the mechanical properties of plastics is now being realized;
- that can reach remarkably high conductivities.
(ii) The exploitation of the high nonlinear optical responses that are inherent to
conjugated materials, either for second-order or third-order effects. The detailed
investigation of the dynamics of the excited state relaxation has proven proves to be an
area of important basic and applied interest.
(iii) The novel chemistry and physics of the polyanilines and other families of
polymers where a simple protonation process can lead to an insulator-to-conductor
transition. The influence of ring motions in the transport properties is a topic of growing
interest. Furthermore, polyaniline fibers appear to display most promising mechanical
properties.
(iv) The achievement of electronic devices such as MISFET's in which
conjugated polymers in the semiconducting state play an active role in the device physics.
Five working groups were organized, that during the week actively discussed the
prospects of conjugated polymers in the areas of synthesis and processabiIity, technological
potentials, exploitation of the electronic properties, nonlinear optics, molecular electronics,
and the key needs in tem1S of theoretical efforts. The reports of the working groups, which
are collected at the end of the Proceedings, highlight the exciting opportunities for
conjugated polymers into the 1990's.
ix
x
That the Workshop ran smoothly and efficiently was due to the collaboration and hard
work of many people. Thanks are due to the University of Mons, especially the President
of the University, Professor Y. Van Haverbeke, and the Administrator, Mr. 1. Quenon,
who fully supported the endeavor; the staff of the Restaurant Universitaire; and the staff of
the Cite Universitaire.
Nothing could have been accomplished without the tremendous help from the members
of the Laboratory for Chemistry of Novel Materials at the University of Mons: especially
Ms. F. Meyers who took care of all the organizational details from the very beginning and
served as Scientific Secretary of the Workshop, Mr. I.M. Toussaint, Dr. G. Lambin, Dr. R.
Lazzaroni, and Dr. 1. Orszagh as well as Mrs. M. Cornez and Mrs. 1. Sauveniere.
The generous financial support from the NATO Division of Scientific Affairs was what
made the Workshop possible. The genuine interest in the Workshop of the NATO team,
especially Professor 1. Ducuing, Dr. C. Sinclair, and Professor L. Da Cunha is gratefully
acknowledged. Support was also received from Exxon Research & Engineering Company.
Finally, we wish to stress the fact that all the participants that presented a talk or a
poster, did write a chapter for these Proceedings, thus making this book very
comprehensive. It would also be impossible not to mention the fruitful late-evening
sessions around special Belgian beers (simply the best) and the high-tech touch brought by
Professor MacDiarmid. He used his own portable machine to fax his working group report
to his secretary at Penn in order to have it typed overnight. Never forget the human
factor, though! Professor MacDiarnlid had to phone her back and dictate the report
because she was not able to read his handwriting!
1.L. Bredas, R.R. Chance
December 1989