Organic Molecules for Nonlinear Optics and Photonics

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 Life Sciences B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change

Series E: Applied Sciences - Vol. 194

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

Organic Molecules for Nonlinear Optics and Photonics edited by

J. Messier Commissariat a l'Energie Atomique, Gif-sur-Yvette, Franca

F. Kajzar Commissariat a l'Energie Atomique, Gif-sur-Yvette, France

and

P. Prasad Department of Chemistry, State University of New York, Buffalo, U.S.A.

Springer Science+Business Media, B.V.

Proceedings of the NATO Advancad Research Workshop on Organic Molecules for Nonlinear Optics and Photonics La Rochelle, Franca August 26 - September 1, 1990

ISBN 978-94-010-5490-4 ISBN 978-94-011-3370-8 (eBook)

DOI 10.1007/978-94-011-3370-8

Printed an acid-free paper

AII Rights Reserved © 1991 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1991 Softcover reprint ofthe hardcover lst edition 1991

No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo­copying, record ing or by any informatien storage and retrieval system, without written permission from the copyright owner.

TABLE OF CONTENTS

Preface

List of Participants

THEORY OF OPTICAL HYPERPOLARIZABILITY IN ORGANIC MOLECULES

Towards the Calculations of Polarizabilities of Infinite Polymeric Chains J. M. Andre and B. Champagne

Conjugated Polymers: On the Parallel Between the Electrical Conduc­tion Mechanism and the Nonlinear Optical Response.

iX

Xi

J. L. Bredas, F. Meyers and A. J. Heeger 23

On the Calculation of the Hyperpolarizabilities of Organic Molecu­les by the Sum Over Virtual Excited States Method J. O. Morley, P. Pavlides and D. Pugh 37

Impact of Electron Quantum Confinement on Optical Nonlinearities J. Hutter and C. Flytzanis 53

Structural and Electronic Properties of Push-Pull Conjugated Mole­cules: A Theoretical Investigation of p-Amino-p'Nitrodiphenylacety­lene Compounds F. Meyers and J. L. Bredas 73

ORGANIC MOLECULES FOR SECOND ORDER NONLINEAR OPTICAL EFFECTS

Polar and Non-Polar Organic Molecules, Crystals and Langmuir­Blodgett Films for Quadratic Nonlinear Optics I. Ledoux and J. Zyss 81

Design Considerations for Multi Component Molecular-Polymeric Nonli­near Optical Materials K.D. Singer, M. G. Kuzyk, T. Fang, W. R. Holland and P. A. Cahill 105

Empirical Systematics of Molecular Quadratic Optical Polarizability Lap-Tak Cheng 121

Surface and Adsorbate Analysis by Second-Harmonic Generation G. Lupke, G. Marowsky and F. Sieverdes 137

New Molecular Design for Noncentrosymmetric Crystal Structures: Lambda shape Molecules for Frequency Doubling T. Watanabe, H. Yamamoto, T. Hosomi and S. Miyata 151

Study of Novel Class of Second Order Nonlinear Optical (NLO) Poly­urethanes R. Meyrueix, G. Mignani and G. Tapolsky 161

EFISH Studies of Stilbene- and Thiophene- Derivatives L. Derhaeg, C. Samyn and A. Persoons 177

Surface Second Harmonic Generation in Total Reflection F. Sieverdes. G. Lupke. G. Marovsky. A. Bratz and B. U. Felderhof 185

Second Order Hyperpolarisabilities and Conformations of Functiona­lized Copolymers T. Verbiest. C. Samyn and A. Persoons 201

NPNN: A New Ferromagnetic Optically Nonlinear Organic Compound G. Puccetti. I. Ledoux and J. Zyss 207

Second Harmonic Generation from Amphiphilic Dyes at the Air-Water Interface G. Gillberg. R. Keosian. L. Pruksarnukul and D. Lupo 215

THIRD ORDER EFFECTS IN THIN FILMS AND IN SOLUTIONS

Strategy for Optimization of Molecular Materials for Nonlinear Optics and Photonics P. N. Prasad 225

Excited State Nonlinear Optics Q. L. Zhou. J. R. Heflin. K. Y. Wong. O. Zamani-Khamiri and A. F. Garito 239

Influence of Conformation on Two-Photon Spectra of Polyalkylthiophene F. Charra. J. Messier. C. Sentein. A. Pron and M. Zagorska 263

Advances in the Synthesis of Electroactive Materials and in the Characterisation of Mechanisms of NLO Activity. L. Yu. D. W. Polis. L. S. Sapochak and L. R. Dalton 273

Thiophene Based Conjugated Polymers: THG Spectroscopy and Transient Photogenerated Polaron Enhancement of Cubic Optical Nonlinearity C. Taliani. G. Ruani. R. Zamboni. F. Kajzar. L. Yang. R. Dorsinville, R. R. Alfano and R. Tubino 301

Electronic Properties of Conjugated Polymers with Aromatic or Hete­ro-Aromatic Cycle S. Lefrant and J. P. Buisson 313

Oriented Conjugated Polymers for Nonlinear Optics: Properties of a Liquid Crystalline Polyacetylene. Epitaxial Growth of a Polydiace­tylene PDCH J. Le Moigne. A. Hilberer. F. Kajzar and A. Thierry 327

Third Order Nonlinear Optical Effects in Conjugated Polymers and Dye Systems C. Bubeck. A. Grund, A. Kaltbeitzel, D. Neher. A. Mathy and G. Wegner 335

Phase Conjugation under Picosecond Two-Photon Absorption in Poly­diacetylenes J. M. Nunzi and F. Charra 345

Relaxation of One- and Two-Photon Excitations in a Polydiacetylene Red Form: Frequency and Phase Resolved Analysis

vii

F. Charra and J. M. Nunzi 359

Excited State Absorption and Optical Limiting in Solutions of Metallo­phthalocyanines J. W. Perry, L. R. Khundkar, D. R. Coulter, D. Alvarez,Jr, S. R. Mar-der, T. H. Wei, M. J. Sence, E. W. Van Stryland and D. J. Hagan 369

Third Order Optical Nonlinearities in Metal Dithiolate Complexes C. S. Winter, S. N. Oliver, J. D. Rush, C. A. S. Hill and A. E. Underhill 383

Nonlinear Optical Studies of Transition Metal Containing Conjugated Organic Monomeric and Polymeric Systems A. P. Davey, D. J. Cardin, H. J. Byrne and W. Blau 391

NONCENTROSYMMETRIC THIN FILMS FOR QUADRATIC OPTICS AND WAVEGUIDING DEVICES

Organic Thin Films for Quadratic Optics F. Kajzar, P. A. Chollet, I. Ledoux,J. Le Moigne, A. Lorin and G. Gadret 403

Poled Epoxy Polymers for Optoelectronics J. D. Swalen, G. C. Bjorklund, W. Fleming, S. Herminghaus, D. Jung­bauer, M. Jurich, W. E. Moerner, B. Reck, B. A. Smith, R. TWieg, C. G. Wilson and R. Zentel 433

Poled Glassy Polymers and Metallated Macrocycles for Nonlinear Optics A. Buckley, J. P. Riggs, J. B. Stamatoff and H. N. Yoon 447

Electrooptic Organic Waveguides: Optical Characterization M. Dumont, Y. Levy and D. Morichere 461

Optoelectronic Devices with Nonlinear Polymers P. Robin, P. Le Barny, D. Broussoux, J. P. Pocholle and V. Lemoine 481

Two-Photon Absorption in Polydiacetylene Based Waveguides: Its Origin and Its Consequences. S. Etemad, P. D. Townsend, G. L. Baker and Z. Soos 489

Second Harmonic Generation from Langmuir Layers and Langmuir­Blodget t Films A. Scheelen, P. Winant and A. Persoons 497

An Adaptation of the Prism-Film Coupler Method Used to Study PVAlChrysoidin Non-linear Waveguides C. Malouin, P. Galarneau and R. A. Lessard 513

WORKING GROUP REPORTS 521

INDEX 535

PREFACE

Photonics is being labelled by many as the technology for the 21st century. Because of the structural flexibility both at the molecular and bulk levels, organic materials are emerging as a very important class of nonlinear optical materials to be used for generating necessary nonlinear optical functions for the technology of photonics. Since the last NATO advanced research workshop on "Polymers for Nonlinear Optics"held in June 1988, at Nice - Sophia Antipolis, France. there has been a tremendous growth of interest worldwide and important development in this field. Significant progress has been made in theoretical modeling, material development, experimental studies and device concepts utilizing organic materials. These important recent developments provided the rationale for organizing the workshop on "Organic Materials for Nonlinear Optics and Photonics" which was held in La Rochelle, France, in August 1990.

This proceeding is the outcome of the workshop held in La Rochelle. The objective of the workshop was to bring together scientists and engineers of varied backgrounds working in this field in order to assess the current status of this field by presenting significant recent developments and make recommendations on future directions of research. The workshop was multidisciplinary as it had contributions from chemists, physicists, materials scientists and device engineers. The participants were both from industries and universities. The workshop included plenary lectures by leading international scientists in this field, contributed research papers and a poster session. Panel discussion groups were organized to summarize important developments and to project future directions.

These proceeding contains the contents of the plenary lectures and research contributions. It covers microscopic theory of optical nonlinearity, materials development, measurements of second and third order optical nonlinearity, and device prospects.

We wish to pay tribute to Dr. Donald R. Ulrich who sadly passed away rec~ntly. It is a tremendous loss for the people in this field as Dr. Ulrich played a key role in the inception of the original idea to organize an advanced research workshop in the field of nonlinear optics of organic and polymeric materials. He was also a valuable colleague and a strong advocate of international scientific co-operation. Dr. Ulrich will be very much missing.

We are highly indebted to the NATO Scientific Affairs Division, the main sponsor of the workshop, as well as to the following cosponsors:Conseil General Charente Maritime, Hoechst Celanese, Hoffman La Roche and Quartz et Silice. We thank also the maire of La Rochelle Mr. M. Crepeau for a very pleasant reception in this beautiful city. We also express our sincere thanks to Prof. S. Lefrant for the help in the organization of this workshop, Mr. M. Lenoir for its efficient managing and Mrs. Nicole Gambier for her enthusiastic and very efficient secretarial work.

Saclay, December 1990

ix

For the organizing committee J. Messier, F. Kajzar, P. N. Prasad and C. Taliani

LIST OF PARTICIPANTS

Prof. J. M. ANDRE Faculte Universitaire Notre Dame de la Paix 61, rue de Bruxelles B-5000 NAMUR

Prof. J. L. BREDAS Universite de l'Etat a Mons Service de Chimie des Materiaux Nouveaux Avenue Maistriau 21 B-7000 MONS Belgium

Dr. A. BUCKLEY Hoechst Celanese Research Division 86 Morris A venue SUMMIT, New Jersey 07922 USA

Dr. P-A. CHOLLET CEA - CEN SACLAY DEIN/LPEM 91191 GIF SUR YVETTE CEDEX France

Mr. L. DERHAEG University of Leuven Lab. of Chemical & Biol.Dynamics Celestijnenlaan 200D B-3030 HEVERLEE Belgium

Dr. S. ETEMAD Bell Communications Research 331 Newman Springs Rd RED BANK, New Jersey 07701-7020 USA

xi

Prof. G. BANFI Universita di Pavia Dipartimento di Elettronica Via Abbiategrasso 209 27100 PAVIA Italy

Dr. Ch. BUBECK MPI fur Polymerforschung Ackermannweg 10 Postfach 3148 D-6500 MAINZ Germany

Dr. H. BYRNE Trinity College Physics Deprtment DUBLIN 2 IRELAND

Prof. L. R. DALTON University of Southern California Department of Chemistry 620 Seaver Science Center LOS ANGELES, Ca 90089-0482 USA

Prof. M. DUMONT Institut d'Optique TMorique et Applique BP. 43, Bat. 503 F-91406 ORSAY France

Prof. J. F. FAUVARQUE Centre de Recherche de la CGE Laboratoire de Marcoussis Route de Nozay 91460 MARCOUSSIS France

xii

Prof. C. FLYTZANIS Ecole Poly technique Laborato i re d' Opt ique Quantique 91128 PALAISEAU France

Dr. F. KAJZAR CEA - CEN SACLAY DEIN/LPEM F-91191 GIF SUR YVElTE CEDEX France

Dr. I. LEDOUX CNET 196, avenue Henri Ravera 92220 BAGNEUX France

Dr. J. LE MOIGNE CNRS - ICS 6, rue Boussingault 67083 STRASBOURG France

Dr. J. LIANG CNET 196, avenue Henri Ravera 92220 BAGNEUX France

Dr. D. LUPO HOECHST AG Applied Physics o - 6230 FRANKFURT Germany

Miss F. MEYERS Universite de l'Etat a Mons Service de Chimie des Materiaux Nouveaux Avenue Maistriau 21 B-7000 MONS

Prof. A. GARITO Uni ver s i ty of Pennsylvania Department of Physics PHILADELPHIA, PA 19104-6396 USA

Dr. LAP-TAK-CHENG E. I. Dupont de Nemours and Co. Inc. Central Research and Development Opt WILMINGTON, Delaware 19898 USA

Prof. S. LEFRANT IPCM 2, rue de la Houssiniere 44072 NANTES Cedex 02 France

Prof. R. A. LESSARD Universite de Laval Department de Physique SAINTE FOY QUEBEC GIK 7P4 Canada

Prof. G. MAROVSKY MPI fur Biophysikalische Chemie Postfach 2841 0-3400 GOTTINGEN Germany

Dr. J. MESSIER CEA - CEN SACLAY DEINILPEM 91191 GIF SUR YVElTE CEDEX France

Dr. R. MEYRUEIX RhOne-Poulenc Recherches 85, avo des Freres Perret, B.P. 62 69192 SAINT FONS France

Prof. S. MIYATA Tokyo University of Agriculture and Technology 2-4-16 Nakamachi Koganei-Shi TOKYO 184 Japan

Dr . J. M. NUNZ I CEA - CEN SACLAY DEIN/LPEM 91191 GIF SUR YVETTE CEDEX France

Prof. A. PERSOONS University of Leuven Lab. of Chemical & Biol.Dynamics Celestijnenlaan 200D B-3030 HEVERLEE Belgium

Prof. D. PUGH University of Strathclyde Dept of Pure and Applied Chemistry Thomas Graham Bldg GLASGOW GI lXl Great Britain

Dr. J. RIGGS Hoechst Celanese Research Division 86 Morris Avenue SUMMIT, New Jersey 07922 USA

Miss C. SENTEIN CEA - CEN SACLAY DEIN/LPEM F-91191 GIF SUR YVETTE CEDEX France

Prof. F. NICOUD CNRS - ICS 6, rue Boussingault 67083 STRASBOURG France

Dr. J. W. PERRY

xiii

Jet Propulsion Laboratory California Institute of Technology Mail Stop 67.201 4800 Oak Grove Rd USA

Prof. P. N. PRASAD State University of New York Department of Chemistry Acheson Hall BUFFALO, New York 14214 USA

Mr. G. PUCETTI CNET 196, avenue Henri Ravera 92220 BAGNEUX France

Dr. Ph. ROBIN THOMSON CSF Corbeville, B. P. 12 914000RSAY France

Dr. F. SIEVERDES MPI fur Biophysikalische Chemie Postfach 2841 D-3400 GOTTINGEN Germany

xiv

Dr. K. D. SINGER AT&T Bell Laboratories PO BOX 900 PRINCETON, New Jersey 08540 USA

Prof. C. TALIANI CNR Istituto di Spettroscopia Molecolare Via de Castagnoli 1 I-40l26-BOLOGNA Italy

Mr. T. VERBIEST University of Leuven Lab. of Chemical & Biol.Dynamics Celestijnenlaan 2000 B-3030 HEVERLEE Belgium

Prof. G. K. WONG Collegge of Arts and Sciences Opt of Physics and Astronomy Northwestern University EVANSTON, Illinois 60208 USA

Dr. J. D. SWALEN IBM, Almaden Research Center 650 Harry Rd SAN JOSE, Ca 95120-6099 USA

Dr. S. VALETTE CEA - LETI, DOPT CEN Grenoble avenue des Martyrs F-38041 GRENOBLE Cedex France

Dr. C. S. WINTER British Telecom Research Laboratory RT2333/BTRL B55/122 MARTLESHAM HEATH IPSWICH Great Britain

Dr. J. ZYSS CNET 196, avenue Henri Ravera F -92220 BAGNEUX France