Organic Thin Films and Surfaces: Directions for the Nineties PDF
Preview Organic Thin Films and Surfaces: Directions for the Nineties
Serial Editors Inorganic Thin Films Organic Thin Films Stephen M. Rossnagel Abraham Ulman IBM Watson Research Center Alstadt-Lord-Mark Professor Yorktown Heights, New York Department of Chemistry and Polymer Research Institute Polytechnic University Brooklyn, New York Editorial Board David L. Allara Jerome B. Lando Pennsylvania State University, Case Western Reserve University University Park Helmut Mohwald Allen J. Bard University of Mainz University of Texas, Austin Nicolai Plate Masamichi Fujihira Russian Academy of Sciences Tokyo Institute of Technology Helmut Ringsdorf George Gains University of Mainz Rensselaer Polytechnic Institute Giacinto Scoles Phillip Hodge Princeton University University of Manchester Jerome D. Swalen Jacob N. Israelachvili International Business Machines University of California, Corporation Santa Barbara Matthew V. Tirrell Michael L. Klein University of Minnesota, University of Pennsylvania Minneapolis Hans Kuhn George M. Whitesides MPI Gottingen Harvard University T h in F i l ms ORGANIC THIN FILMS AND SURFACES: DIRECTIONS FOR THE NINETIES Edited by Abraham Ulman Alstadt-Lord-Mark Professor Department of Chemistry and Polymer Research Institute Polytechnic University Brooklyn, New York Volume 20 ACADEMIC PRESS San Diego New York Boston London Sydney Tokyo Toronto This book is printed on acid-free paper. ® Copyright © 1995 by ACADEMIC PRESS, INC. All Rights Reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopy, recording, or any information storage and retrieval system, without permission in writing from the publisher. Academic Press, Inc. A Division of Harcourt Brace & Company 525 Â Street, Suite 1900, San Diego, California 92101-4495 United Kingdom Edition published by Academic Press Limited 24-28 Oval Road, London NWl 7DX International Standard Serial Number: 1079-4050 International Standard Book Number: 0-12-523485-6 PRINTED IN THE UNITED STATES OF AMERICA 95 96 97 98 99 00 EB 9 8 7 6 5 4 3 2 1 The Physics of Thin Films, consisting of 19 volumes since 1963, is one of the longest running continuing series in thin film science. The series contains some of the highest quality studies of the properties of various thin film materials and systems. Since the origination of the series, the thin film field has expanded many times, becoming the basis for a number of major industries, such as semiconductors, hard coatings, optoelectronics, and magnetic storage. Si- multaneously with the development of inorganic thin films, a special field of organic thin films has emerged and is developing rapidly at present. This latter field is also becoming one of increasing importance in materials science research and applications (e.g., polymer science and biomaterials). In order to reflect the development of today's science and to cover all modern aspects of thin films, this series, beginning with Volume 20, will move beyond the basic physics of thin films. It will address the most important issues of both inorganic and organic thin films, in their theoreti- cal as well as their technological aspects. Correspondingly, the series title has been slightly modified to Thin Films to better reflect modem technol- ogy-oriented problems. Starting with Volume 20, the series will be led by two new editors: Dr. Stephen M. Rossnagel of IBM at Yorktown, who will be responsible for the field of inorganic films and applications; and Dr. Abraham Ulman, Alstadt-Lord-Mark Professor at the Polytechnic University of Brooklyn, New York, whose responsibility will include organic films, their chemistry, technology, and applications. The Thin Films series will continue to be one of Academic Press's premier offerings, with high-quality editions in the science and technology field. Publisher and Editors Preface In 1991 I published a book dedicated to the area of ultrathin organic films.^ There, I covered the developments in the area since 1965, the year before Gaines published his classical book on Langmuir-Blodgett mono- layers.^ That Langmuir-Blodgett and self-assembled monolayers are im- portant is clear from the number of articles published on these subjects. This number is so overwhelming—over one thousand each year—that writing a second edition to my book has become an impossible mission. Reading through the literature, one finds it difficult to pinpoint the truly interesting and existing discoveries and developments in this area. Thus, some guidance may be useful, especially for those who find the area attractive and would like to start contributing. After discussions with a number of distinguished scholars—whose names can be found in the editorial board—I proposed a new series of books whose primary goal is to highlight important contributions. My subsequent discussions with the publisher. Academic Press, led to a conclusion that, instead of the creation of a new series, the volumes on organic thin films could be beneficially published within the existing, highly successful series Physics of Thin Films. Correspondingly, the scope of this series would be broadened and the title slightly modified to Thin Films. For this volume (Volume 20 in the Thin Films series), the editorial board suggested taking a general approach rather than focusing on a specific theme. The papers—all invited—are on many topics and represent some of the most interesting advancements in this area. At the Fifth International Conference on Langmuir-Blodgett Films in Paris, Professor Hans Kuhn gave the closing remarks, summarizing the meeting and pointing to the most important contributions. These remarks expressed tremendous vision and enthusiasm and stimulated the corre- spondence between Professor Kuhn and myself that resulted in the open- ing article of this volume, "Supramolecular Assemblies—Vision and Strat- egy." ^ Ulman, A. An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly, Academic Press, Boston, 1991. ^ Gaines, G. L., Jr. Insoluble Monolayers at Liquid-Gas Interfaces, Interscience, New York, 1966. xv XVI Preface The papers on Langmuir-Blodgett monolayers deal with a number of important issues. Starting from the Langmuir layer at the air-water interface, Riegler and Spratte discuss the on-line structure control of Langmuir-Blodgett films, and Majda reports on the translational diffusion and electron hopping in monolayers at the air-water interface. Gaub et al. report on the formation of recognition pattern by Langmuir-Blodgett techniques, and Fendler reviews years of accomplishments in the area of oriented growth of nanocrystalline particulate films at monolayers. Moving to the transfer of monolayers from the air-water interface onto a solid substrate, Okahata et al. evaluate the transfer process of Langmuir- Blodgett films by using a quartz-crystal microbalance as a substrate. As we proceed to the structure of monolayers, Peterson discusses the phase diagrams and chain order in monolayers of aliphatic chains. As we turn to materials and applications, Palacin et al. discuss building up two-dimensional polymers by the Langmuir-Blodgett technique, Miyasaka describes the photoelectric behavior of bacteriorhodopsin thin films at the solid-liquid interface, and Fujihira reviews many accomplish- ments in the area of artificial photosynthesis and molecular devices, describing photoinduced electron transfer in monolayer assemblies. Fi- nally, Orrit and Bernard describe hole-burning spectroscopy of dye-doped Langmuir-Blodgett Films. In the area of self-assembly, Sagiv et al. write on third-level self-assem- bly and beyond and describe the formation of polar hybrid superlattices via postassembly. Rubinstein et al. describe ion-selective monolayer mem- branes based upon self-assembling tetradentate ligand monolayers on gold electrodes. Finally, Calvert reviews many years of efforts in surface pat- terning, describing lithographically patterned self-assembled films. There are three more papers, each dealing with an important subject. Lahav et al. review some years of work in the studies of Langmuir films of amphiphilic alcohols and surfaces of polar crystals as templates for ice nucleation. Leckband and Israelachvili report on the specific recognition at functionalized interfaces and describe direct force measurements of biomolecular interactions. Finally, McCarthy et al. review their work on polymer surface modification. I would like to thank all the contributors who made this volume possible. Their work and contributions will help advance the area of organic thin films. Last, but not least, I thank the members of the editorial board who helped in the selection of the invited papers and assisted me throughout the process. Abraham Ulman Brooklyn, New York Contributors Numbers in parentheses indicate the pages on which the authors' contributions begin JENS ALS-NIELSEN (145), Department of Physics, Ris ο National Laboratory, DK4000 Roskilde, Denmark KATSUHIKO ARIGA (317), Department of Biomolecular Engineering, Tokyo Institute of Technology, Yokohama 227, Japan TIMOTHY G. BEE (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 GARRY BERKOVIC (41), Department of Materials and Interfaces, The Weiz- mann Institute of Science, Rohovot 76100, Israel JACKY BERNARD (293), Centre de Physique Moleculaire Optique et Hertzi- enne, C.N.R.S. et Universite Bordeaux 1, F-33405 Talence Cedex, France JOAN V. BRENNAN (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 JEFFREY M. CALVERT (109), Center for Bio/Molecular Science & Engineer- ing (Code 6900), Naval Research Laboratory, Washington, D.C. 20375 ELISA M. CROSS (85), Polymer Science and Engineering Department, Uni- versity of Massachusetts, Amherst, Massachusetts 01003 ANTHONY J. DIAS (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 MARTIN EGGER (223), Boehringer Mannheim GmbH, 8182 Tutzing, Ger- many JANOS H. FENDLER (11), Department of Chemistry, Syracuse University, Syracuse, New York 13244 NICOLE L. FRANCHiNA (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 MASAMICHI FUJIHIRA (239), Department of Biomolecular Engineering, Tokyo Institute of Technology, Yokohama 227, Japan xvii xviii Contributors HERMAN E. GAUB (223), Physikdepartment E22, Technische Universitat Miinchen, D-8046 Garching, Germany SVEN-PETER HEYN (223), VDI/BDE Technologiezentrum, 1000 Berlin 30, Germany JACOB ISRAELACHVILI (207), Department of Chemical and Nuclear Engi- neering, and Materials Department, University of California at Santa Barbara, Santa Barbara, California 93106 KRISTIAN KJAER (145), Department of Physics, Ris ο National Laboratory, DK4000 Roskilde, Denmark HANS KUHN (1), MPI fiir Biophysikalische Chemie, D-3400 Gottingen- Nikolausberg, Germany MEIR LAHAV (145), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel DEBORAH LECKBAND (207), Department of Chemical Engineering, State University of New York at Buffalo, Buffalo, New York 14260 KANG-WOOK LEE (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 LESLIE LEISEROWITZ (145), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel MARGIN MAJDA (331), Department of Chemistry, University of California at Berkeley, Berkeley, California 94720 JAROSLAW MAJEWSKI (145), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel RIVKA MAOZ (41), Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel THOMAS J. MCCARTHY (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 TSUTOMU MIYASAKA (279), Ashigara Research Laboratories, Fuji Photo Film Company, Ltd., Minamiashigara, Kanagawa 250-01, Japan YOSHIO OKAHATA (317), Department of Biomolecular Engineering, Tokyo Institute of Technology, Yokohama 227, Japan MICHEL ORRIT (293), Centre de Physique Moleculaire Optique et Hertzi- enne, C.N.R.S. et Universite Bordeaux 1, F-33405 Talence, France SERGE PALACIN (69), CEA/Scrvicc de Chimie Moleculaire, CE. Saclay, 91191 Gif sur Yvette Cedex, France Contributors xix IAN R. PETERSON (367), Institute fur Physikalische Chemie, Johannes Gutenberg-Universitat Jakob, DW-6500 Mainz, Germany RONIT POPOVITZ-BIRO (145), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel FLORENCE PORTEAU (69), CEA/Servicc de Chimie Moleculaire, C.E. Saclay, 91191 Gif sur Yvette Cedex, France HANS RIEGLER (349), Institute fiir Physikalische Chemie, Universitat Mainz, D-6500 Mainz, Germany ANNIE RUADEL-TEIXIER (69), CEA/Servicc de Chimie Moleculaire, C.E. Saclay 91191 Gif sur Yvette Cedex, France ISRAEL RUBENSTEIN (183), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel JACOB SAGIV (41), Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel TILMAN SCHWINN (223), Physikdepartment E22, Technische Universitat Munchen, D-8046 Garching, Germany ABRAHAM SHANZER (183), The Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel MOLLY s. SHOICHET (85), Polymer Science and Engineering Department, University of Massachusetts, Amherst, Massachusetts 01003 KARL SPRATTE (349), Institut fiir Physikalische Chemie, Universitat Mainz, D-6500 Mainz, Germany SUZI STEINBERG (183), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel KENTARO TANAKA (317), Department of Biomolecular Engineering, Tokyo Institute of Technology, Yokohama 227, Japan YITZHAK TOR (183), The Department of Organic Chemistry, The Weiz- mann Institute of Science, Rehovot 76100, Israel ABRAHAM ULMAN (1), Imaging Research and Advanced Development, Eastman Kodak Company, Rochester, New York 14650 JINN-LUNG WANG (145), The Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel RUTH YAM (41), Department of Materials and Interfaces, The Weizmann Institute of Science, Rehovot 76100, Israel THIN FILMS, VOLUME 20 Supramolecular Assemblies: Vision and Strategy HANS KUHN MPI βτ Biophysikalische Chemie, D-3400 Gottingen-Nikolausberg, Germany ABRAHAM ULMAN Polytechnic University, Department of Chemistry Polymer Research Institute, Brooklyn, New York 1.1. Introduction When deciding to climb a mountain we usually have a nebulous vision of how exciting it would be on top, of how important, as a unique experience, such an event would be. Then we develop a strategy to get us there, and before starting we equip ourselves well and undergo a conditional training so we are fit for the climb. Our work in supramolecular assemblies and nanoscopic films resembles the task of climbing a mountain; at this moment, we are nevertheless still at the bottom.^ Self-assembly is a process in which supermolecular hierarchical organi- zation is established in complex systems of interlocking components. In fact, self-assembly is one of the most, if not the most, important phe- nomenon in nature, and the living cell is its best paradigm. It is important to emphasize, however, that self-assembly is not limited to the molecular level, and one can imagine self-assembly of molecular clusters, organic, and inorganic crystals, etc. Taking ideas from nature (biological sciences), scientists prepare model systems and study their properties, thus establishing structure property relationships (physical sciences). Having established a working phe- nomenon and the understanding of both materials and mechanistic issues, scientists look for opportunities where these can be utilized for applica- tions (engineering sciences). Figure 1.1 presents the relationship among the different sciences and emphasizes the fact that self-assembly is at their 1 Copyright © 1995 by Academic Press, Inc. All rights of reproduction in any form reserved. ISBN 0-12-523485-6
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