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Handbook of Conducting Polymers Third Edition
CONJUGATED POLYMERS PROCESSING AND APPLICATIONS
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Handbook of Conducting Polymers Third Edition
CONJUGATED POLYMERS PROCESSING AND APPLICATIONS
Edited by
Terje A. Skotheim and John R. Reynolds
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CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2007 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-10: 1-4200-4360-9 (Hardcover) International Standard Book Number-13: 978-1-4200-4360-0 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com (http:// www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Skotheim, Terje A., 1949Conjugated polymers: processing and applications. -- 3rd ed. / Terje A. Skotheim, John Reynolds. p. cm. Includes bibliographical references and index. Previously published: Handbook of conducting polymers. 2nd ed., rev. and expanded. c1998. ISBN-13: 978-1-4200-4360-0 ISBN-10: 1-4200-4360-9 1. Conducting polymers. 2. Organic conductors. I. Reynolds, John R., 1956- II. Skotheim, Terje A., 1949- Handbook of conducting polymers. III. Title. QD382.C66H36 2006b 620.1’92--dc22 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com
2006036331
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Dedication
This book is dedicated to our spouses, Ellen Skotheim and Dianne Reynolds. Without their understanding and support, we would never have completed this project.
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Preface to Third Edition
The field of conjugated, electrically conducting, and electroactive polymers continues to grow. Since the publication of the second edition of the Handbook of Conducting Polymers in 1998, we have witnessed broad advances with significant developments in both fundamental understanding and applications, some of which are already reaching the marketplace. It was particularly rewarding to see that in 2000, the Nobel Prize in chemistry was awarded to Alan Heeger, Alan MacDiarmid, and Hideki Shirakawa, recognizing their pathbreaking discovery of high conductivity in polyacetylene in 1977. This capstone to the field was celebrated by all of us as the entire community has participated in turning their initial discovery into the important field that it now is, almost 30 years later. The vast portfolio of new polymer structures with unique and tailored properties and the wide range of applications being pursued are far beyond what we could have envisioned when the field was in its infancy. It was developments in polymer synthesis that led to free-standing polyacetylene films and the discovery of conductivity in polymers. The synthesis of p-conjugated chains is central to the science and technology of conducting polymers and is featured in this edition. Examining the synthetic advances across the board, one is struck by refined and careful syntheses that have yielded polymers with well-controlled and wellunderstood structures. Among other things, it has led to materials that are highly processable using industrially relevant techniques. In aspects of processing spin coating, layer-by-layer assembly, fiber spinning, and the application of printing technology have all had a big impact during the last 10 years. Throughout the Handbook, we notice that structure–property relationships are now understood and have been developed for many of the polymers. These properties span the redox, interfacial, electrical, and optical phenomena that are unique to this class of materials. During the last 10 years, we have witnessed fascinating developments of a wide range of commercial applications, in particular, in optoelectronic devices. Importantly, a number of polymers and compositions have been made available by the producers for product development. This has helped to drive the applications developments to marketable products. While conductivity, nonlinear optics, and light emission continue to be important properties for investigation and have undergone significant developments as discussed throughout the Handbook, the advances in semiconducting electronics, memory materials, photovoltaics (solar cells), and applications directed to biomedicine are emerging as future growth areas. As we have assembled this edition, it has become clear that the field has reached a new level of maturity. Nevertheless, with the vast repertoire of synthetic chemistry at our disposal to create new structures with new, and perhaps unpredictable properties, we can expect exciting discoveries to continue in this dynamic field.
Terje A. Skotheim Tucson, Arizona John R. Reynolds Gainesville, Florida
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Editors
Terje Skotheim is the founder and Chief Executive of Intex, a Tucson, Arizona technology company. Dr. Skotheim is an experienced developer of several technologies, a seasoned executive and a successful founder of several startup companies in the United States, Norway, and Russia. His research interests over more than 25 years span several disciplines in materials science and applications, including electroactive and conjugated polymers, molecular electronic materials, solid-state ion conductors, new electronic nanoamorphous carbon- and diamond-like carbon materials, and thin-film and surface science. He has pursued a wide range of technology applications of advanced materials in OLEDs, biosensors, lithium batteries, photovoltaic cells, and MEMS devices. He has held research positions in France, Sweden, and Norway in addition to the United States and was head of the conducting polymer group at Brookhaven National Laboratory before launching his career as an entrepreneur. Skotheim received his B.S. in Physics from the Massachusetts Institute Technology and Ph.D. in physics from the University of California at Berkeley (1979). He is the editor/co-editor of the Handbook of Conducting Polymers (1st and 2nd editions, Marcel Dekker) and Electroresponsive Molecular and Polymeric Systems (Marcel Dekker), the author of more than 300 publications and more than 70 patents. He can be reached at
[email protected] John R. Reynolds is a professor of chemistry at the University of Florida with expertise in polymer chemistry. He serves as an associate director for the Center for Macromolecular Science and Engineering. His research interests have involved electrically conducting and electroactive conjugated polymers for over 25 years, with work focused on the development of new polymers by manipulating their fundamental organic structure in order to control their optoelectronic and redox properties. His group has been heavily involved in the areas developing new polyheterocycles, visible and infrared light electrochromism, along with light emission from polymer and composite light-emitting diodes (LEDs) (both visible and near-infrared) and light emitting electrochemical cells (LECs). Further work is directed to using organic polymers and oligomers in photovoltaic cells. Reynolds obtained his M.S. (1982) and Ph.D. (1984) in polymer science and engineering from the University of Massachusetts. He has published over 200 peer-reviewed scientific papers and served as co-editor of the Handbook of Conducting Polymers, which was published in 1998. He can be reached by e-mail at
[email protected] or visit his Web site http://www.chem.ufl.edu/~reynolds/.
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Contributors
Michal Adler Department of Chemistry Solid State Institute Technion Haifa, Israel
Mary Galvin Department of Materials Science and Engineering University of Delaware Newark, Delaware
Magnus Berggren Dept. of Science and Technology Linko¨ping University Norrko¨ping, Sweden
Elena Gershman Department of Chemistry Solid State Institute Technion Haifa, Israel
Gordon P. Bierwagen Department of Coatings and Polymeric Materials North Dakota State University Fargo, North Dakota Sean Brahim Center for Bioelectronics, Biosensors, and Biochips Clemson University Clemson, South Carolina Hermona Christian-Pandya Department of Biomedical Engineering Northwestern University Evanston, Illinois Chih-Wei Chu Department of Materials Science and Engineering University of California Los Angeles, California Larry R. Dalton Department of Chemistry University of Washington Washington, D.C. Yoav Eichen Department of Chemistry Solid State Institute Technion Haifa, Israel
Oded Globerman Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel Vladimir Gorelik Department of Chemistry Solid State Institute Technion Haifa, Israel Anthony Guiseppi-Elie Center for Bioelectronics, Biosensors, and Biochips (C3B) and Department of Chemical and Biomolecular Engineering and Department of Bioengineering Clemson University Clemson, South Carolina and Abtech Scientific, Inc. Biotechnology Research Park Richmond, Virginia Olle Ingana¨s Biomolecular and Organic Electronics, IFM Linko¨ping University Linko¨ping, Sweden
Terje A. Skotheim / Conjugated Polymers: Processing and Applications
P.C. Innis ARC Centre of Excellence for Electromaterials Science Intelligent Polymer Research Institute University of Wollongong Wollongong, Australia David J. Irvin Naval Air Warfare Center Weapons Division Chemistry Division China Lake, California Jennifer A. Irvin Naval Air Warfare Center Weapons Division Chemistry Division China Lake, California Ghassan E. Jabbour Flexible Display Center and Department of Chemical and Materials Engineering Arizona State University Tempe, Arizona Benjamin R. Mattes Santa Fe Science and Technology University of New Mexico Santa Fe, New Mexico S.E. Moulton ARC Centre of Excellence for Electromaterials Science Intelligent Polymer Research Institute University of Wollongong Wollongong, Australia A.J. Mozer Molecular Process Engineering, Material and Life Science Graduate School of Engineering Osaka, Japan and
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Ian D. Norris Santa Fe Science and Technology University of New Mexico Santa Fe, New Mexico Toribio F. Otero Center for Electrochemistry and Intelligent Materials Universidad Polite´cnica de Cartagena Cartagena, Spain Jianyong Ouyang Department of Materials Science and Engineering University of California Los Angeles, California Ankita Prakash Department of Materials Science and Engineering University of California Los Angeles, California Yevgeni Preezant Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel Noam Rappaport Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel Nathaniel D. Robinson Department of Science and Technology Linko¨ping University Norrko¨ping, Sweden Yohai Roichman Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel
Linz Institute for Organic Solar Cells Physical Chemistry Johannes Kepler University Linz Linz, Austria
N.S. Sariciftci Linz Institute for Organic Solar Cells Physical Chemistry Johannes Kepler University Linz Linz, Austria
Peter Nilsson Biomolecular and Organic Electronics, IFM Linko¨ping University Linko¨ping, Sweden
Elisabeth Smela Department of Mechanical Engineering University of Maryland College Park, Maryland
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Olga Solomesch Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel Geoffrey M. Spinks ARC Centre for Electromaterials Science Intelligent Polymer Research Institute University of Wollongong Wollongong, Australia John D. Stenger-Smith Naval Air Warfare Center Weapons Division Chemistry Division China Lake, California Shay Tal Department of Chemistry Solid State Institute Technion Haifa, Israel Dennis E. Tallman Department of Chemistry, Biochemistry and Molecular Biology and Department of Coatings and Polymeric Materials North Dakota State University Fargo, North Dakota Nir Tessler Nanoelectronic Center Electrical Engineering Department Technion Haifa, Israel Ricky J. Tseng Department of Materials Science and Engineering University of California Los Angeles, California Subramanian Vaidyanathan Solutions Polymers Research—Energy and Electronics BASF AG Ludwigshafen, Germany
Janos Veres Merck Chemicals Manchester, United Kingdom G.G. Wallace ARC Centre of Excellence for Electromaterials Science Intelligent Polymer Research Institute University of Wollongong Wollongong, Australia Bernard Wessling Ormecon International Ormecon GmbH Ammersbek, Germany Ann M. Wilson Abtech Scientific, Inc. Biotechnology Research Park Richmond, Virginia Yang Yang Department of Materials Science and Engineering University of California Los Angeles, California Yuka Yoshioka Flexible Display Center and Department of Chemical and Materials Engineering Arizona State University Tempe, Arizona Vadim Zolotarev Department of Chemistry Solid State Institute Technion Haifa, Israel
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Table of Contents
I:
Processing of Conjugated Polymers
1.
Conductive Polymers as Organic Nanometals ........................................................................... 1-3 Bernard Wessling
2.
Conducting Polymer Fiber Production and Applications......................................................... 2-1 Ian D. Norris and Benjamin R. Mattes
3.
Inkjet Printing and Patterning of PEDOT–PSS: Application to Optoelectronic Devices............................................................................................................ 3-1 Yuka Yoshioka and Ghassan E. Jabbour
4.
Printing Organic Electronics on Flexible Substrates................................................................. 4-1 Nathaniel D. Robinson and Magnus Berggren
II:
Applications and Devices Based on Conjugated Polymers
5.
Polymers for Use in Polymeric Light-Emitting Diodes: Structure–Property Relationships ............................................................................................... 5-3 Hermona Christian-Pandya, Subramanian Vaidyanathan, and Mary Galvin
6.
Organic Electro-Optic Materials ................................................................................................. 6-1 Larry R. Dalton
7.
Conjugated Polymer Electronics—Engineering Materials and Devices................................... 7-1 Nir Tessler, Janos Veres, Oded Globerman, Noam Rappaport, Yevgeni Preezant, Yohai Roichman, Olga Solomesch, Shay Tal, Elena Gershman, Michal Adler, Vadim Zolotarev, Vladimir Gorelik, and Yoav Eichen
8.
Electrical Bistable Polymer Films and Their Applications in Memory Devices ..................... 8-1 Jianyong Ouyang, Chih-Wei Chu, Ricky J. Tseng, Ankita Prakash, and Yang Yang
9.
Electroactive Polymers for Batteries and Supercapacitors........................................................ 9-1 Jennifer A. Irvin, David J. Irvin, and John D. Stenger-Smith
10.
Conjugated Polymer-Based Photovoltaic Devices.................................................................... 10-1 A.J. Mozer and N.S. Sariciftci
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11.
Biomedical Applications of Inherently Conducting Polymers (ICPs).................................... 11-1 P.C. Innis, S.E. Moulton, and G.G. Wallace
12.
Biosensors Based on Conducting Electroactive Polymers....................................................... 12-1 Anthony Guiseppi-Elie, Sean Brahim, and Ann M. Wilson
13.
Optical Biosensors Based on Conjugated Polymers ................................................................ 13-1 Peter Nilsson and Olle Ingana¨s
14.
Conjugated Polymers for Microelectromechanical and Other Microdevices ........................ 14-1 Geoffrey M. Spinks and Elisabeth Smela
15.
Corrosion Protection Using Conducting Polymers ................................................................. 15-1 Dennis E. Tallman and Gordon P. Bierwagen
16.
Artificial Muscles ........................................................................................................................ 16-1 Toribio F. Otero
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I Processing of Conjugated Polymers
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1 Conductive Polymers as Organic Nanometals 1.1
Organic Metals..................................................................... 1-3 Metallic Character and Nanostructure of Conductive Polymers . Nanotechnology with Nanometals
1.2 1.3
Bernard Wessling
1.1
Conductive Polymers–Solvent Systems: Solutions or Dispersions................................................... 1-22 Applications of Organic Metals Emerging from Basic Science: Macroeffects of Nanoparticles ................. 1-23 Introduction Applications
. .
PAni Dispersions and Blends Final Remarks
Organic Metals
The broad potential and the scientific and technical possibilities of organic metals are widely unknown. An interesting publication in Nature shows how scientists are oriented toward nanotechnology with conventional metals, even if the approach is more complicated. In their research work, Erez Braun et al. [1] placed a DNA double strand between the two electrodes to be contacted, and then deposited about 30–50 nm silver particles by the reduction of a Agþ solution on the DNA. When only 10–20 nm silver particles were deposited, they did not make successful electrical contact. This is not surprising in view of the fact that conventional nanometals, like Ag or Au, do not exhibit a very high conductivity, as evident by their conducitivity values of only 1008C), which destroys the nano character, increases the conductivity to the metallic regime. In contrast, the existence of organic metals and their character as true metals, though nanometals, is still widely unknown although they show a much higher conductivity, in spite of their nanosize, after deposition from colloidal dispersion (between 1 and
