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Springer Series in MATERIALS SCIENCE 38 Springer-Verlag Berlin Heidelberg GmbH ONUNE LlBRARY Physics and Astronomy http://www.springer.de/phys/ Springer Series in MATERIALS SCIENCE Editors: R. HuB R. M. Osgood, Ir. H. Sakaki A. Zunger The Springer Series in Materials Science covers the complete spectrum of materials physics, induding fundamental principles, physical properties, materials theory and design. Recognizing the increasing importance of materials science in future device technologies, the book titles in this series reflect the state-of-the-art in understanding and controlling the structure and properties of all important dasses of materials. 26 Gas Source Molecular Beam Epitaxy 33 Supercarbon Growth and Properties of Phosphorus Synthesis, Properties and Applications Containing III-V Heterostructures Editors: S. Yoshimura and R. P. H. Chang By M. B. Panish and H. Temkin 34 Computational Materials Design 27 Physics ofNew Materials Editor: T. Saito Editor: F. E. Fujita 2nd Edition 35 Macromolecular Science 28 Laser Ablation and Engineering Principles and Applications New Aspects Editor: J. C. Miller Editor: Y. Tanabe 29 Elements of Rapid Solidification 36 Ceramics Fundamentals and Applications Mechanical Properties, Failure Editor: M. A. Otooni Behaviour, Materials Selection By D. Munz and T. Fett 30 Process Technology for Semiconductor Lasers 37 Technology and Applications Crystal Growth and Microprocesses ofAmorphousSilicon By K. Iga and S. Kinoshita Editor: R. A. Street 31 Nanostructures and Quantum Effects 38 Fullerene Polymers By H. Sakaki and H. Noge and Fullerene Polymer Composites Editors: P. C. Eklund and A. M. Rao 32 Nitride Semiconductors and Devices ByH.Morkos; Series homepage - http://www.springer.de/physlbooks/ssms/ Volumes 1-25 are listed at the end of the book. Peter C. Eklund Apparao M. Rao (Eds.) Fullerene Polymers and Fullerene Polymer Composites With 224 Figures and 19 Tables , Springer Professor Dr. Peter C. Eklund Dr. Apparao M. Rao Department of Physics and Astronomy and Center for Applied Energy Research University of Kentucky Lexington, KY 40506-0055 USA Series Editors: Prof. Robert Hull Prof. H. Sakaki University ofVirginia Institute ofIndustrial Science Dept. of Materials Science and Engineering University of Tokyo Thornton Hall 7-22-1 Roppongi, Minato-ku Charlottesville, VA 22903-2442, USA Tokyo 106, Japan Prof. R. M. Osgood, Ir. Prof. Alex Zunger Microelectronics Science Laboratory NREL Department of Electrical Engineering National Renewable Energy Laboratory Columbia University 1617 Cole Boulevard Seeley W. Mudd Building Golden Colorado 80401-3393, USA New York, NY 10027, USA Library of Congress Cataloging-in-Publication Data Fullerene polymers and fullerene polymer composites / [edited by] Peter C. Eklund and Apparao M. Rao. p. cm. -- (Springer series in materials science, ISSN 0933-033X ; 38) Includes bibliographical references and index. I. Fullerene polymers. 2. Polymerie composites. I. Eklund, P. C. II. Rao, Apparao M., 1961-III. Springer series in materials science; v. 38. QD383.F84 F85 1999 620.1 '92--dc21 99-050347 ISSN 0933-033x ISBN 978-3-642-08441-6 ISBN 978-3-662-04269-4 (eBook) DOI 10.1007/978-3-662-04269-4 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. @ Springer-Verlag Berlin Heidelberg 2000 Originally published by Springer-Verlag Berlin Heidelberg Ne w York in 2002 Softcover reprint of the hardcover 1st edition 2002 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: EDV-Beratung F. Herweg, Hirschberg Cover concept: eStudio Calamar Steinen Cover production: design & production GmbH, Heidelberg Printed on acid-free paper SPIN: 10688559 57/3144/mf -5 4 3 210 Preface The discovery of carbon cage moleeules C2n (or "fullerenes"), by Smalley, Kroto and coworkers in 1985, launched an intensive interdisciplinary inquiry into the fundamental properties of these highly symmetrie molecules. The subsequent observation by Kratschmer, Huffman and coworkers that C and 60 C could be produced in large enough quantities to be studied in the solid 70 state opened up this research area to physicists, chemists and materials sci entists, and the field of fullerene-based materials was born. In addition to the interesting chemieal, physieal and photophysieal properties of the iso lated molecules, many exciting materials properties were discovered when they were assembled in the solid state. In this research monograph, we have attempted to collect important re sults in the partieular sub-field of fullerenes devoted to polymerie materials containing, or built from, C60 and C70. These materials can be sub-divided into three main classes: (1) "all-fullerene" polymers formed by inducing co valent connections (bonds) between the cages, (2) polymers formed by the chemieal addition of C to the backbone of a conventional polymer, and (3) 60 composite materials formed by the physieal mixt ure of C and conventional 60 polymers. Herein will be found eleven chapters written by internationally recog nized researchers in this sub-field of fullerene research. The first two chapters provide introductory material for the non-experts. Chapter 1, "Fundamen tal Properties of Fullerenes", provides an overview of the structure, bond ing, electronie and vibrational states, and physical properties of fullerene moleeules and fullerene solids. Chapter 2, "Introduction to Electronic, Opti cal and Transport properties of Conducting Polymers and Fullerene Polymer Composites", serves as a second cornerstone for the book, introducing some of the key photophysical and transport concepts from the perspective of poly mer scientists. Of the remaining ni ne chapters, three are contributions from prominent theorists. They have applied molecular dynamics and state-of-the art electronic energy band calculations to explain the structural, electronic and vibrational properties of C dimers, trimers and various C polymer 60 60 systems. This information has proven useful in identifying the various poly merie phases obtained under different experimental conditions. Theoretical discussion ofth e polymerization mechanism(s) is also presented in these chap- VI Preface ters. Three chapters are devoted to the observed properties of "all-fullerene" polymers, where polymerization (or covalent bonding between molecules) was driven either by the application of light, heat and press ure , or charge trans fer doping. The remaining three chapters deal with the unusual physical and photophysical properties of composites of C60 - polymer systems, formed by the physical mixture of C60 with various conventional polymers; photodevice applications based on these materials are also discussed. The authors are indebted to Dr. G. Sumanasekera for help with the prepa ration of the final electronic file of the text, and to the United States National Science Foundation for partial support during the preparation and editing of this manuscript. We gratefully acknowledge many helpful discussions with Prof. M.S. Dresselhaus and Dr. G. Dresselhaus yielding furt her insight into the properties of these novel materials. November 1999 Peter C. Eklund Apparao M. Rao Contents 1. Fundamental Properties of Fullerenes M.S. Dresselhaus, G. Dresselhaus ................................. 1 1.1 Introduction to Fullerenes as Polymerie Materials and Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1.1 Historieal Background to Fullerenes. . . . . . . . . . . . . . . . . . . . 1 1.1.2 Historieal Background to Fullerene Polymers and Fullerene-Polymer Composites . . . . . . . . . . . . . . . . . . . . . 3 1.2 Structural Properties of Fullerene Molecules . . . . . . . . . . . . . . . . . . . 3 1.2.1 Structure of C60 .•........................•.......... 3 1.2.2 Structure of C and Higher Mass Fullerenes. . . . . . .. . . . . 6 70 1.2.3 Structure of Metallofullerenes. . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.3 Synthesis.................................................. 7 1.4 Structure in Condensed Phases .............................. 8 1.4.1 Crystalline C60 ...•...........•.•.............••..... 9 1.4.2 Crystalline C70 .....................................• 11 1.4.3 Crystalline Phases for Higher Mass Fullerenes ........... 11 1.4.4 Intercalated Fullerene Structures . . . . . . . . . . . . . . . . . . . . . .. 12 1.5 Polymerized Fullerenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 14 1.5.1 Photopolymerization of C60 ........................... 15 1.5.2 Electron Beam-Induced Polymerization of C60 . . . . . . . . . .. 17 1.5.3 Pressure-Induced Polymerization of C60 . . . . . . . . . . . . . . . .. 17 1.5.4 Plasma-Induced Polymerization of C60 . . . . . . . . . . . . . . . . .. 18 1.5.5 Photopolymerization of C Films. . . . . . . . . . . . . . . . . . . . .. 18 70 1.6 Vibrational Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 19 1.6.1 Infrared-active Modes in C60 ...............•.......... 21 1.6.2 Raman-active Modes in C60 . . . . . . . . . . . . . . . . . . . . . . . . . .. 21 1.6.3 Silent Modes in C60 . . . . . . . . . . . • • . . . . . . . . . . . . . . . . . . . .. 24 1.6.4 Vibrational Spectra for C70 .................•..••..... 24 1.6.5 Vibrational Modes in Doped Fullerene Solids . . . . . . . . . . .. 24 1.6.6 Vibrational Properties of Phototransformed Fullerenes. . .. 27 1.7 Electronie Properties ....................................... 31 1.8 Optieal Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35 1.8.1 Introduction to Molecular Photophysics. . . . . . . . . . . . . . . .. 35 1.8.2 Optical Transitions in Photopolymerized C60 . . . . . . . . . . .. 44 VIII Contents 1.9 Transport and Photoconductivity ..... . . . . . . . . . . . . . . . . . . . . . .. 46 1.9.1 Electrical Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 46 1.9.2 Photoconductivity................................... 48 1.10 Superconductivity.......................................... 52 1.11 Concluding Remarks ....................................... 57 References ................................................... .. 58 2. Introduction to Electronic, Optical, and Transport Properties of Conducting Polymers and Fullerene-Polymer Composites P.A. Lane, Z.V. Vardeny ......................................... 69 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 69 2.2 Electronic States in Conducting Polymers . . . . . . . . . . . . . . . . . . . .. 69 2.3 Absorption Studies of Conducting Polymers. . . . . . . . . . . . . . . . . .. 76 2.4 Excited State Optical Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79 2.5 Optical Studies of t-(CH)x .................................. 81 2.6 Optical Studies of Polythiophene . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 84 2.7 Optical Properties of C60: Polymer Composites ................ 89 2.8 Transport Properties of Conducting Polymers. . . . . . . . . . . . . . . . .. 91 2.9 Device Applications of Conducting Polymers. . . . . . . . . . . . . . . . . .. 94 2.10 Summary................................................. 97 References ..................................................... 98 3. Supramolecular Photophysics and Photovoltaic Devices of Fullerene-Conjugated Polymer Composites N.S. Sariciftci .................................................. 101 3.1 Introduction ............................................... 101 3.1.1 Semiconducting, Conjugated Polymers as Photoexcited Electron Donors ....................... 101 3.1.2 Buckminsterfullerene, C60, as Electron Acceptor ......... 102 3.2 Experimental Results: Ultrafast, Reversible, Photoinduced Electron Transfer in Conjugated Polymer/Fullerene Composite Films ............. 104 3.2.1 Linear Absorption and Photoluminescence .............. 104 3.2.2 Near Steady State Photoinduced Absorption ............ 107 3.2.3 Sub-Picosecond Photoinduced Absorption ............... 111 3.2.4 Sub-Picosecond Photoinduced Dichrosim ................ 120 3.2.5 Steady State Infrared Photoinduced Absorption .......... 123 3.2.6 Sensitization of Photoconductivity ..................... 124 3.2.7 Direct Experimental Evidence for the Metastable Charge Separation: Light Induced Electron Spin Resonance (LESR) ............................................. 127 3.3 Effect of the Surrounding Medium: Solution Studies ............ 129 Contents IX 3.4 Photovoltaic and Photodetector Applications: A Molecular Approach to High Efficiency Photovoltaic Cells Using Photoinduced Electron 'fransfer ........................ 130 3.4.1 Conjugated Polymer/C6o Heterojunction Photodiodes .... 131 3.4.2 Diodes Made of Conjugated Polymer Composites with a Network of Internal Heterojunctions .............. 135 3.5 Future Areas ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 139 References ..................................................... 140 4. Optical Studies of Covalently Linked C Solids 60 A.M. Rao, P.C. Eklund .......................................... 145 4.1 Introduction ............................................... 145 4.2 Pristine C60 ............................................... 147 4.3 Vibrational Modes of Solid C60 .............................. 149 4.4 Polymerized C60 Structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 152 4.4.1 Photopolymerized C60 ................................ 153 4.4.2 Cha,rge 'fransfer Excitons: a Possible 'frigger Mechanism for Photopolymerization .............................. 163 4.4.3 Theoretical Predictions ............................... 165 4.4.4 Experimental Evidence for CT Excitons in C60 .......... 166 4.5 Photo-induced Hardening of C60 Crystals ..................... 168 4.6 Pressure-induced C60 Polymers .............................. 169 4.7 M1C60 Polymers ........................................... 178 4.7.1 Na4C60 Polymer ..................................... 180 References ..................................................... 182 5. First-Principles Molecular Dynamical Studies of Polymerized C 60 G.B. Adams, J.B. Page .......................................... 185 5.1 Method: First-Principles Quantum Molecular Dynamics ......... 185 5.2 Simulation One: Polymerized C60 ............................ 188 5.2.1 Structure and Energy ................................. 188 5.2.2 Vibrational Properties ................................ 197 5.2.3 Electronic Eigenvalues ................................ 210 5.2.4 Energy Barrier to Dimer Separation .................... 212 5.2.5 Summary for Photopolymerized C60 .................... 213 5.2.6 Other Forms of Polymerized C60 .......•............... 215 5.3 Simulation Two: CUg ....................................... 216 5.3.1 Predicting the Structure .............................. 216 5.3.2 Properties of the Predicted Structure ................... 219 5.3.3 Summary for CUg ................................... 222 References ..................................................... 224 X Contents 6. Covalent Bonding Between Fullerenes M. Menon, KR. Subbaswamy .................................... 229 6.1 Introduetion ............................................... 229 6.2 Theoretieal Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 6.3 Covalent Bonding Between Fullerenes. . . . . . . . . . . . . . . . . . . . . . . . . 230 6.3.1 C Dimer .......................................... 230 60 6.3.2 C Dimer .......................................... 235 70 6.3.3 Curvature Dependenee of Covalent Bonding ............. 238 6.3.4 Summary ........................................... 238 Referenees ..................................................... 239 7. Polymerized Fullerite Structures: Experiment and Theory M. Nunez-Regueiro, L. Marques, J.L. Rodeau, C.R. Xu, G.E. Seuseria . 241 7.1 Introduetion ............................................... 241 7.2 Bonding Under Pressure .................................... 242 7.2.1 Organie Moleeules Under Pressure ..................... 242 7.2.2 Carbon Under Pressure and New Possible Carbon Struetures ................................... 243 7.2.3 C Under Pressure .................................. 244 60 7.2.4 Polymerizing C60 •........................•....•..... 246 7.2.5 C Dimers ......................................... 247 60 7.3 The Polymerized Fullerite Struetures ......................... 250 7.3.1 1-D Polymers ........................................ 251 7.3.2 2-D Polymers ........................................ 255 7.3.3 3-D Polymers ........................................ 257 7.4 Conelusions ............................................... 260 Referenees ..................................................... 261 8. Polymerization of Charged Cao Moleeules R. Kuzmany, J. Winter .......................................... 265 8.1 Introduetion ............................................... 265 8.2 Phases of AC60, A = K, Rb, Cs .............................. 266 8.2.1 Phase Separation Versus Struetural Phase Transition to the Orthorhombie Phase for AC60 ..••............... 267 8.2.2 Strueture of the Polymerie Phase ...................... 271 8.3 Physieal Properties of the Polymerie Phases ................... 274 8.3.1 Vibrational Speetra and Optieal Transitions ............. 274 8.3.2 Magnetie Resonanee .................................. 283 8.3.3 Transport ........................................... 287 8.4 Eleetronie Structure of AC60 ................................ 289 8.5 Stability Versus Atmospherie Conditions ...................... 291 8.6 Dimerie Phases and Annealing After Quenehing of AC60 ........ 292

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