Table Of ContentH. Kuzmany 1. Fink M. Mehring S. Roth (Eds.)
Electronic Properties
of Fullerenes
Proceedings of the International Winterschool on
Electronic Properties of Novel Materials,
Kirchberg, Tirol, March 6-13, 1993
With 238 Figures
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona
Budapest
Professor Dr. Hans Kuzmany
Universitat Wien, Institut fiir Festkorperphysik
Strudlhofgasse 4, A-l090 Wien, Austria
Dr. J6rg Fink
Kernforschungszentrum Karlsruhe, Institut fiir Nukleare Festkorperphysik
Postfach 3640, D-76021 Karlsruhe, Germany •
Professor Dr. Michael Mehring
Universitat Stuttgart, Physikalisches Institut II
Pfaffenwaldring 57, D-70550 Stuttgart, Germany
Dr. Siegmar Roth
Max-Planck-Institut fiir Festkorperforschung
Heisenbergstrasse I, D-70569 Stuttgart, Germany
Series Editors:
Professor Dr., Dres. h. c. Manuel Cardona
Professor Dr., Dr. h. c. Peter Fulde
Professor Dr., Dr. h. c. Klaus von Klitzing
Professor Dr., Dres. h. c. Hans-Joachim Queisser
Max-Planck-Institut fiir Festkorperforschung, Heisenbergstrasse I
D-70569 Stuttgart, Germany
Managing Editor:
Dr. Helmut K. V. Lotsch
Springer-Verlag. Tiergartenstrasse 17, D-69l21 Heidelberg. Germany
ISBN-13: 978-3-642-85051-6 e-ISBN-13: 978-3-642-85049-3
DOl: 10.1007/978-3-642-85049-3
Library of Congress Cataloging-in-Publication Data. Electronic properties of fullerenes: proceedings of the
international winterschool. Kirchberg. Tirol. March 6-13. I 993/[edited by] J. Fink ... let al.]. p. cm. - (Springer
seris in solid-state sciences: 117) "[Proceedings of] the International Winter School on the Electronic Properties of
Fullerenes and Related Compounds" - Pref. Includes bibliographical references and index. ISBN 3-5-l0-57-l15-
8 (Berlin: acid-free I. -ISBN 0-387-57415-8 (New York: acid-free) I. Fullerenes-Electric Properties-Congresses.
I. Fink. J. (Jorg), 1938-. II. International Winter School on the Electronic Properties of Fullerenes and Related
Compounds (1993: Kirchberg am Wechsel. Austria) III. Series. QDI8l.C IE-l5 1993 5-l6·.681-dcl0 93-38-l0-l CIP
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
microfilms 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 1993
Softcover reprint of lbe hardcover 1s t edition 1993
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: Camera-ready copy from the authors/editors
54/3140 - 5 431 1 0 - Printed on acid-free paper
Preface
The First International Winter School on the Electronic Properties of Fullerenes
and Related Compounds took place between March 6 -13, 1993, in Kirchberg
(Tirol) Austria and, like its predecessors, was organized in cooperation with the
"Bundesministerium fur Wissenschaft und Forschung" in Austria, and with the
"Bundesministerium fur Forschung und Technologie" in Germany. Consistent
with the ideology of the previous meetings, the goal was to provide an opportunity
for experienced scientists from universities and industry to discuss their most
recent results and for students and young scientists to become familiar with the
present status of research and applications in this new but rapidly developing
field.
Since 1991, research in the field of organic carbon materials has developed
at a rapid pace due to the advent of the fullerenes and related materials. These
forms of carbon are considered as a missing link between the previously dis
cussed electroactive polymers and the oxidic superconductors. It was therefore
challenging to select this topic for an international winter school in Kirchberg.
Although still in its infancy, research on the physics and chemistry offullerenes
and related compounds has already led to a wealth of results, which was reflected
in the wide range of topics covered and the numerous discussions which emerged
at the meeting. For C6Q itself, preparation methods and crystal growth techniques
continue to evolve, while the understanding of the electronic and structural prop
erties of its solid state continues to pose challenges to experimental and theoretical
physicists. The ever-expanding range of higher fullerenes and related materials,
such as nanotubes and onions, poses a daunting but exciting task for researchers.
For synthetic chemists, fullerenes represent the basis of a whole new range
of synthetic compounds. The prospect of a periodic table of endohedral fullerene
complexes has been discussed, and exohedrally complexed metal-fullerenes have
already attracted the attention of physicists. The first endohedral materials are
now available.
The success of this winter school, the first to focus on fullerenes and related
materials, resulted from the range of the topics of interest, as well as from the
merging of the many disciplines represented by the participants. As pointed out
in the final discussion, the fullerene is a unique material, not only due to its
molecular structure and symmetry, but more so due to the diversity of phenom
ena observable in its solid state; structural phase transitions, glass transitions,
metallic phases, superconducting phases, phototransformation and more, have al
ready been observed. This diversity requires an interdisciplinary approach to the
v
scientific research on these materials. We have met this challenge by providing
an interdisciplinary discussion at this meeting.
This book summarizes the tutorial and research lectures as well as the poster
displays presented at the winter school in Kirchberg. We acknowledge all the
authors for their contributions and all those who took part in the discussions for
their stimulating remarks, which were an essential ingredient to this exciting and
informative event.
We are in particular grateful to the "Bundesministerium fiir Wissenschaft und
Forschung" in Austria, the "Bundesministerium flir Forschung und Technologie"
in Germany and to the "US-Army Research, Development and Standardization
Group", as well as to the many sponsors from industry, for their financial support.
This support was more than just a great help; it was, in fact, indispensable in
attaining the goal of the meeting.
Finally we are indebted, as ever, to the manager of the Hotel Sonnalp, Herr
J.R. Jurgeit, and his staff for their continuous support and for their patience with
the many special arrangements required during the meeting.
Vienna H. Kuzmany
Karlsruhe J. Fink
Stuttgart M. Mehring
June 1993 S. Roth
VI
Contents
The Birth of C6o: Buckminsterfullerene
By H. Kroto ......................................... 1
Part I Chemistry and Sample Preparation
Fullerene Intercalation Compounds
By MJ. Rosseinsky, D.W. Murphy, A.P. Ramirez, R.M. Fleming,
and O. Zhou ......................................... 11
Chemical and Structural Aspects
of the Interaction Between C60 and Molecular Oxygen
By H. Werner, M. Wohlers, D. Bublak, Th. Belz, W. Bensch,
and R. Sch16g1 (With 9 Figures) ............................ 16
A New Apparatus for Fullerene Production
By L. Dunsch, F. Ziegs, J. Frohner, U. Kirbach, K. Klostermann,
A. Bartl, and U. Feist (With 3 Figures) ....................... 39
Implantation into Fullerites
By K. Misof, G. Vogl, P. Fratzl, R. Sielemann, B. Keck, and Y. Yoshida
(With 2 Figures) ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 44
Voltammetric Studies on Fullerenes C60 and C70
in Low-Polarity Solvents
By K. Meerholz, P. Tschuncky, and J. Heinze (With 3 Figures) 48
Buried K-Fullerides by Ion Implantation
By J. Kastner, L. Palmetshofer, P. Bauer, G. Stingeder, and H. Kuzmany
(With 4 Figures) ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 52
C6o-Fullerene in Water Solution, l-Cyclodextrin Complex
and Cluster of C60: An NMR and a Photophysical Study
By T. Andersson, M. Sundahl, O. Wennerstrom, and G. Westman
(With 8 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 56
Pulse Radiolytic Redox and Alkylation Studies on C60
By D.M. GuIdi, H. Hungerbiihler, and K.-D. Asmus (With 1 Figure) 64
Photoionization Dynamics of C60
By T. Drewello, W. Kriitschmer, M. Fieber-Erdmann, and A. Ding
(With 2 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 69
VII
Application of Fullerenes as Sensor Materials
By A.W. Synowczyk and J. Heinze (With 5 Figures) 73
Generation of Graphitic Onions
By D. Ugarte and W.A. de Heer (With 3 Figures) ................ 78
Part IT Electronic Structure and Electron Spectroscopy
Electronic Properties of Fullerenes in the Molecular and Solid Phases:
A Brief Introductory Course to Theoretical Approaches
By W. Andreoni (With 5 Figures) . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
Experimental Investigation of the Electronic Structure
of Gas-Phase and Solid C60
By S. Krummacher, M. Biermann, M. Neeb, A. Liebsch,
and W. Eberhardt (With 2 Figures) .......................... 93
Low-Energy Electron Diffraction and High-Resolution Electron Energy-
Loss Spectroscopy of Heteroepitaxial C60 Thin Films on GeS(OOl)
By G. Gensterblum, L.-M. Yu, J.-J. Pireaux, P.A. Thiry, and R. Caudano
(With 5 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 99
Electron Energy-Loss Studies on Rb-and Ca-Doped Fullerenes
By M. Roth, H. Romberg, E. Sohmen, P. Adelmann, and J. Fink
(With 1 Figure) ....................................... 105
Electron Energy-Loss Spectroscopy of Free Fullerenes
By A.W. Burose, T. Dresch, and A.M. Ding (With 2 Figures) ........ 110
=
High-Resolution Photoemission Studies of A3C60 (A K, Rb)
By M.S. Golden, M. Knupfer, M. Merkel, J. Fink, O. Gunnarsson,
and V.P. Antropov (With 1 Figure) .......................... 114
Electronic Structure of Alkaline-Earth Fullerides
By I. Turek and J. Hafner (With 4 Figures) .................... 119
Jahn-Teller Distorted Excited States of C60
By P.R. Surjan, K. Nemeth, and L. Udvardi (With 1 Figure) 126
The C60 Molecule with the Step-Potential Model
By C. Kuhn (With 5 Figures) .............................. 131
Part TIl Structure and Structural Phase Transitions
Structure and Dynamics of C60 and C70
By K. Prassides (With 5 Figures) ........................... 139
K-C60: Growth Structures, Phase Formation, and Electronic Properties
By J.H. Weaver, D.M. Poirier, and Y.B. Zhao (With 5 Figures) . . . . . .. 146
Structure and Lattice Dynamics of C 0 Single Crystals
7
By G. Meijer (With 2 Figures) ............................. 154
VIII
fuelastic Neutron Scattering Study of the External Vibrations in C60
By L. Pintschovius, S.L. Chaplot, R. Heid, M. Haluska,
and H. Kuzmany (With 6 Figures) .......................... 162
Is K3C60 a Line Phase?
By Q. Zhu, J.E. Fischer, and D.E. Cox (With 2 Figures) 168
Structural and Morphological Characterization of Fullerite Crystals
Prepared from the Vapor Phase
By M. Haluska, P. Fejdi, M. Vybornov, and H. Kuzmany
(With 2 Figures) ............. . . . . . . . . . . . . . . . . . . . . . . . . .. 173
Low-Frequency Elastic Response in Single-Crystal C60
By W. Schranz, A. Fuith, P. Dolinar, H. Warhanek, M. Haluska,
and H. Kuzmany (With 3 Figures) .......................... 177
Electron Microscopy of C60 and C70 Fullerites
By G. Van Tendeloo and S. Amelinckx (With 5 Figures) ........... 182
Orientational Order and Electron Density of C60 at Room Temperature
Studied by Combined Neutron and X-Ray Diffraction on Single Crystals
By R.I. Papoular, G. Roth, G. Heger, M. Haluska, and H. Kuzmany
(With 3 Figures) ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 189
Orientational Glass Transition in Solid C60
By C. Meingast, F. Gugenberger, R. Heid, P. Adelmann, M. Braun,
H. Wiihl, M. Haluska, and H. Kuzmany (With 3 Figures) ... . . . . . . .. 195
Orientational Ordering and Molecular Structure in Solid C60
By D. Lamoen and K.H. Michel (With 1 Figure) . . . . . . . . . . . . . . . .. 200
Molecular Dynamics Calculations on C6o-Based Crystals
By G. Bortel, G. Faigel, G. Oszllinyi, S. Pekker, and M. Tegze
(With 3 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 207
Orientational Order in A3C6o: Effects on Valence Bands
and fufrared Optical Spectra
By A.1. Liechtenstein, 1.1. Mazin, O. Gunnarsson, O.K. Andersen,
S.E. Burkov, and V.P. Antropov (With 3 Figures) ................ 211
Optical and SEM Studies of Morphology in C60 Films
By L. Akselrod, H.I. Byrne, J. Callaghan, A. Mittelbach, and S. Roth
(With 7 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 219
Characterization of a Pure C60 Powder
Using Transmission Electron Microscopy
By A. Loiseau, G. Van Tendeloo, and P. Bernier (With 5 Figures) ..... 223
Surface Imaging by Scanning Tunneling Microscopy
of C60170 Thin Films on Au(111) with Different C60/C70 Ratios
By H.P. Lang, V. Thommen-Geiser, R. Hofer, and H.-J. Giintherodt
(With 3 Figures) ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 228
IX
Low-Temperature Scanning Tunneling Microscopy Study of C60 Fullerite
By S. Behler, H.P. Lang, S.H. Pan, V. Thommen-Geiser, R. Hofer,
M. Bernasconi, and H.-J. Gilntherodt (With 2 Figures) ............. 232
Layer Disorder in C6o-Ether Clathrates
By M. Tegze, G. Oszhinyi, G. Bortel, G. Faigel, and S. Pekker
(With 2 Figures) ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 236
Part N Infrared and Raman Spectroscopy, Luminescence,
Transient Optics, and NLO
Vibrational Spectroscopic Studies of Solid C60 Films
By P.e. Eklund, Z.-H. Dong, Y. Wang, M.J. Holden, K.A. Wang,
P. Zhou, A.M. Rao, G. Dresselhaus, and M.S. Dresselhaus
(With 5 Figures) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 243
Crystal Field Effects and Electronic Excitations in Single-Crystal C60
By P.H.M. van Loosdrecht (With 3 Figures) . . . . . . . . . . . . . . . . . . .. 249
Stability of Single-Crystal and Thin-Film Raman Spectra in C60
By M. Matus, J. Winter, and H. Kuzmany (With 3 Figures) ......... 255
Resonant Raman Scattering of the Normal and Superconducting State
=
of A3C6o Films (A Rb,K)
Bye. Taliani, V.N. Denisov, A.A. Zakhidov, G. Stanghellini, G. Ruani,
and R. Zamboni (With 2 Figures) ........................... 259
Raman Scattering and Lattice Dynamics of Fullerides M6C6o
(M = K, Rb, Cs)
By V.N. Denisov, A.S. Lipin, B.N. Mavrin, A.A. Zakhidov, G. Ruani,
R. Zamboni, and e. Taliani (With 2 Figures) ................... 267
Stability of the Fulleride Phase KIC60
as Observed from Raman Spectroscopy
By J. Winter and H. Kuzmany (With 4 Figures) 273
Raman Spectra of l3C-Substituted and Li-Intercalated Fullerenes
By S. Lefrant, J.P. Buisson, P. Bernier, J.M. Lambert, A. Zahab,
and e. Mathis (With 2 Figures) ............................ 277
Charge Transfer and Electron-Vibrational Mode-Coupling
in Alkali-Metal-Doped C60
By T. Pichler and H. Kuzmany (With 3 Figures) ................. 281
Fullerene-Doped Conducting POlymers: Effects of Enhanced
Photoconductivity and Quenched Photoluminescence
By K. Yoshino, X.H. Yin, K. Muro, S. Kiyomatsu, S. Morita,
A.A. Zakhidov, T. Noguchi, and T. Ohnishi (With 4 Figures) ........ 286
x
Femtosecond Time-Resolved Optical Studies
of Photoexcited States in C60
By T.N. Thomas, R.A. Taylor, J.F. Ryan, D. Mihailovic, and R. Zamboni
(With 3 Figures) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 292
Broadband Electroluminescence in Fullerene Crystals
By A.T. Werner, J. Anders, H.J. Byrne, W.K. Maser, M. Kaiser,
A. Mittelbach, and S. Roth (With 3 Figures) . . . . . . . . . . . . . . . . . . .. 297
Nonlinear Phenomena in the Highly Excited State of C60
By H.J. Byrne, W.K. Maser, M. Kaiser, L. Akselrod, J. Anders,
W.W. Riihle, X.-Q. Zhou, A. Mittelbach, and S. Roth
(With 6 Figures) ....................................... 301
Linear and Nonlinear Optical Properties of Fullerenes
and Some Metal Derivatives
By J. Callaghan, D.N. Weldon, F.Z. Henari, W. Blau, and D.J. Cardin
(With 4 Figures) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 307
Optical Properties of C6o-Diethyl Ether Clathrate Single Crystals
By K. Kamanls, V.G. Hadjiev, C. Thomsen, M.K. Kelly, M. Stutzmann,
S. Pekker, K. Fodor-Csorba, G. Faigel, and M. Tegze
(With 3 Figures) ............. . . . . . . . . . . . . . . . . . . . . . . . . .. 312
Optical Properties of Some New Fulleroids and Fullerene Polymers
By A. Hassanien, T. Mrzel, P. Venturini, F. Wudl, D. Mihailovic,
J. Gasperic, B. Kralj, D. Zigon, S. Milicev, and A. Demsar
(With 4 Figures) ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 316
Part V Magnetic Resonance and Magnetic Ordering
13C Nuclear Relaxation in the Normal State
of the K3C60 Superconductor
By K. Holczer (With 3 Figures) ............................ 323
Is the l3C Nuclear Spin-Lattice Relaxation
=
in A3C60 (A Rb, K) Unconventional?
By M. Mehring ....................................... 330
NMR In)ll.estigation of K3C60 Under Pressure
By G. Quirion, C. Bourbonnais, R. Kerkoud, E. Barthel, P. Auban,
D. Jerome, J.M. Lambert, A. Zahab, P. Bernier, C. Fabre, and A. Rassat
(With 2 Figures) ............. . . . . . . . . . . . . . . . . . . . . . . . . .. 334
NMR on Alkali-Doped C60
By G. Zimmer, M. Helmle, M. Mehring, F. Rachdi, J. Reichenbach,
L. Firlej, and P. Bernier (With 4 Figures) . . . . . . . . . . . . . . . . . . . . .. 339
XI
EPR and Overhauser Shift on [Pq>4]Cio and KxC60
By H. Klos, U. Becker, V. Dyakonov, G. RosIer, B. Gotschy,
G. Denninger, and A. Hirsch (With 3 Figures) .................. 344
NMR Studies of Fullerene C6o-Based Compounds
By P. Bernier, F. Rachdi, M. Ribet, J. Reichenbach, L. Firlej,
J.M. Lambert, A. Zahab, Z. Belahmer, and R. Aznar (With 3 Figures) .. 348
QENS and NMR Investigation of Reorientational Dynamics in C61H2
By L. Cristofolini, M. Ricco, G. Viola, and E. Dalcanale
(With 2 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 354
NMR Study of Orientational Ordering in C60 and the Magnetic Transition
in TDAE-C
60
By R. Blinc, J. Dolinsek, D. Areon, D. Mihailovie, and P. Venturini
(With 2 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 358
The Quest for New Magnetic Fullerene Material
By B. Gotschy, H. Klos, W. Schutz, G. Denninger, A. Hirsch,
and H. Winter (With 2 Figures) ............................ 363
Pulsed EPR on the Photoexcited Triplet State of C
60
By A. Grupp, M. Bennati, and M. Mehring (With 4 Figures) 367
Electron Transfer from End-Capped Quaterthiophene to Photoexcited C6o:
A Pulsed EPR Investigation
By M. Bennati, A. Grupp, P. Bauerle, and M. Mehring
(With 3 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 372
Part VI Electrical Transport and Superconductivity
Transport Measurements of the Normal State and Superconducting
Properties of Fulleride Superconductors
By X.-D. Xiang, J.G. Hou, and A. Zettl (With 3 Figures) . . . . . . . . . .. 379
Magnetic Investigations of Superconducting Fullerenes
By M. Baenitz, E. Straube, M. Kraus, M. Kanowski, H. Werner,
R. Sch16gl, and K. Luders (With 5 Figures) .................... 387
The Electrodynamic Response in Superconducting Fullerenes
By L. Degiorgi (With 2 Figures) ...... . . . . . . . . . . . . . . . . . . . . .. 395
Pairing on Small Clusters in the Peierls-Hubbard Model:
Implications for C60
By J.T. Gammel, F. Guo, D. Guo, K.C. Ung, and S. Mazumdar
(With 4 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 401
Broadening and Anomalous Infrared Activity of the Hg-Derived Phonons
in the MetaIlic Fullerides
By M.J. Rice, H.-Y. Choi, E.J. Mele, and M. Deshpande
(With 2 Figures) .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 406
XII
