Optoelectronic Properties of Inorganic Compounds

421 Pages·1999·9.896 MB·English

by  Gary M. Gray, Christopher M. Lawson (auth.), D. Max Roundhill, John P. Fackler Jr. (eds.)

Optoelectronic Properties
of Inorganic Compounds
MODERN INORGANIC CHEMISTRY
Series Editor: John P. Fackler, Jr., Texas A&M University
Recent volumes in the series:
CARBON-FUNCTIONAL ORGANOSILICON COMPOUNDS
Edited by Vaclav Chvalovsky and Jon M. Bellama
COMPUTATIONAL METHODS FOR THE DETERMINATION OF
FORMATION CONSTANTS
Edited by David J. Leggett
COOPERATIVE PHENOMENA IN JAHN-TELLER CRYSTALS
Michael D. Kaplan and Benjamin G. Vekhter
GAS PHASE INORGANIC CHEMISTRY
Edited by David H. Russell
HOMOGENEOUS CATALYSIS WITH METAL PHOSPHINE COMPLEXES
Edited by Louis H. Pignolet
INORGANOMETALLIC CHEMISTRY
Edited by Thomas P. Fehlner
THE JAHN-TELLER EFFECT AND
VIBRONIC INTERACTIONS IN MODERN CHEMISTRY
I. B. Bersuker
METAL COMPLEXES IN AQUEOUS SOLUTIONS
Arthur E. Martell and Robert D. Hancock
MOSSBAUER SPECTROSCOPY
APPLIED TO INORGANIC CHEMISTRY
Volumes 1 and 2. Edited by Gary J. Long
Volume 3 • Edited by Gary J. Long and Fernande Grandjean
MOSSBAUER SPECTROSCOPY
APPLIED TO MAGNETISM AND MATERIALS SCIENCE
Volumes 1 and 2. Edited by Gary J. Long and Fernande Grandjean
OPTOELECTRONIC PROPERTIES OF INORGANIC COMPOUNDS
Edited by D. Max Roundhill and John P. Fackler, Jr.
ORGANOMETALLIC CHEMISTRY OF THE TRANSITION ELEMENTS
Florian P. Pruchnik
Translated from Polish by Stan A. Duraj
PHOTOCHEMISTRY AND PHOTOPHYSICS OF METAL COMPLEXES
D. M. Roundhill
A Continuation Order Plan is available for this series. A continuation order will bring delivery
of each new volume immediately upon publication. Volumes are billed only upon actual
shipment. For further information please contact the publisher.
Optoelectronic Properties
of Inorganic Compounds
Edited by
D. Max Roundhill
Texas Tech University
Lubbock. Texas
and
John P. Fackler, Jr.
Texas A&M University
College Station. Texas
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
LIbrary of Congress Ca~aloglng-ln-Publlca~lon Da~a
OptoelectronIc propertIes of InorganIc compounds I edIted by O. Max
RoundhIll and John P. Fackler, Jr.
p. cm. -- (Modern InorganIc chemIstry)
Includes bIblIographical references and Index.
ISBN 978-1-4419-3273-0 ISBN 978-1-4757-6101-6 (eBook)
DOI 10.1007/978-1-4757-6101-6
1. InorganIC co.pounds--Optlcal propertIes. 2. InorganIC
co.pounds--Electronlc properties. 3. OptoelectronIc devlces
-MaterIals. I. RoundhIll, D. M. II. Fackler, John P.
III. SerIes.
00171.067 1998
620.1'1295--dc21 98-7495
CIP
ISBN 978-1-4419·3273-0
© 1999 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1999
Softcover reprint of the hardcover lst edition 1999
http://www.plenum.com
All rights reserved
109 8765432 I
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise,
without written permission from the Publisher
Contributors
Zerihun Assefa • Oak Ridge National Laboratory, Chemical and
Analytical Sciences Division, Oak Ridge, TN 37831-6375, USA
Paul E. Burrows. Center for Photonic and Optoelectronic Materials,
Department of Electrical Engineering, Princeton University, Princeton,
NJ 08544, USA
John P. Fackler, Jr. • Department of Chemistry, Texas A&M Univer
sity, College Station, TX 77843-3255, USA
Stephen R. Forrest. Center for Photonic and Optoelectronic Materi
als, Department of Electrical Engineering, Princeton University, Prin
ceton, NJ 08544, USA
Jennifer M. Forward. Department of Chemistry, Texas A&M Univer
sity, College Station, TX 77843-3255, USA
M. Griitzel • Laboratory for Photonics and Interfaces, Swiss Federal
Institute of Technology, CH-1015 Lausanne, Switzerland
Gary Gray. Department of Chemistry, The University of Alabama at
Birmingham, UAB Station, Birmingham, AL 35294, USA
K. Kalyanasundaram • Laboratory for Photonics & Interfaces, Swiss
Federal Institute of Technology, CH-1015 Lausanne, Switzerland
John W. Kenney, 11/ • Chemical Physics Laboratory, Department of
Physical Sciences and Chemistry, Eastern New Mexico University,
Portales, NM 88130, USA
Stephen V. Kershaw. BT Labs, Martlesham Heath, Ipswich, Suffolk
1P 5 3RE, U.K.
Minh C. Ko • Department of Chemistry, Johns Hopkins University,
Baltimore, MD 21218, USA
Christopher M. Lawson • Department of Physics, The University of
Alabama at Birmingham, UAB Station, Birmingham, AL 35294, USA
Nicholas J. Long. Department of Chemistry, Imperial College of
Science, Technology and Medicine, South Kensington, London SW7
2AY, U.K.
v
vi Contributors
Gerald J. Meyer. Department of Chemistry, Johns Hopkins Univer
sity, Baltimore, MD 21218, USA
D. Max Roundhill. Department of Chemistry and Biochemistry,
Texas Tech University, Lubbock, TX 79409-1061, USA
S. Shi • S5-ALL Technologies Co., Singapore 079903
Scott Sibley. Department of Chemistry, University of Southern
California, Los Angeles, CA 90089-0744, USA
Mark E. Thompson. Department of Chemistry, University of South
ern California, Los Angeles, CA 90089-0744, USA
Preface
This book is intended to offer the reader a snapshot of the field of optoelectronic
materials from the viewpoint of inorganic chemists. The field of inorganic
chemistry is transforming from one focused on the synthesis of compounds
having interesting coordination numbers, structures, and stereochemistries, to one
focused on preparing compounds that have potentially useful practical applica
tions. Two such applications are in the area of optics and electronics. These are
fields where the use of inorganic materials has a long history. As the field of
microelectronics develops the demands on the performance of such materials
increases, and it becomes necessary to discover compounds that will meet these
demands.
The field of optoelectronics represents a merging of the two disciplines. Its
emergence is a natural one because many of the applications involve both of these
properties, and also because the electronic structure of a metal compound that
confers novel optical properties is often one that also influences its electron
transfer and conductivity characteristics. Two of the more important growth areas
that have led to these developments are communications and medicine. Within
the communications field there is the microelectronics that is involved in
information storage and transmittal, some of which will be transferred into the
optical regime. Within the medical field there are chemical probes that transmit
analytical information from an in vivo environment. This information needs to be
readily accessible from an external site, and then quickly converted into images or
data that yield accurate and inexpensive diagnoses.
These rapidly developing applications of optoelectronic materials place
unusually high demands on any new compounds. For communications applica
tions the materials must have good thermal and optical stability, and must
function both rapidly and energy efficiently in their required mode. The presence
of impurities must be either eliminated or carefully controlled. From the rationale
of high performance materials the observed properties must be carefully corre
lated with the solid state structure of the compound. Inorganic compounds are
particularly suited to these applications because of the broad range of elements
vii
viii Preface
that are available for incorporation into new compounds, and also because heavier
elements such as transition metals, lanthanides, and actinides have closely spaced
energy levels that strongly influence the optical and electrical properties of their
compounds.
Among the demands that are being imposed by the new technologies are the
needs for compounds that have nonlinear optical and photoconducting properties,
compounds that have novel emissive properties, and compounds that have tunable
emissive or electroactive centers that can act as selective sensors for organic,
inorganic, and biochemical substances. Other compounds are being sought whose
optical properties are sensitive to external changes such as pressure. The chapters
in this book reflect many of these aspects, and provide an up-to-date description
as to the present state of the art in these fields.
Clearly this is an emerging field that has a very broad scope both in the types
of compounds that are being synthesized and in the applications that are being
satisfied by these compounds. The topics chosen for this volume are ones that we
believe will have long-term significance and importance. Predicting such an
outcome is at best speculative, however, because this will be driven both by the
desired optoelectronic applications and by the properties of the compounds that
are still to be discovered. The discovery and practical application of new
optoelectronic materials will require close collaboration between scientists of a
multitude of different skills and interests, in addition to a considerable amount of
intuition, imagination, and serendipity. We hope that this book will encourage
young scientists to venture down this road.
July 1998
D. Max Roundhill
John P. Fackler, Jr
Contents
1. Structure-Property Relationships in Transition Metal-Organic
Third-Order Nonlinear Optical Materials
Gary M Gray and Christopher M Lawson
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Applications and Requirements for Third-Order Nonlinear
Optical Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2. Metal-Organic NLO Materials. . . . . . . . . . . . . . . . . . . . . . 2
1.2.1. Transition Metal Complexes with Planar n-Conjugated
Tetradentate Ligands. . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2. Organometallic Transition Metal Complexes
Containing n-Conjugated Ligands. . . . . . . . . . . . . . . 5
1.2.3. Metal Cluster Complexes. . . . . . . . . . . . . . . . . . . . . 7
1.3. Status of Structure-Property Relationships for Metal-Organic
Third-Order NLO Materials. . . . . . . . . . . . . . . . . . . . . . . . 7
2. Experimental Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1. Wavelength-Tunable DFWM Experiments . . . . . . . . . . . . .. 10
2.2. Z-Scan Experiments. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11
3. Third-Order NLO Susceptibilities of Metal-Organic
Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
3.1. Bis(salicylatoaldehyde)ethylenediimine or
Bis(acetylacetonate)ethylenediimine Complexes. . . . . . . . .. 13
3.2. Transition Metal Complexes with Phosphorus-Donor Ligands. 17
=
3.2.1. DFWM Studies of Mo(CO)6_n(PPh2X)n (n 1,2)
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 17
3.2.2. Z-Scan Studies of Pd and Pt Complexes of
PPh3_n(2-thienyl)n Ligands . . . . . . . . . . . . . . . . . .. 20
4. Summary and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 23
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
ix
x Contents
2. Electroluminescence in Molecular Materials
Scott Sibley, Mark E. Thompson, Paul E. Burrows,
and Stephen R. Forrest
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 29
2. Photo- and Electroluminescence in Molecular Solids . . . . . . . . .. 31
3. OLED Heterostructures for Improved Injection Efficiency. . . . . .. 33
4. Molecular Origins of Luminescence . . . . . . . . . . . . . . . . . . . .. 38
5. Electrons and Holes in Molecular Organic Materials. . . . . . . . .. 40
6. Charge Transport and Electroluminescence in the Presence
of Traps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42
7. Fitting the Model to TPD/AI<b OLEDs . . . . . . . . . . . . . . . . . .. 46
8. Transparent OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 49
9. Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 52
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 53
3. Nonlinear Optical Properties of Inorganic Clusters
S. Shi
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 55
1.1. Optical Nonlinearity and Its Applications . . . . . . . . . . . . .. 55
1.2. Optical Bistable Devices. . . . . . . . . . . . . . . . . . . . . . . . .. 56
1.3. Inorganic Clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 61
2. Butterfly-Shaped Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62
2.1. Figure of Merit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62
2.2. Design, Syntheses, and Structures . . . . . . . . . . . . . . . . . .. 63
2.3. Minimization of Linear Absorption. . . . . . . . . . . . . . . . . .. 66
2.4. Measurement ofNLO Refraction (Z-Scan). . . . . . . . . . . . .. 67
3. Nest- and Twin Nest-Shaped Clusters. . . . . . . . . . . . . . . . . . .. 70
3.1. Syntheses and Structures . . . . . . . . . . . . . . . . . . . . . . . .. 70
3.2. Effective Third-Order NLO Behavior. . . . . . . . . . . . . . . .. 72
3.3. Photodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 74
3.4. Temporal Profile of Transmitted Laser Pulses. . . . . . . . . . .. 79
3.5. Dispersion of n2 . • • • . . • . • . . • • • • • . . . . . • . • . • • . . .. 81
4. Cubic Cage-Shaped Clusters . . . . . . . . . . . . . . . . . . . . . . . . .. 83
4.1. Syntheses and Structures . . . . . . . . . . . . . . . . . . . . . . . .. 83
4.2. Optical Limiting Effect. . . . . . . . . . . . . . . . . . . . . . . . . .. 85
4.3. Evidence of Excited State Absorption. . . . . . . . . . . . . . . .. 86
4.4. Influence of Excited State Population . . . . . . . . . . . . . . . .. 89
4.5. Diffuseness of Electron Clouds . . . . . . . . . . . . . . . . . . . .. 90
4.6. Hexagonal Prism-Shaped Derivatives. . . . . . . . . . . . . . . .. 91
5. Half-Open Cage-Shaped Clusters. . . . . . . . . . . . . . . . . . . . . .. 95
5.1. Syntheses and Structures . . . . . . . . . . . . . . . . . . . . . . . .. 94