Luminescence of Solids

434 Pages·1998·22.121 MB·English

by  V. P. Gribkovskii (auth.), D. R. Vij (eds.)

Luminescence of Solids
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Contributors
L. Yu. Brovko, Department of Chemistry, Lomonosov Moscow State University,
Moscow, Russia.
B. P. Chandra, Department of Postgraduate Studies and Research in Physics, Rani
Durgavati University, Jabalpur 482001, India.
Sean M. Cordry, Department of Physics and Astronomy, University of Mississippi,
Mississippi 38677, United States.
Lawrence A. Crum, Applied Physics Laboratory, University of Washington, Seattle,
Washington 98105, United States.
E. 1. Dementieva, Department of Chemistry, Lomonosov Moscow State University,
Moscow, Russia.
Debabrata Ghose, Saha Institute of Nuclear Physics, Bidhan Nagar, Calcutta 700064,
India.
V. P. Gribkovskii, B. I. Stepanov Institute of Physics, Academy of Sciences of Belarus,
Minsk, 220072, Byelorussia.
H.-E. Gumlich, Institut fUr Festkorperphysik, Technische UniversiHit, D-10623,
Berlin, Germany.
Rainer Hippler, FakulHit fUr Physik, UniversiHit Bielefeld, D-33501, Bielefeld,
Germany. Present address: Institut fUr Physik, Universitat Greifswald, Domstrasse
lOa, D-Germany.
R. Mauch, Heinrich Hertz, Institut, 10117 Berlin, Germany.
A. Meijerink, Department of Condensed Matter, Universitat Utrecht, 3508 TA,
Utrecht, The Netherlands.
Stefan Myhajlenko, Center for Solid State Electronics Research, College of Engineer
ing and Applied Sciences, Arizona State University, Tempe, Arizona 85287, United
States.
v
vi CONTRIBUTORS
George T. Reynolds, Department of Physics, Princeton University, Princeton, New
Jersey 08544, United States.
Shigeo Shionoya, Professor Emeritus, The University of Tokyo, Japan.
N. N. Ugarova, Department of Chemistry, Lomonosov Moscow State University,
Moscow, Russia.
D. R. Vij, Department of Physics, Kurukshetra University, Kurukshetra, India.
A. Zeinert, Universite de Picardie Jules Verne, F80035 Amiens, France.
Preface
The past three decades have witnessed rapid growth in research and development of
luminescent materials because of their diverse applications. Studies have been carried
out in almost all branches of luminescence, including photoluminescence, cath
odoluminescence, electroluminescence, thermoluminescence, and lyoluminescence,
among others, with a view toward inventing and preparing new materials of practical
use.
It has become possible to observe new phenomena in known luminescent
substances: e.g., saturation and absorption of luminescence, induced dichroism,
depolarization of luminescence with increasing excitation power, two-photon ab
sorption, luminescence at forbidden transitions, hot luminescence, radiation of
biexcitons, electron-hole drops, ultrafast processes, self-focusing of light, and non
linear phenomena.
Moreover, the range of luminescent substances has been broadened owing to
the production of complex materials and, frequently, materials that do not exist in
nature, at all, i.e., hyperfine films of crystals, quantum-dimensional structures,
stressed layers, and superlattices.
This volume is the outcome of a clear need to review the recent trends in
research on luminescent inorganic materials and new physical phenomena in all the
various branches of the field. It has been designed to provide an overview of different
areas of luminescence and related properties of important luminescent materials
from a practical point of view.
The individual chapters offer in-depth but concise reviews of different classes of
luminescence so that the reader can utilize the information to examine the various
phenomena with the right perspective.
The volume begins with a chapter on the theory of luminescence, wherein an
attempt has been made to present the achievements that led to the establishment of
the fundamental laws of luminescence. Phenomenological expressions are given
relating to the most important characteristics of luminescence, such as power,
spectra, polarization, quantum efficiency, rise and decay times, light sum, and so
forth, utilizing quantum theory and different basic models. The second chapter deals
vii
viii PREFACE
with the conventional and modem experimental techniques, different types of light
sources, light-dispersing elements, and the detectors in current use in luminescence
spectroscopy of solids.
The rest of the volume is a survey of nearly all the different types of classes of
luminescence-photo-, cathodo-, iono-, electro-, thermo-, lyo-, sono-, and
mechanoluminescence-with each chapter being devoted to a particular type.
In addition to historical background, emphasis has been placed on the models
and mechanisms, on materials with their preparation methods and characteristics,
measurement techniques, and on future trends. The last chapter is devoted to Bio
and Chemiluminescence, which although not generally exhibited by inorganic solids,
have been introduced not only to apprise readers of this class of luminescence, but
to provide a complete presentation that includes all the branches of luminescence in
one volume.
This book is a valuable collection by a diverse group of outstanding and
experienced researchers, and it has an international flavor inasmuch as the contribu
tors are from United States, Germany, Japan, India, Russia, and The Netherlands.
It is hoped that it will help advanced students taking courses in luminescence and
serve as a review for researchers going into the field. It should be useful as well for
material physicists, chemists, biologists, engineers, and all the professionals asso
ciated with luminescence spectroscopy.
It is my pleasant duty to express my thanks to the contributors, who made this
volume possible. My own efforts in the planning and preparation of this volume have
benefited greatly from many fruitful interactions with colleagues in the Physics
Department of Kurukshetra University over the past 30 years. I am also indebted
to all those authors and publishers who promptly granted permission to reproduce
their copyrighted materials. The patient encouragement of the staff at Plenum Press
in New York is also acknowledged with gratitude. The help of Mr. S. C. Verma in
connection with the typing of the manuscript is greatly appreciated. Last but not the
least, I wish to express my deep appreciation to my wife, Meenakshi, and my
daughters, Surabhi and Monica, for their support, encouragement, and patience
throughout this time-consuming and seemingly endless task of writing and editing
this volume.
D. R. Vij
Kurukshetra
Spring 1998
Contents
1. Theory of Luminescence
V. P. Gribkovskii
1. Introduction . 1
2. Characteristics of Luminescence 3
2.1. Luminescence Power .. 3
2.2. Luminescence Spectrum 4
2.3. Excitation Spectrum. . 5
2.4. Luminescence Polarization 5
2.5. Optical Indicatrix . . . . 6
2.6. Energy and Quantum Yields 8
2.7. Anti-Stokes Luminescence 9
2.8. Luminescence Rise and Decay. 10
2.9. Light Sum . . . . . . 11
2.10. Thermoluminescence .. 12
2.11. Negative Luminescence. 12
2.12. Hot Luminescence. . . 13
2.13. Superluminescence or Amplified Luminescence . 14
2.14. Near- and Far-Field Patterns ....... _ . 15
3. Fundamentals of the Quantum Theory of Radiation . 16
3.1. Classical, Quantum-Mechanical (Semiclassical), and
Quantum-Electrodynamic Methods. . 16
3.2. Electronic States in an Ideal Crystal . 19
3.3. Lattice Vibrations: Phonons . 21
3.4. Impurity Levels and Bands . _ . . . 22
3.5. Excitons and Biexcitons. . . 24
3.6. Probabilities of Spontaneous and Induced Transitions. 26
3.7. Nonradiative Transitions . . _ . . . . . . _ . 27
4. Theoretical Models and Mechanisms of Luminescence. 27
4.1. The Harmonic Oscillator . . _ . . . . . . _ . 27
ix
x CONTENTS
4.2. Two-, Three-, and N-Levd Systems ..... 28
4.3. Band-to-Band Absorption and Luminescence. 30
4.4. Luminescence in Impurity Solids. . . . . 32
4.5. Donor-Acceptor-Pair Luminescence . . . 34
4.6. Luminescence of Free and Bound Excitons . 35
4.7. Streamer Luminescence . . 37
5. Conclusions and Future Trends 39
References . . . . . . 40
2. Experimental Techniques
A. M eijerink
1. Introduction 45
2. Absorption and Luminescence Spectroscopy . 46
2.1. Absorption . . . . . 46
2.2. Luminescence .... 50
3. Spectroscopic Components 53
3.1. Excitation Sources . . 53
3.2. Light-Dispersing Elements. 58
3.3. Light Detection . . . . . 62
4. Time-Resolved Spectroscopy .. 67
5. Hole-Burning, Fluorescence Line-Narrowing, and Photon Echo 71
5.1. Optical Hole-Burning. . . . 72
5.2. Fluorescence Line-Narrowing ...... . 73
5.3. Photon Echo ............. . 73
6. Quantum Efficiency and Nonradiative Processes. 77
7. Polarization and Perturbation Spectroscopy. 81
7.1. Polarization Spectroscopy . 81
7.2. Perturbation Spectroscopy. 84
8. New Developments. . . . . . 87
8.1. Ultrafast Spectroscopy 87
8.2. Single-Molecule Spectroscopy 89
8.3. Near-Field Optical Spectroscopy . 91
References . . . . . . . . . . . . . . 93
3. Photoluminescence
Shigeo Shionoya
1. Introduction . . . . . . . . . . . . 95
2. Classification of Photoluminescence in Solids 96
2.1. Intrinsic Luminescence 96
2.2. Extrinsic Luminescence . . . . 97
3. Band-to-Band Luminescence. . .. 99
3.1. Direct and Indirect Transitions. 99
3.2. Luminescence Transition Rates and Spectra . 101
3.3. Recombination Cross Sections and Impurities . 102
CONTENTS xi
4. Wannier Exciton Luminescence ...... . 103
4.1. Energy States of Wannier Excitons. . . . 103
4.2. Luminescence of Free and Bound Excitons . 104
4.3. Luminescence of Self-Trapped Excitons. . 105
4.4. Luminescence of Excitonic Molecules. . . 106
5. Characteristics of Localized-Center Luminescence . 108
5.L Configuration-Coordinate Model ..... 108
5.2. Theoretical Treatments of Spectral Shapes. . 109
5.3. Examples of Typical Spectra. . . . . . . . 111
5.4. Temperature Dependence of Luminescence Efficiency. 113
6. Extrinsic Luminescence of Unlocalized Type. . . 114
6.1. Donor-Acceptor Pair Luminescence. . . . 114
6.2. Luminescence Owing to Isoelectronic Traps . 119
7. Extrinsic Luminescence of Localized Type. . . . 120
7.1. Luminescence of Allowed-Transition-Type Ions. 120
7.2. Luminescence of Forbidden-Transition-Type Ions. 124
8. Luminescence of Low-Dimensional Systems . 130
References . . . . . . . . . . . . . . . . . . . . . 133
4. Cathodoluminescence
Stefan Myhajlenko
L Introduction . . 135
1.1. Historical Perspective . 135
1.2. Current Outlook . . . 135
2. Fundamental Aspects. . . 136
2.1. Electron-Beam Interactions in Solids . 136
2.2. Luminescence Processes in Solids . 140
2.3. Cathodoluminescence Generation . 145
2.4. Cathodoluminescence Modeling . 147
3. Experimental Aspects. . . . . . . . 150
3.1. Basic Design and Instrumentation 150
3.2. Configurational Permutations 154
3.3. Operational Considerations 159
4. Materials Applications 166
4.1. Semiconducting Materials . 166
4.2. Minerals ., . . . . . . 167
4.3. Ceramics and Superconductors . 169
5. Recent Applications. . . . . . . . 170
5.L Stress Anisotropy in Thin Films . 170
5.2. High-Spatial-Resolution Imaging of Defects and Epitaxial
Films . . . . . . . . . . . . . . ... 173
5.3. Surface- and Depth-Resolved Information. 179
5.4. Time-Resolved Measurements 180
6. Future Trends 182
References . . . . . . . . . . . . 183