Table Of ContentTopics in Applied Physics Volume 20
Topics in Applied Physics Founded by Helmut K. V. Lotsch
Volume 1 Dye Lasers 2nd Edition Editor : F. P. Schafer
Volume 2 Laser Spectroscopy of Atoms and Molecules
Editor: H. Walther
Volume 3 Numerical and Asymptotic Techniques in Electromagnetics
Editor: R. Mittra
Volume 4 Interactions on Metal Surfaces Editor: R. Gomer
Volume 5 Miissbauer Spectroscopy Editor: U. Gonser
Volume 6 Picture Processing and Digital Filtering Editor: T. S. Huang
Volume 7 Integrated Optics Editor: T. Tamir
Volume 8 Light Scattering in Solids Editor: M. Cardona
Volume 9 Laser Speckle and Related Phenomena Editor: J. C. Dainty
Volume 10 Transient Electromagnetic Fields Editor: L,. B. Felsen
Volume 11 Digital Picture Analysis Editor: A. Rosenfeld
Volume 12 Turbulence Editor: P. Bradshaw
Volume High-Resolution Laser Spectroscopy Editor: K. Shimoda
Volume Laser Monitoring of the Atmosphere Editor: E. D. Hinkley
Volume Radiationless Processes in Molecules and Condensed Phases
Editor: F. K. Fong
Volume Nonlinear Infrared Generation Editor: Y.-R. Shen
Volume Electroluminescence Editor: J. I. Pankove
Volume Ultrashort Light Pulses. Picosecond Techniques and
Applications Editor: S. L. Shapiro
Volume 19 Optical and Infrared Detectors Editor: R. J. Keyes
Volume 20 Holographic Recording Materials Editor: H. M. Smith
Volume 21 Solid Electrolytes Editor: S. Geller
Volume 22 X-Ray Optics. Applications to Solids
Editor: H.-J. Queisser
Volume 23 optical Data Processing. Application., Editor: D. Casasent
Volume 24 Acoustic Surface Waves Editor: A. A. Oliner
cihpargoloH
gnidroceR slairetaM
Edited by H. M. Smith
With Contributions by
R. A. Bartolini K. Biedermann J. Bordogna
R. C. Duncan, Jr. S.A. Keneman D. Meyerhofer
H. M. Smith D.L. Staebler J.C. Urbach
With 69 Figures
Springer-Verlag Berlin Heidelberg New York 7791
Howard M. Smith, Ph. D.
Eastman Kodak Company, 343 State Street
Rochester, NY 14650, USA
ISBN 3-540-08293-X Springer-Verlag Berlin Heidelberg New York
ISBN 0-387-08293-X Springer-Verlag New York Heidelberg Berlin
Library of Congress Cataloging in Publication Data. Main entry under title: Holographic recording materials. (Topics in applied
physics; v. 20). Includes bibliographical references and index. I. Holography-Equipment and supplies. .1 Smith, Howard Michael,
1938-. II. Bartolini, Robert A. TA 1542.H 64 621.36 77-24503
This work is subject to copyright. All rights are reserved, whether the whole or part of Ihe material is concerned, specifically
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)~( by Springer-Verlag Berlin Heidelberg 1977
Printed in Germany
The use of registered names, trademarks, etc. in this publicatic, n 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 general use
Monopholo lypesetliug, offset printing, and bookbinding: Briihlsche Universitiitsdi uckerei, I,ahn-Giefen
2 53/3130/543210
Preface
With most new or advancing technologies, the period of discovery and
initial investigation of fundamental principles is immediately followed by a
period of intensive search for materials. This is the period when potential
applications are being explored and engineering and design begin. The
recent discoveries of the transistor and the laser are two prime examples of
this type of technological evolution. A third example is the invention and
recent renaissance of holography. Following the revival in 1962 to 1964 there
came a prolonged (and indeed, ongoing) search for an ideal recording
material. The purpose of this volume is to present the up-to-date results of
this search.
The timing is right for a book devoted solely to recording materials,
not only because so much work has been done, but also because the
science and engineering of holography have done a good deal of "settling-in".
The needs, aims, and applications have become well defined and the range
of useful applications has been narrowed to the extent that whether or not
a particular application is viable may well depend on the availability
of a suitable recording material. These reasons, and also the fact that, in most
cases, each different holographic application has its own unique requirement
for a recording material, point up the need for a book on the subject of
recording materials.
It is the aim of this volume to satisfy this need. The basic theory
and principles of holography have been covered in a summary fashion in
the introductory chapter. The purpose here is simply to acquaint the reader
with the basic theory and terminology so that the ensuing chapters can be
devoted totally to describing recording materials. I have tried to ensure that
every known holographic (or laser) recording material is covered. The authors
have ensured that each chapter represents the present state-of-the-art, even
to the extent that some material is presented here for the first time.
The book is intended to be a monograph, but with so many individual
contributors there is bound to be some overlap and inconsistency of notation
in spite of the best efforts of the editor. For these I apologize, but I would
hope that their effect will be minor and in no way detract from the content
of each chapter.
Rochester, New York H. M. Smith
June, 1977
Contents
1. Basic Holographic Principles. By H. M. Smith (With 7 Figures) 1
1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Basic Description . . . . . . . . . . . . . . . . . . . . 2
1.3 Classification . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Diffraction Efficiency . . . . . . . . . . . . . . . . . . . 5
1.4.1 Plane Holograms . . . . . . . . . . . . . . . . . . 6
Amplitude Holograms . . . . . . . . . . . . . . . . 6
Phase Holograms . . . . . . . . . . . . . . . . . . 9
1.4.2 Volume Holograms . . . . . . . . . . . . . . . . . 10
Coupled Wave Theory . . . . . . . . . . . . . . . . 10
Transmission Holograms . . . . . . . . . . . . . . . 13
Reflection Holograms . . . . . . . . . . . . . . . . 16
Summary . . . . . . . . . . . . . . . . . . . . . 17
1.5 Noise . . . . . . . . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . 91
2. Silver Halide Photographic Materials. By K. Biedermann
(With 25 Figures) . . . . . . . . . . . . . . . . . . . . . . 21
2.1 The Holographic Process . . . . . . . . . . . . . . . . . 22
2.2 The Silver Halide Emulsion . . . . . . . . . . . . . . . . 22
2.3 The Practical Procedure of Making Holograms and Spatial Filters 25
2.3.1 Photographic Materials Available . . . . . . . . . . . 25
2.3.2 Recording a Hologram . . . . . . . . . . . . . . . 26
Aspects on Material, Size, and Geometry . . . . . . . . 26
A Deviation on Antireflection Treatment . . . . . . . . 26
More on Choosing Material, Size, and Geometry .... 26
Intensity Ratio K and Exposure . . . . . . . . . . . . 27
2.3.3 Processing . . . . . . . . . . . . . . . . . . . . . 28
Standard Procedures . . . . . . . . . . . . . . . . 28
Special Developers . . . . . . . . . . . . . . . . . 13
2.3.4 Reconstruction . . . . . . . . . . . . . . . . . . . 13
2.3.5 Real Time Interferometer with in Situ Development 32
2.4 Characteristic Parameters of Thin Amplitude Holograms and
Their Evaluation . . . . . . . . . . . . . . . . . . . . . 34
2.4.1 The Two-Step Transfer Process . . . . . . . . . . . . 34
VIII Contents
2.4.2 The Macroscopic Characteristic . . . . . . . . . . . . 34
2.4.3 The Microscopic Characteristic . . . . . . . . . . . . 36
The Modulation Transfer Function (MTF) . . . . . . . 36
The MTF in Coherent Light . . . . . . . . . . . . . 37
Methods for Measuring MTF at High Spatial Frequencies 38
The Microdensitometer . . . . . . . . . . . . . . . . 38
The Diffraction Method . . . . . . . . . . . . . . . 39
The Multiple-Sine-Slit Microdensitometer . . . . . . . . 41
Modulation Transfer Data of Silver Halide Materials 43
2.4.4 Scattered Flux Spectrum . . . . . . . . . . . . . . . 44
2.4.5 Figure of Merit and Attempts to Improve Photographic
Materials . . . . . . . . . . . . . . . . . . . . . 48
Holographic Exposure Index . . . . . . . . . . . . . 48
Ways of Increasing the Holographic Exposure Index 49
Extending Sensitivity to Infrared Radiation . . . . . . . 49
2.4.6 Holography vs. Photography . . . . . . . . . . . . . 50
2.5 Effects . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.5.1 Macroscopic Nonlinear Transfer . . . . . . . . . . . 51
2.5.2 Microscopic Nonlinear Transfer . . . . . . . . . . . 53
2.5.3 Complex Grating Formation . . . . . . . . . . . . . 55
2.5.4 "Emulsion Stress" . . . . . . . . . . . . . . . . . 56
2.6 Experimental Data on Diffraction Efficiency and Signal-to-Back-
ground Ratio of Thin Amplitude Holograms . . . . . . . . . 57
2.7 Phase Holograms . . . . . . . . . . . . . . . . . . . . 59
2.7.1 Principles of Phase Grating Generation . . . . . . . . 59
2.7.2 Bleaching Procedures . . . . . . . . . . . . . . . . 61
Gelatine Relief Formation . . . . . . . . . . . . . . 61
Bleaching . . . . . . . . . . . . . . . . . . . . . 62
Gaseous Bleaching . . . . . . . . . . . . . . . . . 63
Reversal Processes . . . . . . . . . . . . . . . . . 64
2.7.3 Experimental Data on Diffraction Efficiency and Signal-to-
Background Ratio . . . . . . . . . . . . . . . . . 64
2.8 Thick Holograms . . . . . . . . . . . . . . . . . . . . 66
2.8.1 Characteristics of Thick Photographic Emulsions .... 66
2.8.2 Materials Available; Problems . . . . . . . . . . . . 67
2.8.3 Holograms of Extended Thickness . . . . . . . . . . . 68
2.8.4 Experimental Data on Diffraction Efficiency and Signal-to
Background Ratio of Thick Holograms . . . . . . . . 68
2.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . 70
References . . . . . . . . . . . . . . . . . . . . . . . . . 71
3. Dichromated Gelatin. By D. Meyerhofer (With 5 Figures) ..... 75
3.1 Basic Photochemistry . . . . . . . . . . . . . . . . . . . 76
3.1.1 Dichromated Colloid Layers . . . . . . . . . . . . . 76
Contents XI
3.1.2 The Properties of Gelatin . . . . . . . . . . . . . . 77
3.1.3 Photosensitivity of the Dichromate Ion . . . . . . . . . 78
3.2 Dichromated Gelatin as a Photosensitive Medium . . . . . . 79
3.2.1 Dichromated Gelatin as a Photoresist . . . . . . . . . 79
3.2.2 PhotochemistryofPrehardened Dichromated Gelatin Layers 80
3.2.3 The Shankoff Technique of Phase Shift Enhancement 82
3.2.4 Variation in Emulsion Thickness During Processing . . 85
3.3 Preparation and Processing of Hardened Dichromated Gelatin
Plates for Thick Holograms . . . . . . . . . . . . . . . . 87
3.3.1 Preparation of Plates . . . . . . . . . . . . . . . . 87
3.3.2 Development Procedure . . . . . . . . . . . . . . . 89
3.3.3 Stability of Dichromated Gelatin Holograms . . . . . . 91
3.4 Holographic Properties of Hardened Dichromated Gelatin . . . 91
3.4.1 Phase Shift Available . . . . . . . . . . . . . . . . 91
3.4.2 Sensitivity . . . . . . . . . . . . . . . . . . . . . 93
3.4.3 Resolution . . . . . . . . . . . . . . . . . . . . . 95
3.4.4 Image Quality and Noise . . . . . . . . . . . . . . . 95
3.4.5 Storage Capacity . . . . . . . . . . . . . . . . . . 96
3.5 Applications . . . . . . . . . . . . . . . . . . . . . . 97
3.5.1 Holographic Optical Elements . . . . . . . . . . . . 97
3.5.2 Duplicate Holograms in Dichromated Gelatin ..... 98
References . . . . . . . . . . . . . . . . . . . . . . . . . 98
4. Ferroelectric Crystals. By D. L. Staebler (With 13 Figures) . . . . . 101
4.1 Theory of Mechanisms . . . . . . . . . . . . . . . . . . 102
4.1.1 Storage . . . . . . . . . . . . . . . . . . . . . . 102
4.1.2 Erasure . . . . . . . . . . . . . . . . . . . . . . 108
4.1.3 Fixing . . . . . . . . . . . . . . . . . . . . . . . 109
4.1.4 Electrical Enhancement . . . . . . . . . . . . . . . 114
4.2 Materials and Preparation . . . . . . . . . . . . . . . . . 115
4.2.1 Lithium Niobate (LiNbO3) . . . . . . . . . . . . . . 115
4.2.2 Strontium Barium Niobate (SBN) . . . . . . . . . . . 117
4.2.3 Barium Titanate (BaTiO3) . . . . . . . . . . . . . . 118
4.2.4 Barium Sodium Niobate . . . . . . . . . . . . . . . 118
4.2.5 Lithium Tantalate (LiTaO3) . . . . . . . . . . . . . 118
4.2.6 Potassium Tantalate Niobate (KTN) . . . . . . . . . . 118
4.2.7 PLZT Ceramics . . . . . . . . . . . . . . . . . . . 119
4.3 Methods of Use . . . . . . . . . . . . . . . . . . . . . ! 19
4.3.1 Read/Write . . . . . . . . . . . . . . . . . . . . 120
4.3.2 Read/Write with Nondestructive Readout (NDRO) 120
4.3.3 Read-Only . . . . . . . . . . . . . . . . . . . . . 121
4.3.4 Multiphoton Absorption . . . . . . . . . . . . . . . 121
4.3.5 Layered Memory . . . . . . . . . . . . . . . . . . 122
4.3.6 Holographic Page Synthesis . . . . . . . . . . . . . 123
X Contents
4.4 Holographic Properties . . . . . . . . . . . . . . . . . . 123
4.4.1 Sensitivity . . . . . . . . . . . . . . . . . . . . . 123
4.4.2 Dynamic Range . . . . . . . . . . . . . . . . . . 126
4.4.3 Resolution . . . . . . . . . . . . . . . . . . . . . 128
4.4.4 Storage Time . . . . . . . . . . . . . . . . . . . . 128
4.4.5 Noise and Distortion . . . . . . . . . . . . . . . . 129
References . . . . . . . . . . . . . . . . . . . . . . . . . 130
5. Inorganic Photochromic Materials. By R. C. Duncan, .rJ and
D. L. Staebler (With 20 Figures) . . . . . . . . . . . . . . . . 133
5.1 Basic Model . . . . . . . . . . . . . . . . . . . . . . . 134
5.2 Photochromic CaF 2, SrTiO3, CaTiO3 . . . . . . . . . . . . 135
5.2.1 Optimum Dopants and Concentrations . . . . . . . . 135
5.2.2 Photochromic Absorption Spectra . . . . . . . . . . . 136
5.2.3 Optical Recording Modes . . . . . . . . . . . . . . 139
5.2.4 Optical Readout at 514.5 nm . . . . . . . . . . . . . 140
Thickness Effects . . . . . . . . . . . . . . . . . . 140
Contrast Ratio . . . . . . . . . . . . . . . . . . . 141
5.2.5 Erase Mode Sensitivity at 514.5 nm . . . . . . . . . . 141
5.2.6 Sensitometric Characteristics and Time-Intensity Reci-
procity . . . . . . . . . . . . . . . . . . . . . . 145
CaF z : La, Na and CaF 2 : Ce, Na . . . . . . . . . . . 146
SrTiO3 : Ni, Mo, A1 and CaTiO3 : Ni, Mo . . . . . . . . 148
5.3 Hologram Storage . . . . . . . . . . . . . . . . . . . . 151
5.3.1 Sensitivity . . . . . . . . . . . . . . . . . . . . . 152
5.3.2 Maximum Efficiency . . . . . . . . . . . . . . . . 154
5.3.3 Storage Capacity . . . . . . . . . . . . . . . . . . 155
5.4 Photodichroics . . . . . . . . . . . . . . . . . . . . . 156
5.4.1 Model . . . . . . . . . . . . . . . . . . . . . . . 156
5.4.2 Hologram Storage . . . . . . . . . . . . . . . . . 158
References . . . . . . . . . . . . . . . . . . . . . . . . . 159
6. Thermoplastic Hologram Recording. By .J C. Urbach
(With 14 Figures) . . . . . . . . . . . . . . . . . . . . . . 161
6.1 Process Description . . . . . . . . . . . . . . . . . . . 161
6.1.1 Thermoplastic Electron Beam Recording . . . . . . . . 162
6.1.2 Photosensitive Recording . . . . . . . . . . . . . . 163
Photoplastic Devices . . . . . . . . . . . . . . . . 164
Thermoplastic-Overcoated Photoconductor Devices . . 166
Device and Process Variations . . . . . . . . . . . . 167
6.1.3 Process Models and Theories . . . . . . . . . . . . . 168
Theories of Random Deformation . . . . . . . . . . . 170
6.1.4 Materials . . . . . . . . . . . . . . . . . . . . . . 171
Contents IX
Substrates and Conductive Coatings . . . . . . . . . . 171
Photoconductors . . . . . . . . . . . . . . . . . . 172
Special Photoconductors . . . . . . . . . . . . . . . 176
Thermoplastic Materials . . . . . . . . . . . . . . . 177
6.1.5 Fabrication Techniques . . . . . . . . . . . . . . . 181
Substrates and Conductive Coatings . . . . . . . . . . 181
Photoconductor Fabrication . . . . . . . . . . . . . 182
Thermoplastic Fabrication . . . . . . . . . . . . . . 184
Overcoating and Matrixing . . . . . . . . . . . . . . 185
6.2 Holographic Properties . . . . . . . . . . . . . . . . . . 186
6.2.1 Bandwidth and Resolution . . . . . . . . . . . . . . 186
6.2.2 Sensitivity and Diffraction Efficiency . . . . . . . . . 191
Diffraction Efficiency Considerations . . . . . . . . . 192
Experimental Exposure Response Results . . . . . . . 194
6.2.3 Noise . . . . . . . . . . . . . . . . . . . . . . . 197
Experimental Noise Measurements . . . . . . . . . . 199
6.2.4 Cyclic Operation . . . . . . . . . . . . . . . . . . 201
6.2.5 Other Physical Properties . . . . . . . . . . . . . . 202
Shelf Life . . . . . . . . . . . . . . . . . . . . . 202
Latent Image Life . . . . . . . . . . . . . . . . . . 203
Archival Life . . . . . . . . . . . . . . . . . . . . 203
Mechanical Durability and Contamination . . . . . . . 204
6.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . 205
References . . . . . . . . . . . . . . . . . . . . . . . . . 206
7. Photoresists. By R. A. Bartolini (With 11 Figures) . . . . . . . . . 209
7.1 Types of Photoresists . . . . . . . . . . . . . . . . . . . 211
7.2 Theory of Mechanism . . . . . . . . . . . . . . . . . . 211
7.3 Hologram Nonlinearities . . . . . . . . . . . . . . . . . 213
7.4 Diffraction Efficiency and Signal-to-Noise Ratio . . . . . . . 215
7.5 Shipley AZ-1350 Photoresist Characteristics . . . . . . . . . 217
7.5.1 Shipley AZ-1350 Material Nonlinearity Considerations . 218
7.5.2 Shipley AZ-1350 Resolution Capability . . . . . . . . 220
7.5.3 Shipley AZ-1350 Relief Phase Hologram Design Procedure 221
References . . . . . . . . . . . . . . . . . . . . . . . . . 226
8. Other Materials and Devices. By J. Bordogna and S. A. Keneman
(With l Figure) . . . . . . . . . . . . . . . . . . . . . . . 229
8.1 Magneto-Optic Films . . . . . . . . . . . . . . . . . . . 230
8.2 Metal Films . . . . . . . . . . . . . . . . . . . . . . . 231
8.3 Layered Devices with Photoconductor Write-In . . . . . . . 232
8.3.1 Ferroelectric-Photoconductor Devices . . . . . . . . . 232
8.3.2 Liquid-Crystal-Photoconductor Devices . . . . . . . . 235
8.3.3 Photoconductor-Pockel's Effect Devices . . . . . . . . 236
