Table Of ContentPOCT KPHCTAnnOB
ROST KRISTALLOV
GROWTH OF CRYSTALS
VOLUME 12
Growth of Crystals
Volume 12
Edited by
A. A. Chernov
Institute of Crystallography
Academy of Sciences of the USSR, Moscow
Translated by
J. E. S. Bradley
Senior Lecturer in Physics
University of London
@C ONSULTANTS BUREAU· NEW YORK AND LONDON
The Library of Congress cataloged the first volume of this title as follows:
Growth of crystals. v. [1)
New York, Consultants Bureau, 1958-
v. illus., diagrs. 28 cm.
Vols. 1,3 - constitute reports of 1st- Conference on Crystal
Growth, 1956 - v. 2 contains interim reports between the 1s t and
2nd Conference on Crystal Growth, Institute of Crystallography,
Academy of Sciences, USSR.
"Authorized translation from the Russian" (varies slightly)
Editors: 1958- A. V. Shubnikov and N. N. Shefta!.
I. Crystal-Growth. I. Shubnikov, Aleksei Vasil'evich, ed. II.
Sheftal', N. N., ed. III. Consultants Bureau Enterprises, inc., New
York, IV. Soveshchanie po rostu kristallov. V. Akademiia nauk
SSSR. Institut kristallografii.
QD92l.R633 548.5 58-1212
ISBN 978-1-4615-7118-6 ISBN 978-1-4615-7116-2 (eBook)
DOI 10.1007/978-1-4615-7116-2
The original Russian text, published for the Institute of Crystallography of the
Academy of Sciences of the USSR by Nauka Press in Moscow in 1977, has been
corrected by the editor for this edition.
© 1984 Consultants Bureau, New York
Softcover reprint of the hardcover 1st edition 1984
A Division of Plenum Publishing Corporation
233 Spring Street, New York, N.Y. 10013
All rights reserved
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
PREFACE
Volumes 11 and 12 contain the papers read at the Fourth All-Union Conference on Crystal
Growth in Tsakhkadzor, September 17-22, 1972; this volume contains papers on crystal growth
from melts, from low-temperature solutions, hydrothermal solutions, and hot solutions, and
also from the gas state, including processes involving reactions. In addition, there are papers
on crystal perfection in relation to conditions of formation and the effects of electric and mag-
netic fields on crystallization.
These papers reflect researches directed to the development and industrial production
of perfect crystals required for advanced techniques in solid-state physics and chemistry, as
well as for other purposes such as novel materials.
There are many different scientific and technical problems in producing large perfect
single crystals, and advances in this area made in the USSR and elsewhere are reflected in
the papers in both volumes. On the one hand, any particular defective structure in a crystal
originates from some mechanism and growth conditions; in particular, inclusions are trapped
on account of the physicochemical parameters of the melt, the surface processes, and the sta-
bility of the growth front under particular crystallization conditions. Further, impurity trap-
ping is decisively influenced by the surface kinetics, growth-front stability, composition and
structure of the boundary layer, any complexes present in the liquid, and (of course) the crys-
tallochemical relationships between the impurity and the crystal. Hydrodynamic flows and
related phenomena also have their effect, as well as fluctuations in independent external fac-
tors such as the temperature, which can influence the zoning. Internal stresses and disloca-
tions are discussed in many of the papers in Volume 12, and these are produced primarily by
temperature distribution in the crystal during growth and cooling. Further, any inhomogeneity
in the impurity distribution has a major influence on the dislocations.
The processes occurring in a crystal after formation also influence the defect structure;
examples are plastic strain, accumulation of dislocations at block boundaries, impurity re-
distribution, and the decomposition of solid solutions.
Close control of the crystallization mechanism and of the composition of the medium im-
pose very stringent specifications on the equipment, growth methods, and initial substances;
many of these problems are made worse by the use of high temperatures and the need for
high purity in the crystals. In particular, the papers in this volume discuss crucible ma-
terials and gas compositions during crystallization appropriate to particular conditions. A
related topic is the choice of sealing flux. All these aspects require careful analysis of the
available phase diagrams and the construction of new ones, as well as research on the sta-
bility of compounds and transport kinetics. It is extremely important to stabilize the growth
front, i.e., to stabilize the temperature pattern and to eliminate internal sources of tem-
perature or concentration fluctuation, e.g., convection in solutions and melts. The growth
front can also show self-excited oscillation.
v
vi PREFACE
The production of perfect crystals would be inconceivable without the analysis of defects
in crystals; an extensive section of Volume 12 deals with these aspects. An entire range of
methods has been used, including ones that provide information on defects at the elementary
level. Unfortunately, it is rarely possible to observe the formation of defects directly during
growth. This is an aspect that should receive close attention in the near future.
There is also a small section on crystallization in electric and magnetic fields, which
gives an overview of a very interesting area in which there are many problems whose solution,
even in principle, is not clear.
Volume 12 was prepared for publication by the team from the Institute of Crystallography,
Academy of Sciences of the USSR, and Erevan University that prepared Volume 11; we are in-
debted to all those for their efforts in producing these books.
A. A. Chernov
Kh. S. Bagdasarov
E. I. Givargizov
P. O. Sharkhatunyan
CONTENTS
RUSS.
PAGE PAGE
1. GROWTH FROM VAPOR
High-Temperature Chemical Transport: Experimental Methods
and Fundamental Aspects of Crystal Growth. E. Kaldis •. 3 5
Chern ical Crystallization of Diamond. B. V. Deryagin
and B. V. Spitsyn ..•.•• 0 •••••• 0 ••••••••••• 0 0 • 25 28
Crystal Growth from Melts in Combination with Partial Chemical
Transport. A. Rabenau and H. Rau ....•...•..••.••..•...•. 31 32
Growth of Tungsten Single Crystals from the Vapor State by Chemical
Transport Reaction. G. W. Weise and W. Richter .•............ 34 36
Growth of Gallium Phosphide Whiskers. S. I. Radautsan
and Yu. I. Maks imov •••••.••••..• 0 ••••••••••• 38 39
Growth and Transformation of SiC Whiskers. G. A. Bootsma,
W. F. Knippenberg, and G. Verspui •••.•••••••••.••...•..•. 42 44
Growth of Silicon Carbide Whiskers. V. S. Postnikov, S. A. Ammer,
K. S. Kutakov, V. N. Petrov, A. F. Tatarenkov,
and A. A. Shchetinin •..•......•.•••..••.••...•........ 51 54
The Influence of Annealing on Thin Films of f3-SiC. C. E. Ryan,
I. Berman, R. C. Marshall, and J. R. Littler •..••.•....•. 0 •••• 56 58
A Unique High-Temperature, High-Pressure Crystal Growth System
for Silicon Carbide. R. C. Marshall, J. R. Littler, C. E. Ryan,
I. Berman, and J. J. Hawley •.••.•.•.••...•.•.•••..••...• 61 64
Formation and Growth of SiC in Carbon Ion Bombardment of Silicon.
P. V. Pavlov, E. 1. Zorin, D. 1. TetePbaum, G. M. Ryzhkov,
and V. P. Lesnikov ..••.•....•..•..•••••••...•.••••... 67 70
II. GROWTH FROM SOLUTION AND HYDROTHERMAL SYNTHESIS
The Growth Mechanism of Synthetic Quartz. L. I. Tsinober,
V. E. Khadzhi, L. A. Gordienko, and L. T. Litvin .••••••.•.••..• 73 75
Chemical Crystallography and Hydrothermal Synthesis of Silicates
and Germanates: The Genetic Relationship between Ca and TR
Silicates. E. N. Belova, L. N. Dem 'yanets, V. V. ilyukhin,
B. A. Maksimov, and Yu. A. Kharitonov •••.•••••••..•..••.•. 85 87
Crystallization in Complex Silicate and Germanate Systems.
B. N. Litvin ..•••.••.••.•......•.•••.•.•....•.••.••. 90 92
vii
viii CONTENTS
Crystallization of Manganese Silicates in the Na20- MnO- Si02- H20
System with MnO;Si02 > 1. B. N. Litvin, V. S. Fonin,
D. Yu. Pushcharovskii, and E. A. Pobedimskaya .......•..•...• 94 96
Adsorption in Solution of Cadmium Ions on {100} and {111} of NaCl.
R. Boistelle, M. Mathieu, and B. Simon •.••..•.•...••...•... 99 100
Fluctuations and Anomalous Temperature Dependence in the Growth Rates
of KAI(S04)2 • 12H20 and KN03• A. A. Chernov, V. F. Parvov,
S. M. Eskin, and V. V. Sipyagin• .•.....•......•.......•... 103 103
Fluctuations in Crystal Shape. I. V. Melikhov and B. D. Nebylitsyn ..... . 108 108
Layers of Foreign structure on a Growing Sphalerite Crystal.
A. A. Shternberg ........•.••.•..........•........... 116 115
Gel Growth of Lead Sulfate Single Crystals. A. R. Patel and H. L. Bhat .. . 122 120
Theory of Diffusion Methods of Growing Crystals. G. K. Kirov ........ . 126 124
Effects of Growth Conditions on the Structure and Shape of KDP
Crystals. N. S. stepanova, V. N. Portnoy, S. S. Fridman,
Yu. M. Fishman, and A. V. Belyustin ...................... . 131 129
Trends in Crystal Splitting during Growth. T. P. UI 'yanova,
Yu. O. Pun in, and T. G. Petrov .•......................... 135 133
ill. GROWTH FROM SOLUTION IN MELTS
Recent Development in Crystal Growth from High-Temperature
Solutions. J. W. Nielsen .........•..•.................. 143 139
The Peak in the Fusibility Curve for Srl-xGdxF2+X Solid Solutions.
K. B. Seiranyan, R. 0. Sharkhatunyan, and B. p. Sobolev ......... . 155 150
Crystallization of Phlogopite KMg3[AlSi30101F2 from Melts.
I. N. Anikin .........................•.............. 158 152
Growth of Single Crystals of Solid Solutions with the Sillenite
Structure. A. A. Maier, L. P. Fomchenkov, V. A. Lomonov,
and N. G. Gorashchenko ..•.••.....•...•..........•...•. 168 162
Epitaxial Growth of ZnSnAs2 and ZnSnP2 Films. I. Bert6ti ........... . 174 167
Shape Changes in Growing Diamonds. V. A. Laptev
and G. V. Khatelishvili .........•.................... 181 173
Crystallization Conditions for Various Crystallographic Forms
of Diamond. D. F. Korolev ..•...•..•...•........•.... 185 176
IV. GROWTH FROM MELTS
Synthesis of Optical-Grade Refractory Crystals.
Kh. S. Bagdasarov .•...•..•...•...•....•..•.•....•. 189 179
Production of Perfect Corundum Single Crystals.
Kh. S. Bagdasarov,E.R. Dobrovinskaya, V. V. Pishchik,
M. M. Chernik, and Yu. Yu. Kovalev •........•..•... 204 195
Advances in the Production of Oxide Crystals. F. R. Charvat ....... . 210 202
Production and Examination of Barium-Sodium Niobate Single
Crystals. Part 1. E. V. Zharikov, Yu. S. Kuz'minov,
V. V. Osiko, and T. M. Sarzhevskaya .....••.•••..•.....•• 225 219
Production and Examination of Barium-Sodium Niobate Single
Crystals. Part 2. E. V. Zharikov, V. F. Kalabukhova,
Yu. S. Kuz'minov, and V. V. Osiko •.•.••......••....••... 231 224
Czochralski Growth of Single Crystals Using High-Pressure
Techniques. J. F. Wenckus •..•.•.•.........•.•..•..•• 237 229
CONTENTS ix
Growth, Activation, and Optical Characteristics of Calcium
and Lead Fluorophosphate and Fluorovanadate Single
Crystals. A. M. Korovkin, Yu. M. Lagunenko,
A. M. Morozov, and P. P. Feofilov ..•.•....•.•••..•..•.. 242 234
Automatic Crystal Growth: Measurement of Some Important
Growth Parameters. W. Uelhoff and K. J. Gartner• .•.•....•.. 246 238
Banding in Co- 8 at. % Fe Crystals. A. Modrzejewski .••........•. 252 243
Production of Profiled Germanium Single Crystals by Stepanov's
Method. P. I. Antonov and A. V. stepanov. .....•..••....... 255 246
Crystallization of SnSb. N. V. Kazitsyn and V. "A. Yurkov •.......... 261 252
v. IMPERFECTIONS AND CRYSTAL GROWTH
Production of Perfect Semiconductor Single Crystals
by Crystallization from Melts. M. G. Mil'vidskii
and V. B. Osvenskii ........•.....•...•......•....•. 267 257
X-Ray Diffraction Topography of Growth Defects in Crystals.
E. P. Kostyukova, V. G. Lyuttsau, and Yu. M. Fishman •........ 278 269
Origin of the Dislocation structure in an Alkali Halide Single
Crystal Grown from the Melt. V. I. Goriletskii,
A. D. Podlesnaya, and L. G. Eidel'man ...•..•.•.....•....• 292 284
Thermoelastic stresses and Dislocation Structures of Semiconductor
Crystals Grown by Czochralski's Method.
S. S. Vakhrameev, M. G. Mil'vidskii, V. B. Osvenskii,
V. A. Smirnov, and Yu. F. Shchelkin .••.••..•.••...•..... 296 287
studies of Dendrites Grown Utilizing Intersecting Twin Planes.
H. M. Liaw and J. W. Faust, Jr. • ..••.••.•••.••....•..• 302 293
Lonsdaleite Inclusions as a Possible Cause of Yellow-Green
Fluorescence in Diamonds. M. O. Kliya and V. A. Milyuvene 308 298
X-Ray Diffraction Topography of Dislocation structures and Block
Boundaries in Tungsten Single Crystals. E. F. Sidokhin,
L. P. Chupyatova, L. M. Utevskii, and M. V. Pikunov .•....•..• 316 307
Growth Conditions, Structure, and Magnetic Parameters of Ticonal
Single Crystals. V. V. Sergeev and R. Ya. Larichkina .•.•.•... 320 310
structures of Thin Films of Rare-Earth Metals. N. T. Gladkikh,
M. N. Naboka, and M. A. Chekarev .•...••.•••.••.•.••••• 326 316
VI. GROWTH IN ELECTRIC AND MAGNETIC FIELDS
Effects of Static Magnetic Fields and Alternating Electromagnetic Fields
on Crystallization from Aqueous Solution. C. Barta, L. M. Belyaev,
G. F. Dobrzhanskii, J. Zemlicka, O. L. Kreinin,
and M. P. Shaskol'skaya .••.•..••.......••.••.•.•.... 333 322
Field-Induced Instability in a Planar Crystallization Front
in Amorphous Selenium. I. E. Bolotov
and L. I. Komarova. .....•..••.....•..••..........•. 336 325
Crystallization-Condition Effects on the Antimony Sulfide Distribution
in an SbSI Crystal. V. D. Spitsyna, V. A. Lyakhovitskaya,
L. M. Belyaev, and S. F. Chistov• •••••..••.•.•••..•.••.. 340 328
The Effects of Electric Fields on the Epitaxial Growth
of Gallium Arsenide. O. E. Korobov, V. N. Maslov,
and V. V. Nechaev ...•....••.......•.••••••.•...••. 344 332
x CONTENTS
Effects of an Electric Field during Growth on the Parameters of Bi
and PbS Single-Crystal Films. M. I. Kozlovskii,
V. I. Burchakova, and I. I. Melent'ev •...••....••....••.. 350 337
PART I
GROWllI FROM VAPOR
