Semiconducting II–VI, IV–VI, and V–VI Compounds

260 Pages·1969·6.986 MB·English

by  Professor Nikolai Khrisanfovich Abrikosov, V. F. Bankina, L. V. Poretskaya, L. E. Shelimova, E. V. Skudnova (auth.)

SEMICONDUCTING
11-VI, IV-VI, V-VI
anct
COMPOUNDS
MONOGRAPHS IN SEMICONDUCTOR PHYSICS
Valurne 1:
Heavily Doped Semiconductors
by Viktar I. Fistul'
Valurne2:
Liquid Semiconductors
by V. M. Glazav, S. N. Chizhevskaya, and N. N. Glagaleva
Valurne 3:
Semiconducting II-VI, IV-VI, and V-VI Compounds
by N. Kh. Abrikasav, V. F. Bankina, L. V. Paretskaya,
L. E. Shelirnava, and E. V. Skudnav.a
In preparation:
Switching in Semiconductor Diodes
by Yu. R. Nasav
SEMICONDUCTING
11-VI, IV-VI, V-VI
anct
COMPOUNDS
N. Kh. Abrikosov, V. F. Bankina,
L. V. Poretskaya, L. E. Shelimova,
and
E. V. Skudnova
A. A. Baikov Institute of Metallurgy
Academy of Seiences of the USSR
Translated from Russian by
Albin Tybulewicz
Editor, Soviet Physics-Semiconductors
~ Springer Science+B usiness Media, LLC 1969
Professor Nikolai Khrisanfovich Abrikosov, who is Director of Laboratories at
the A. A. Baikov Institute of Metallurgy, has been engaged in research on rare
earth meta! alloys since 1936 and work on semiconducting materials since 1950.
He is a member of the Scientific Council on the Chemistry and Tcchnology of
Semiconductors of the Academy of Seiences of the USSR, as weil as a member
of the scientific boards of the A. A. Baikov Institute of Metallurgy, the N. S.
Kurnakov Institute of General and Inorganic Chemistry, the State Scientific
Research Institute for Rare and Less Common Metals, and the Moscow Institute
for Steel and Alloys.
Library of Congress Catalog Card Number 69-12527
The original Russian text, published by Nauka Press in Moscow in 1967, has been
corrected and updated by the authors for the present edition.
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POLUPROVODNIKOVYE SOEDINENIYA, IKH POLUCHENIE I SVOISTA
© 1969 Springer Science+ Business MediaNe w York
Originally published by Plenum Press in 1969
Softcover reprint of the hardcover 1st edition 1969
All rights reserved
No part of this publication may be reproduced in any form
without written permission from the publisher.
ISBN 978-1-4899-6185-3 ISBN 978-1-4899-6373-4 (eBook)
DOI 10.1007/978-1-4899-6373-4
PREFACE
This monograph deals with the semiconducting compounds
formed from elements of groups II, IV, or V and sulfur, selenium,
or tellurium. These compounds are attracting increasing atten
tion because they have interesting physical properties. The mono
graph describes the crystal structures of these compounds, and
presents the published data on their polymorphic transitions, in
cluding transitions observed at high pressures. The problems of
chemical binding are discussed.
In the sections dealing with the phase diagrams, special at
tention is paid to the departures of semiconducting compounds
from stoichiometry and investigation methods are described for
the precise determination of the composition of these compounds.
Analysis of the published material has shown that the character
istic feature of semiconducting compounds with a predominantly
covalent type of chemical binding is a departure from stoichiom
etry. This departure is sometimes very small, representing
hundredths and thousandths of 1%, but it strongly affects the physi
cal properties of these compounds.
The composition of these compounds does not remain con
stant, but is affected by external conditions: temperature, pres
sure, and the concentration of the third component. Because of
this, the phase diagrams of the "temperature-composition" type
are insufficient for many of these systems. It is also necessary
to know the equilibrium phase diagrams of the "pressure-tempera
ture-composition" (P-T-X) type. Knowledge of the P-T-X dia
grams is particularly important in the synthesis of semiconduct
ing compounds having high vapor pressures. The monograph in
cludes all the published P-·T-X diagrams for the compounds dis
cussed and describes a method for plotting these diagrams. Inves-
V
vi PREFACE
tigations of the P-T-X diagrams of semiconducting compounds
are of relatively recent origin and it is hoped that the review of
these investigations will attract more attention of research workers
to such diagrams. The more important physicochemical proper
ties of the compounds are also given in the monograph. Unfortu
nately, the published material is insufficient for a full description
of the thermodynamic properties of many of the compounds con
sidered. More work should be done on these properlies.
The main physical properties of the compounds are given:
the forbidden band width, the carrier mobility, the effective
masses of carriers, the electrical conductivity, and the thermo
electric power.
The monograph consists of three chapters. The first deals
with chalcogenides of elements in group II: zinc, cadmium, and
mercury. The second discusses semiconducting compounds of
elements in group IV: germanium, tin, and lead. These com
pounds are used in some photoelectric and thermoelectric devices.
And the third describes investigations of compounds of elements of
group V: arsenic, antimony, and bismuth. Allthese chalcogenides,
as well as solid solutions based on them, are of great importance
because of their application as thermoelectric materials in low
temperature thermoelectric converters and cooling devices.
The monograph does not cover chalcogenides of elements in
group III (aluminum, gallium, and indium), since a book by Z. S.
Medvedeva dealing with these compounds is being published simul
taneously with the present monograph. We have also excluded the
data on semiconducting glasses because these materials deserve
a separate book.
The monograph includes the published data (right up to the
second half of 1966) on the crystal structure, physicochemical
properties, and phase diagrams of important semiconducting com
pounds which are used in various bl'anches of engineering. Some
of these compounds have been investigated by the authors of the
present monograph.
The authors will be grateful for any comments from readers.
N. Kh. Abrikosov
CONTENTS
CHAPTER I. AllE VI Compounds
§ 1. C rystal structure. • • • • • • • • , • • • • • • • . • . 1
§ 2. Crystallographic Polarity . • • • . • . • • . • • • • 6
§ 3. Chemical Binding of All B VI Compounds • • • • • 8
§4. Phase Diagrams of All-E VI Binary Systems • 11
§ 5. Thermodynamic Properties • • • • • • • • • • • • • 23
§ 6. Physical Properties • • • • • • • . • • • • • . • . • • 26
§ 7. Preparation Methods • • • • • • • • . . • • . • • • • 33
§ 8. Systems Based on AllE VI Compounds • • • • • • 43
Literature Cited. • • • • • . • • • . • • • • • • • • • • • • • 59
CHAPTER ll. AJVB VI Compounds
§ 1. Phase Diagrams of Al V-B VI Binary Systems • 65
§2. Crystal structure and Chemical Binding..... 74
§3. Departures from Stoichiometry • • • • . . • • • • 82
§4. Properties of AIVB VI Compounds ••••••• , • 103
§ 5. Preparation Methods • • • • • • • • • • • • • . • • • 116
§6. Chalc~enides of AIVBi'!, A~VB{'I, and
AlVB4 Type. • • • • • • • • • • • • • • • . • • . • • • 122
§ 7. Systems Based on AlVB VI Compounds. . • . • • 127
Literature Cited. • • • • . . . • • • . . . • • • • • • • • • • 151
CHAPTER III. AYBi'l Compounds
§ 1. Phase Diagrams of A V-B VI Binary Systems • 159
§ 2. Crystal Structure and Chemical Binding. • . . • 175
§3. Departures from Stoichiometry of Compounds
with Tetradymite structure • • • • • . • • • • • • • 183
§4. Properties of AYBi'l Compounds • • • • • • • • • 186
§ 5. Preparation Methods • • • • • • • • • • • • • • • • • 199
vii
viii CONTENTS
§6. Systems BasedonA;'B~ Compounds • • • • • • • 201
§ 7. AIVB VI-A;'Bi'l Systems. • • • • . . • • • • . • • • 23 0
Literature Cited. • • • • . • . . • • • . • • • • • • . • • . • 240
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
CHAPTER I
A11 COMPOUNDS
BVI
1. CRYSTAL STRUCTURE
Almost all compounds of the All B VI type crystallize in such
a manner that each atom of one element is located at the center of
a regular tetrahedron, the apices of which are occupied by atoms
of the other element. Two possible structures can be formed from
such tetrahedra: the sphalerite (cubic type) and the wurtzite (hex
agonal) type. The sphalerite structure is very similar to the struc
ture of diamond, but it differs from the latter by the alternation of
atoms of two different elements. In the sphalerite structure, the
atoms of one elementare located at the sites of an fcc lattice,
while the atoms of the second element occupy centers of four (out
of a total of eight) small cubes (Fig. 1). The space group is F43m
(Tj ) . The coordination number is 4 for atoms of both elements.
Figure 2 shows the wurtzite structure. Its space group is
P63mc (C~v). Again the coordination number is 4 for atoms of
both elements.
The crystal structures of the AIIB VI-type compounds are
listed in Table 1 [1-15].
The sphalerite and the wurtzite structures are very similar.
This similarity is due to the same number of atoms in the first
and second coordination spheres. In both structures, each atom
in the second coordination sphere is surrounded by 12 atoms of
the same element; there are only certain differences in the distri
bution of the atoms, which are due to the different paclting in cubic
and hexagonal crystals. The basic difference between the two
1