Semiconducting Lead Chalcogenides

387 Pages·1970·10.93 MB·English

by  Yu. I. Ravich, B. A. Efimova, I. A. Smirnov (auth.), L. S. Stil’bans (eds.)

SEMICONDUCTING
LEAD CHALCOGENIDES
MONOGRAPHS IN SEMICONDUCTOR PHYSICS
1969
Volume 1
HEAVilY DOPED SEMICONDUCTORS
by Viktor I. Fistul'
Volume2
LIQUID SEMICONDUCTORS
by V. M. G/azov, S. N. Chizhevskaya, and N. N. G/agoleva
Volume3
SEMICONDUCTING II-VI, IV-VI, and V-VI COMPOUNDS
by N. Kh. Abrikosov, V. F. Bankina, L. V. Poretskaya,
L. E. Shelimova, and E. V. Skudnova
Volume4
SWITCHING IN SEMICONDUCTOR DIODES
by Yu. R. Nosov
1970
Volume 5
SEMICONDUCTING lEAD CHAlCOGENIDES
by Yu. I. Ravich, B. A. Efimova, and I. A. Smirnov
In preparation
ORGANIC SEMICONDUCTORS AND BIOPOlY MERS
by L. I. Boguslavskii and A. V. Vannikov
SEMICONDUCTING
LEAD CHALCOGENIDES
Yu. 1. Ravich, B. A. Efimova, al'ld 1. A. Smirnov
Institute of Semiconductors
Academy of Sciences of the USSR, Leningrad
Edited by L. S. Stil'bans
Institute of Semiconductors
Academy of Sciences of the USSR, Leningrad
Translated from Russian by Albin Tybulewicz
Editor, Soviet Physics-Semiconductors
SPRINGER SCIENCE+BUSINESS MEDIA, LLC 1970
Yurii /saakovich Ravich was born in 1937 in the city of Pskov.ln 1959 he was graduated
from the Physics Department of the Leningrad State University. He then joined the Insti-
tute of Semiconductors of the Academy of Sciences of the USSR, where he investigated
the theory of photoelectric phenomena in semiconductors. At present, Ravich is a senior
member of the scientific staff of the Institute. He is working on the band structura and
carrier scattering mechanisms in semiconducting materials suitable for thermoelectric
converters. Among his publications is a book on the "Photomagnetic Effect in Semicon-
ductors and lts Applications."
Bel/a Anatol'evna Efimova was born in 1932 in Volgograd. After graduation from the Ural
State University in 1954, she joined the Institute of Semiconductors. At present she is a
senior member of the scientific staff of the Institute and is working on thermoelectric
properties of semiconducting materials.
/gor' Aleksandrovich Smirnov was born in 1932 in Leningrad. In 1955 he was graduated
from the M. 1. Kalinin Leningrad Polytechnical Institute and promptly joined the Institute
of Semiconductors, where he is now the head of the Laboratory for Thermal Phenomena.
His major field of study is the thermal properties of solids. In 1964 Smirnov was awarded
the A. F. loffe Prize for Solid State Physics.
The original Russian text, published by Nauka Press in Moscow in 1968 as a pari of a
series on "Physics of Semiconductors and Semiconducting Devices," has been corrected
by the authors for this edition. The English translation is published under an agreement
with Mezhdunarodnaya Kniga, the Soviet book export agency.
Paeutt /Opuu HcaaKoeu•t,
EfjJuMoea BeA/la AHamoAbeBHa,
CMupHoa Hzopb AlleKcaHi)poBll'l
MrTOJ\bi HCCJif'J\OBaHllH noJiynpoBO)UIHKOB
B npHMeHeHlUi K X3JlbKOI'eHH}l;a:\1 CBHIC~a
PbTe, PbSe H PbS
METODY ISSLEDOVANIYA POLUPROVODNIKOV
V PRIMENENII K KHAL'KOGENIDAM SVINTSA
PbTe, PbSe 1 PbS
Library of Congress Catalog Gard Number 77-107542
SBN 306-30426-0
ISBN 978-1-4684-8609-4 ISBN 978-1-4684-8607-0 (eBook)
DOI 10.1007/978-1-4684-8607-0
© 1970 Springer Science+Business Media New York
Originally published by Plenum Press, New York in 1970
Softcover reprint of the hardcover 1s t edition 1970
Ali rights reserved
No part of this pub/ication may be reproduced in any form
without written permission from the pub/isher
PREFACE TO THE
AMERICAN EDITION
Many new papers on lead chalcogenides have been published
in the two years since the completion of the manuscript of the
Russian edition of this book. A considerable amount of new in-
formation has become available on the mechanisms of carrier
scattering. Higher values of the thermoelectric figure of merit
have been reported and more accurate phYSical parameters of lead
chalcogenides have been obtained. This new material required a
revision or a fuller treatment of some of the topics.
In the preparation of the American edition we have not at-
tempted to give references to all the new work but we have selec-
ted only those papers which alter substantially or give important
new information on subjects dealt with in the Russian edition. We
hope that the inclusion of the new material will make the book more
useful and we are grateful to Plenum Publishing Corporation for
the opportunity to make corrections and additions in the American
edition.
Yu. I. Ravich
B. A. Efimova
I. A. Smirnov
v
EDITOR'S PREFACE
The last decade has seen radical changes in our understand-
ing of the physical properties of semiconductors. It has been es-
tablished that the energy spectrum of electrons is much more
complex than had originally been predicted: in many cases, there
are several energy bands with different parameters. It has been
found that the effective carrier mass, which had been assumed to
be constant for a given material, depends on the carrier energy,
temperature, pressure, and even the nature and number of de-
fects. Our understanding of the mechanism of the motion and scat-
tering of carriers, recombination mechanisms, and interaction with
electromagnetic radiation has also changed. New applications of
semiconducting materials have been discovered and old ones have
been extended; these include high-power devices, devices sensitive
to infrared radiation, and lasers. The visible evidence of the pro-
gress is in the form of hundreds of publications, some of which re-
port extremely refined and comprehensive investigations of semi-
conducting materials.
A scientist concerned with investigations or applications of
semiconducting materials or devices cannot ignore these publica-
tions because of the possibility of repeating work already done or
of committing serious error.s. On the other hand, a beginner would
require years to obtain a thorough understanding of the literature
in his own narrow subject, and in many cases this process would
be like the chase of a tortoise by Achilles in the paradox of Zeno
of Elea (495-435 B.C'>.* For this reason, we should always wel-
come the appearance of monographs, such as the present one,
which summarize the results of decades of inve~tigations of semi-
·See, for example, E. Kasner and J. Newman, Mathematics and the Imagination,
Simon and Schuster, New York (1950), pp. 37 -38, 57 -58.
vii
viii EDITOR'S PREFACE
conducting materials that are scientically and technologically im-
portant. Such monographs help young scientists throughout the
world to reach a certain level of understanding of their subject
much more easily.
The importance of the present monograph is greatly ~n­
hanced by the fact that the available textbooks and monographs do
not include the recent data on semiconducting materials, and do not
describe the latest theoretical achievements and the new methods
for analyzing the experimental data. This gap is filled by the the-
oretical briefs which preface each chapter of the present book.
This treatment extends the monograph's usefulness to a very wide
range of readers, including scientists, engineers, postgraduate
and undergraduate students.
The monograph describes in detail the optical properties of
semiconductors, phenomena in quantizing magnetic fields, the meth-
ods of calculating effective masses (the k.p perturbation theory),
methods for calculating the parabolicity of energy bands (a simpli-
fied variant of the Kane theory), as well as group-theory methods
for analyzing the influence of the symmetry of a crystal on the
energy spectrum of electrons.
The emphasis is on the presentation of the results of investi-
gations of the physical (optical, electrical, photoelectric, thermal,
thermoelectric, and magnetic) properties of lead chalcogenides
and on the structure of their energy bands, carrier scattering mech-
anisms, and phonon spectra, which can be deduced from the ex-
perimental data and theoretical calculations. The physicochemical
properties of lead chalcogenides are described, as well as methods
of synthesizing these materials and growing their single crystals.
The applications of these materials are also briefly reviewed.
Certain phenomena, which are interesting from the point of view
of the physics of semiconductors as a whole, were observed most
clearly - and for the first time - in lead chalcogenides. Such phe-
nomena include, for example, the strong temperature dependence
of the effective mass and the large relativistic corrections which
are necessary in the energy band structure calculations. Lead
chalcogenides were found to be convenient materials in the first
observations of the de Haas-van Alphen effect, helicon waves, and
quantum oscillations of the absorption of ultrasound.
EDITOR'S PREFACE ix
The book is written by leading specialists in theoretical and
experimental investigations of semiconductors, and, therefore, it
is not simply a compilation of the available data but a critical and
generalized interpretation of them.
B. A. Efimova contributed §§1.1-1.4 and 7.1; 1. A. Smirnov
was responsible for §§1.5 and 4.2; the remainder of the book was
written by Yu. I. Ravich.
L. S. Stil'bans
CONTENTS
Notation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
CHAPTER I. PHYSICOCHEMICAL PROPERTIES. . . . . . . 13
§1.1. Crystal Structure and the Nature of Chemical
Binding. . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
§1.2. Preparation Methods. . . . . . . . . . . . . . . . . . . 15
A. Preparation of Polycrystalline Materials. . 16
B. Methods for Single-Crystal Growth. . . . . . 21
§1.3. Phase Diagrams. . . . . . . . . . . . . . . . . . . . . . 26
§1.4. Control of the Stoichiometry and the Doping
Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
§1.5. Diffusion........... . . . . . . . . . . . . . . .. 36
A. Diffusion in Undoped Single Crystals. . . . . 39
B. Diffusion in Doped Single Crystals. . . . . . . 40
C. Diffusion in Polycrystalline Samples . . . . 40
CHAPTER II. OPTICAL AND PHOTOELECTRIC
PROPERTIES. . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
§2.1. Absorption and Reflection of Light. . . . . . . . . . 43
A. Optical Parameters and Measurement
Methods . . . . . . . . . . . . . . . . . . . . . . . . 43
B. Microscopic Processes of Interaction
between Light and a Semiconductor. . . . . . 48
C. Fundamental Absorption Edge. . . . • . . . . . 51
D. Dispersion and Absorption at Long
Wavelengths . . . . . . . . . . . . . . . . . . . . . 56
E. Dispersion a.nd Absorption at Short
Wavelengths . • . . . . . . . . . . . . . . . . . . . 63
xi