CHAPTER 5

The Effects of Hydrostatic Pressure on the Properties

of 111-V Semiconductors
Robert W . Keyes

I.INTRODUCTION . . . . . . . . . . . . . . . . 321
11.EFFECTOF PRESSURE ON ENERGY BANDS . . . . . . . . 328
111.OPTICAL ABSORPTION SPECTRUM . . . . . . . . . . . 329
IV. ELECTROLUMINESCENCE . . . . . . . . . . . . . 33 1
V. ELECTRICAL CONDUCTIVITY . . . . . . . . . . . . 332
VI .OTHERELECTRICAL PROPERTIES . . . . . . . . . . . 336
1. Piezoresistance . . . . . . . . . . . . . . . 336
2. Hall Effect and Thermoelectric Power of GaSb . . . . . . 337
3. Microwaae Oscillations . . . . . . . . . . . . 338
VII. PHASETRANSITIONS. . . . . . . . . . . . . . 338
VIII. ELASTICPROPERTIES . . . . . . . . . . . . . . 341

I. Introduction
Many years ago P. W. Bridgman inaugurated the study of the electrical
properties of semiconductors under high hydrostatic pressures. Bridgman’s
work pre-dated the development of modern semiconductor technology and
science, and only a few semiconducting materials of relatively low purity
were available to him. Nevertheless, significant results were achieved, and
the high pressure laboratory of Harvard University was established as a
leader in the investigation of semiconductors at high pressure. This leadership
has been maintained by the work of W. Paul and his students.
The more recent era of highly developed semiconductor technology and
science has made a large number of semiconducting materials available to
the physicist and has made possible intensive study of the effect of pressure
on the properties of semiconductors. Many additional high pressure labora-
tories have come into existence and made notable contributions to this field
of study. Two laboratories have stood out, however. That of Harvard Uni-
versity, as already mentioned, has produced a continuing series of important
results under the leadership of Professor Paul. Professor Drickamer’s
laboratory at the University of Illinois has extended the range of a variety
of physical measurements to nearly hydrostatic pressures of a few hundred
thousand kg/crn2. The high pressure investigations have played an important
327
328 ROBERT W. KEYES

role in the growth of semiconductor science, and, in particular, in the

formulation of models of the band structures of the 111-V semiconducting
compounds. General features of the picture that has emerged will be de-
scribed in the next part. Succeeding parts will describe the changes in various
electronic properties which result from the changes in the energy bands with
pressure. Finally, the phase transitions which have been found in many
diamond and zinc-blende semiconductors at very high pressures will be
described and the last part will treat elastic properties.

11. Effect of Pressure on Energy Bands

Many measurements of the changes of the electronic properties of the 111-V
semiconductors with pressure have been carried out since these compounds
became prominent in the semiconductor field in the early 1950’s. It has been
found that the pressure variation of electronic properties can be understood
as straightforward consequences of the change in the electronic band
structure of the compounds with pressure. The changes in electronic band
structure have, of course, been derived by interpretation of the pressure
dependence of electronic properties. The picture of the band structures of the
111-V semiconductors and the way in which they are affected by pressure
which will be used in the present work has been largely derived by W. Paul
and H. Drickamer and their collaborators from the work in their laboratories
at Harvard University and the University of I l l i n ~ i s . ’ ~ ~
The maximum energy of the valence band of the 111-V semiconductors
occurs at the point [OOO] of k space.4 This maximum has a complex structure
which exhibits large changes when the cubic symmetry of the crystal is
destroyed by shear strains. The complex structure need not concern us here,
however, since hydrostatic pressure does not destroy the cubic symmetry,
and experiments have shown that pressure produces very little effect on the
properties of the valence band.
The lowest energy of the conduction band may occur at three different
points in the k space.4 These are (apart from a factor with dimensions of
inverse length) :
[OOO], the same point as the maximum of the valence band.
[OOl], apoint on thefourfoldaxis.Therearesixequivalent pointsofthis type.
[ l l l l , a point on the threefold axis at the Brillouin zone boundary.
There are four equivalent points of this type.
’ A. L. Edwards, T. E. Slykhouse, and H. G. Drickamer, J . Phys. Chem. Solids 11, 140 (1959).
W. Paul, J . Appl. Phys. 32,2082 (1961).
W. Paul and D. M. Warschauer, in “Solids Under Pressure” (W. Paul and D. M. Warschauer,
eds.), p. 179. McGraw-Hill, New York, 1963.
For a review of the band structures of the Ill-V compounds, see H. Ehrenreich, J . Appl. Phgs.
32, 2155 (1961).
 5 . EFFECTS OF HYDROSTATIC PRESSURE ON 111-vSEMICONDUCTORS 329

The energy differences between the various conduction band extrema are
frequently small in 111-Vsemiconductors, so that the effects of extrema other
than the lowest may appear in physical phenomena. Many of the most
striking high pressure effects are produced by proximity in energy of two
kinds of band extrema.
Work of the laboratories of Paul and Drickamer has shown that most of
the effects of pressure on the electronic properties of the 111-Vsemiconductors
can be explained by a model in which pressure changes the energies of the
three types of conduction band extrema relative to the valence band and
to one another without affecting the nature of the extremum.'--3 The same

TABLE I
PRESSURE DEPENDENCE
OF THE ENERGY
GAP BETWEEN THE VALENCEBAND A N D
THE VARIOUSCONDUCTION
BANDMINIMA'

Conduction band dE,ldP in

minimum 10- 6eV/(kg/cm2)

[0001 + 12
[1111 + 5
[loo1 - 1.5

After Zallen."

work has further established that the rate of change of the energies of the
various extrema is about the same for all of the diamond and zinc-blende
type semiconductors. The rates of change of the energy of the three types of
conduction band minima with respect to the valence band are shown in
Table I. The effects of pressure on the electronic properties of all of the 111-V
semiconductors can be almost completely understood in terms of the simple
model which is quantitatively characterized by Table I.

111. Optical Absorption Spectrum

The most important feature of the optical absorption spectrum of a semi-
conductor, and the only one which has been very extensively studied, is the
intrinsic absorption edge, the energy at which absorption of light by excitation
of electrons from the valence band to the conduction band sets in. The
absorption constant increases very rapidly with increasing photon energy
in the vicinity of the energy gap of the semiconductor. In the simplest model
case, the absorption spectrum shifts in energy with the gap as the pressure
is varied. Then the change in absorption spectrum with pressure can be
330 ROBERT W . KEYES

immediately inferred from the facts presented in the foregoing section if the
location of the conduction band minimum in k space is known.
The simplest behavior, a shift of the absorption spectrum with pressure
without change in shape, is not always found, h ~ w e v e r . ’ , ~If , the
~ shape
changes, more complex and less general interpretations, which have been
discussed at some length for the example of germanium, are r e q ~ i r e d . ~ , ~ ~ ~
These more complicated cases usually result from the participation of more
than one conduction band minimum in the absorption process. Nevertheless,
a useful way to summarize measurements of the effect of pressure on optical
absorption is to plot the photon energy at which the absorption constant
has a fixed value versus the pressure.
A plot of the photon energy at which the absorption constant of InP is
’
30 cm- as a function of pressure is given in Fig. 1, for example. It closely
resembles a plot of the energy gap in InP against pressure. The minimum

1.3 -

0 20 40 60 I 0
P (lo3 kg/cm2)
FIG.1. The pressure dependence of the absorption edge of InP, defined as the energy at which
’.
the absorption constant is 30 cm- (After Edwards and Drickamer.’) At low pressures the [OOO]
conduction band minimum is lowest and at high pressures the [OOI] is lowest.

energy of the conduction band is at the [OOO] point of k space at low pressure.
The energy gap increases with increasing pressure, as explained in Part 11.
Since the energy of the [loo] minimum decreases with pressure, a certain
H. Y. Fan, M. L. Shepherd, and W. G. Spitzer, in “Photoconductivity Conference” (R. G.
Breckenridge, B. R. Russell, and E. E. Hahn, eds.). Wiley, New York, 1956.
D. M. Warschauer and W. Paul, quoted by Professor Brooks in “Photoconductivity
Conference” (R. G . Breckenridge, B. R. Russell, and E. E. Hahn, eds.), p. 201. Wiley, New York,
1956.
’ W. Paul and D. M. Warschauer, J . Phys. Chem. Solids 5, 89 (1958).
L. J. Neuringer, Phys. Rev. 113, 1495 (1959).
 5. EFFECTS OF HYDROSTATIC PRESSURE ON 111-V SEMICONDUCTORS 331

pressure exists at which the [loo] minimum becomes the lower one. The
energy gap decreases with increasing pressure above this transition pressure.
Of course, the shape of the absorption spectrum varies in a complicated way
in the transition region. The use of plots such as that of Fig. 1 to investigate
the changes of energy gaps to very high pressures has been extensively ex-
ploited by Edwards, Drickamer, and Slykhouse. 1,9
In addition to InP, the pressure dependence of the optical energy gaps of
A1Sb,9 GaP,',''"' GaAs,' GaSb,'393'2InSb,I2" and InAs'','2 has been
measured. The measurements of Zallen and Paul on GaP are of especial
interest in that several features of the optical absorption and reflectivity
spectra which are not close to the gap in energy were also studied."." These
other features apparently represent transitions involving band edges other
than those which bound the gap. The study of many such transitions illus-
trates a potential for determining the pressure variation of a large part of the
energy band structure rather than just that part which is close to the gap.

IV. Electroluminescence
The effects of pressure on the electroluminescent spectrum and on the
optical absorption spectrum are closely related. The recombination of an
electron and a hole, the process which produces luminescence, is the inverse
of the absorption process, in which a photon creates an electron and a hole.
Photons resulting from recombination of an electron in the conduction
band with a hole in the valence band have an energy close to the gap energy.
This radiation near the gap energy constitutes the main emission in 111-V
semiconductors with [OOO] conduction band minima, and can be very efficient.
Injection lasers operating in the main line can be made by passing large
currents through a p-n junction incorporated in a Fabry-Perot laser struc-
ture.
The discovery of efficient p-n junction electroluminescence and of injection
lasing in gallium arsenide stimulated several investigations of the effect
of pressure on electroluminescence.lo~l 3,14 It has been found, as anticipated,
that the energy of the main line shifts in the same way as the gap energy with
pressure in GaAs. The emission of GaAs lasers shifts at the same average
rate as the peak of the main line.'3,'4 However, since the laser emission is

' A. L. Edwards and H. G. Drickamer, Phys. Rev. 122, 1149 (1961).

R. Zallen and W. Paul, Phys. Rev. 134, A1628 (1964).
' R. Zallen, Thesis, Harvard University, 1964 (unpublished).
'' J. H. Taylor, Bull. Am. Phys. Soe. 3, 121 (1958).
l Z T . C. Bradley and H. A. Gebbie, Phys. Letters 16, 109 (1965).
l3 J. Feinleib, S. Groves, W. Paul, and R. Zallen, Phys. Rev. 131, 2070 (1963).
l4 G. E. Fenner, J . Appl. Phys. 34,2955 (1963).
332 ROBERT W. KEYES

restricted to certain distinct modes, the shift occurs by jumping of the emis-
sion from mode to mode rather than continuously. The frequency of any
given mode changes slowly with pressure because of changes of the dimen-
sions of the laser and of the dielectric constant.
Similarly, the “edge emission” of G a P has been found to vary in the same
way as the energy gap with pressure.” The electroluminescent spectra of
G a P diodes, and, also, of most GaAs diodes, contain lines of considerably
less energy than the gap. These lines arise from recombination of a hole
(electron) with an electron (hole) which has been trapped in some deep
donor (acceptor) state. The dependence of the position of the low energy
lines on pressure usually is weaker than the dependence of the gap on pres-
sure. The weaker dependence is believed to be a result of the tendency of
levels deep in the forbidden gap to maintain a fixed position with respect to
the valence band when pressure is applied, and suggests that the low energy
photons come from the recombination of a hole with a trapped e1ectr0n.I~
Electroluminescence spectra provide a very convenient way to study the
pressure dependence of impurity levels in the gap, as the impurity transitions
are frequently much more prominent in electroluminescence than in optical
absorption.

V. Electrical Conductivity
Electrical conductivity in the 111-V compounds at the temperatures at
which high pressure experiments are ordinarily performed may be divided
into two general types, intrinsic and extrinsic, which are conveniently dis-
cussed separately.
At ordinary temperatures, 111-V semiconductors most often show extrinsic
conductivity, in which the number of carriers is determined by the concentra-
tion of impurities and is independent of pressure and temperature. Effects
of pressure on conductivity then arise from effects of pressure on mobility.
The mobility of holes in 111-V semiconductors is essentially independent of
pressure. An example is shown in Fig. 2.
The mobility of electrons may be affected by pressure in two ways. If the
[OOO] minimum of the conduction band is lowest, the effective mass of the
electrons is changed by pressure because the effective mass is roughly
proportional to the gap between the [OOO] minimum and the valence
Effective mass and mobility are, however, closely related physical
properties, low effective mass generally being associated with high mobility.
Thus, since the [OOO] gap increases with pressure, the mobility and the con-
ductivity of extrinsic n-type semiconductors with [OOO] conduction band
l5 D. Long, Phys. Rev. 99, 388 (1955).
l6 R. W. Keyes, Phys. Rev. 99,490 (1955).
R. W. Keyes, Solid State Phys. 11, 149 (1960).
 5. EFFECTS OF HYDROSTATIC PRESSURE ON Ill-V SEMICONDUCTORS 333

20 -

10 -

0 5-
K
\
a

0 10
I ‘ 20 3
PRESSURE (lo3 kg/cm2)

FIG.2. The pressure dependence of the extrinsic resistivity of some 111-V semiconductors.
(Measurements of Howard and Paul.’) The large effects in n-type GaSb and GaAs are caused by
near degeneracies of two kinds of conduction band minima.

decrease with increasing pressure. The magnitude of the effect on the con-
ductivity is approximately inversely proportional to the energy gap, as is
illustrated in Table II.”

TABLE I1
THEPRESSURE DEPENDENCE
OF THE MOBILITY I N THE [OOO] BAND
OF 111-V SEMICONDUCTORS
AND ITS RELATION
TO THE ENERGY GAP’

~~~~~

InSb 60 x 0.27 16
InAs 35 x 0.47 16
GaAs 9.6 x 1.51 14
InP 8 x 10-6 1.42 11

After Keyes. * ’

The second kind of dependence of electron mobility on pressure arises

when two of the conduction band extrema are at nearly the same energy,
so that both contain electrons. The relative position of the two bands changes
with pressure and electrons are transferred from the one whose energy is
increased to the one whose energy is decreased. Since the electron mobility
is different in the two bands, the average electron mobility is changed by the
transfer of electrons. In addition, when the two bands are near in energy the
334 ROBERT W. KEYES

states of both bands are available as final states for scattering of electrons in
either band. As the bands shift with pressure the scattering rates change and
the mobilities within each band are pressure dependent.
Pressure dependence of n-type extrinsic conductivity caused by these
interband effects is known in GaSb and in GaAs and its alloys with phos-
, ' ~ , ' ~ of the large changes in resistivity produced by the
p h o r ~ ~ . ~ Examples
interband effects are given in Fig. 2.
Most of the charge carriers in intrinsic conductivity are present because
of thermal excitation of carriers across the gap. Therefore the number of
carriers changes rapidly if the gap is changed by pressure. The conductivity
is proportional to the number of carriers and thus also changes rapidly
with pressure. The conductivity may also be affected by changes in the
mobility with pressure, as discussed above, but the changes in number
dominate the effects of pressure on intrinsic conductivity in the 111-V com-
pounds.
An example is given in Fig. 3, which shows the effect of pressure on a
specimen of p-type InSb. At 85°C and zero pressure the InSb is intrinsic.

Pressure (lo3 hg/crnz)

FIG.3. The pressure dependence of the conductivity of lnSb in the intrinsic regime. (After
Keyes.I6) Pressure increases the energy gap and decreases the number of intrinsic carriers.

A. Sagar, Phys. Rev. 117,93 (1960).

l9 G. E. Fenner, Phys. Rev. 134, A1 13 (1964)
 5. EFFECTS OF HYDROSTATIC PRESSURE ON 111-V SEMICONDUCTORS 335

The energy gap increases and the number of intrinsic carriers and the con-
ductivity decrease with increasing pressure. Above 6000 kg/cm2 the con-
centration of intrinsic carriers becomes so small thpt the extrinsic carriers
start to dominate the Conductivity. The rapid decrease of conductivity
begins to disappear and the conductivity approaches a pressure-independent
extrinsic value at high pressures.
The energy gap of most of the 111-V semiconductors is so large that intrinsic
conductivity occurs only at high temperatures, temperatures beyond the
range of ordinary high pressure apparatus. The pressure dependence of
intrinsic conductivity has been studied only in InSb’5,’6720and InAs.21
The interpretation of the changes in intrinsic conductivity primarily due to
changes in the number of carriers excited across the gap has also been
confirmed by measurements of the pressure dependence of the Hall coefficient
in these materials.20’21
The sample of Fig. 3 contains a negligible number of intrinsic carriers
at 0°C above 4000 kg/cm2. The pressure independence of the conductivity
at higher pressures further illustrates the small effect of pressure on p-type
extrinsic conductivity.
The pressure dependence of a third type of conductivity has also been
studied in GaAs, namely, the conductivity due to carriers thermally excited
from traps far from the band extremum.22 If the depth of the trap depends
on pressure, the number of thermally excited electrons and the conductivity
will depend on pressure. It was found that the energy difference between the
trap level and the conduction band increases with pressure, so that the con-
ductivity decreases with pressure. The effect is quite large ; the trap depth
increases at about the same rate as the energy gap and the conductivity
decreases by almost an order of magnitude on application of 6 kilobars at
300°K. The interpretation of the conductivity change as a change in electron
concentration was confirmed by measurements of the pressure dependence
of the Hall constant.22
Minomura and Drickamer measured the resistance of many 111-V semi-
conductors at pressures up to several hundred thousand k g / ~ r n ’ .They ~~
found very large increases (two to five orders of magnitude) in the resistivity
of InP and InAs. These large increases are probably similar to the increases
studied by Sladek in GaAs, that is, they are probably due to increases in the
binding energy of deep trapping centers.

2o J. Gielessen and K. H. von Klitzing, 2. Physik 145, 151 (1956).

J. H. Taylor, Phys. Rev. 100, 1593 (1955).
22 R. J. Sladek, Bull. Am. Phys. SOC.9, 258 (1964): “Physics of Semiconductors” (Proc. 7th
Intern. Conf.), p. 545. Dunod, Paris and Academic Press, New York, 1965.
23 S. Minomura and H. G. Drickamer, J . Phys. Chern. Solids 23,451 (1962).
336 ROBERT W. KEYES

VI. Other Electrical Properties

1. PIEZORESISTANCE
Piezoresistance is the effect of stress on electrical resistance. It may be
large in both p - and n-type semiconductors, but for different reasons. Shear
stresses destroy the symmetry of the valence band and produce complex
changes in the structure of the electronic energy levels which lead to large
changes in the electrical conductivity. Hydrostatic pressure has little effect
on the valence band and does not change the piezoresistance coefficients of
p-type semiconductors a p p r e ~ i a b l yExamples
.~~ are given in Fig. 4.

1
[I p- lnSb
B Y

0 - 0
65c " - 4
50C
0
- O W "
n n
p-Ge
n
V
-
"
-
0

1 I

Pressure (lo3kg/cm2)
FIG. 4. The pressure dependence of large shear piezoresistance coefficients of p-type InSb
and p-type Ge. (After Keyes and P ~ l l a k .The
~ ~ )curves show the independence of the properties
of the valence band of the covalent semiconductors on pressure, a feature which was also illus-
trated by Fig. 2.

Multivalley n-type semiconductors have large shear piezoresistance co-

efficients because shear strains can destroy the symmetry which caused all
valleys to have the same energy and the same number of carrier^.'^.'^
Shear strain produces a transfer of electrons between valleys and a change in
the form of the resistivity tensor. This electron transfer effect does not occur
in semiconductors with [0:000]conduction band minima, however. Thus,
when pressure shifts the energy of the conduction band minima enough to
make a new kind of minimum the lowest, a striking change in the nature of
the piezoresistance tensor takes place.
This effect is illustrated for the case of GaSb in Fig. 5. At zero pressure
most of the electrons are in the [OOO] minimum and cause no piezoresistance.
The [ 1111 minima are not much above the [OOO] minimum and contain some
electrons which contribute to the piezoresistance coefficient 7 ~ Application
~ ~ .

24 R. W. Keyes and M. Pollak, Phys. Rev. 118, 1001 (1960).

l5 C. S. Smith, Phys. Rev. 94,42 (1954).
26 C. Herring, Bell System Tech, J . 34,237 (1955).
 5. EFFECTS OF HYDROSTATIC PRESSURE ON 111-V SEMICONDUCTORS 337

FIG.5. The pressure dependence of the piezoresistance coefficients of n-type GaSb. (After
Keyes and Pollak.") The data show that electrons are being transferred from the [OOO] to the
[I 1 I] minima as pressure is increased.

of pressure raises the energy of the [OOO] minimum, transferring electrons to

the [ l l l ] band where they contributed to n44.The n44 increases. The process
is nearly completed at 12,000 kgicm', most of the electrons are in the [ l l l ]
band, and nd4 is approaching a constant value which is characteristic of the
[I 113 band and is similar to that found in germanium, for example.
+
The piezoresistance coefficients ( n l l - n12) and (nll 2n1,)/3 are also
plotted in Fig. 5. The quantity (nll - n12)is the shear coefficient produced
by electrons in the [loo] band. Since there are no electrons in the [loo] band
in GaSb in the pressure range covered, n, - 7t12 is small throughout.
The combination grill + 2nI2) is simply the derivative of the resistivity
with respect to pressure. It is large whenever the effects described in Part V
produce pressure dependence of the resistivity. Thus n l l+ 2x1, is large
and positive in GaSb because the transfer of electrons to the low-mobility
[ l l l ] bands increases the resistivity. As the transfer nears completion the
pressure derivative decreases toward zero.
2. HALLEFFECTAND THERMOELECTRIC
POWEROF GaSb
Sagar originally formulated the [OOOI-[lll] model of the band structure
of GaSb from his studies of piezoresistance and the effect of pressure on
resistivity.'* He confirmed the details of the model in other experiments
with Miller." The Hall constant and the thermoelectric power depend on

'' A. Sagar and R. C . Miller, J . Appl. Phys. 32,2073 (1961).

338 ROBERT W. KEYES

pressure qualitatively in the expected way. The transfer of electrons from

the low-mass [OOO] band to the high-mass [l 111 band increases the thermo-
electric power. A value characteristic of the [I 111 band is approached at high
pressure. In the case of the Hall constant, the Hall constant is larger than its
normal value of about (llne) at low pressure because of the two-band effect.’*
At high pressures when most of the electrons are in the [ l l 13 band, the two-
band effect disappears. Thus the Hall constant decreases with increasing
pressure. The exact values of the thermoelectric power and the Hall constant
and the precise way in which they change with pressure depend on details
of the scattering processes in the two bands and can be fitted to models of
the s ~ a t t e r i n g . ’ ~ . ~ ’
3. MICROWAVE
OSCILLATIONS
Gunn discovered that coherent electrical oscillations of the current through
a GaAs specimen occur when a steady voltage which produces a field above
a certain threshold field is applied to the specimen.29The effect presumably
occurs because the threshold field (which is in the hot electron range) in-
creases the temperature of the electrons sufficiently that an appreciable
number of them are in the higher energy [loo] band. The electron mobility
in the [loo] band is much lower than the mobility in the [OOO] band. An
increase in field can, by transferring more electrons to the low mobility [loo]
band, produce a decrease in current. Gunn has shown that this kind of
current instability causes periodic propagation of electric shock waves
through the specimen and can lead to oscillatory behavior of the current.30
It can be seen that when the energy difference between the [loo] and [OOO]
bands is decreased by the application of pressure, the threshold field for the
Gunn effect should decrease. The decrease was indeed found by Hutson
et al., who observed oscillations up to 25,000 k g / ~ m ’ . ~ ’The threshold
field at the highest pressure was 213 of the threshold at zero pressure. The
range of voltage over which the effect existed decreased in the high end of the
pressure range and no instability was observed above 26.000 kg/cm2.

VII. Phase Transitions

The 111-V semiconductors all have the type of crystal structure known as
“zinc blende.” The zinc-blende structure is very loosely packed ; each atom
has only four near neighbors. The energetic stability of such a loosely packed
28 See, for example, J.-P. Jan, Solid State Phys. 5, l(1957).
29 J. B. Gunn, IBM J . Res. Develop. 8, 141 (1964).
30 J. B. Gunn, unpublished.
’‘ A. R. Hutson, A. Jayaraman, A. G. Chynoweth, A. S. Coriell, and W. L. Feldmann, Phys. Reu.
Letters 14, 639 (1965).
 5 . EFFECTS OF HYDROSTATIC PRESSLJRE ON 111-V SEMICONDUCTORS 339

structure is reduced by high pressures. The free energy of a substance con-

tains a term PK so that phases of low volume tend to become more stable
at high pressures. High pressure experiments now reach several hundred
thousand kg/cm2, at which pressures the PV term in the free energy ap-
proaches 100 kcal/mole and is an important part of the free energy.
It is indeed found that other crystal structures become more stable than
the zinc blende when the 111-V semiconductors are subjected to sufficiently
high pressure^.^^,^^-^^ Phase transitions to more closely packed structures
take place. The volume of the material decreases by about 20 % in the transi-
tion to the high pressure form.34 A typical transition of this kind has been
known for a long time in tin, the cr-Sn--P-Sn transition. The cr-Sn structure is
closely related to the zinc-blende structure and the high pressure phase of the
111-V semiconductors is frequently nearly the P-Sn structure. Similar transi-
tions also take place in germanium and silicon and in 11-VI com-
pounds.9s2336-39
Although the high pressure P- (or 11) phases usually have a P-Sn-like
structure, the high pressure phase has the NaCl structure in a few 111-V
c o m p o ~ n d s . ~ Table
~ * ~ *I11, ~lists
~ ~known
~ high pressure transitions in
the 111-V semiconductors and parameters of the transition and the high
pressure phase^.^^.^^ J a m i e ~ o nobserved
~~ that the transition pressures
seem to be roughly a function of the energy gaps of the semiconductors and
also the remarkable fact that the approximate difference in Gibbs free energy
between the low pressure and high pressure phases (transition pressure x
difference in volume) is close to half of the energy gap. Ail of the physical
properties of the 111-V semiconductors vary in systematic ways with pro-
gression through the periodic table, and thus all appear to be correlated with

32 H. A. Gebbie, P. L. Smith, I. G. Austin, and J. H. King, Nature 188, 1095 (1960).

33 A. Jayaraman, R. C. Newton, and G. C. Kennedy, Nature 191, 1288 (1961).
34 J. C. Jamieson, Science 139, 845 (1963).
35 A. Jayaraman, W. Klement, Jr., and G. C. Kennedy, Phys. Rev. 130,540 (1963).
36 J. C. Jamieson, Science 139, 762 (1963).
3’ R. G. McQueen, S. P. Marsh, and J. Wackerle, Bull. Am. Phys. SOC.7,447 (1962)
38 C. H. Bates, W. B. White, and R. Roy, Science 137, 993 (1962).
39 C. H. Bates, W. B. White, and R. Roy, Science 147, 860 (1965).
40 P. L. Smith and J. E. Martin, Nature 1%, 762 (1962).
41 A. J. Darnel1 and W. F. Libby, Science 139, 1301 (1963).
42 M. D. Banus, R. E. Hanneman, A. N. Mhriano, E. P. Warekois, H. C. Gatos, and J. A. Kafalas,
Appl. Phys. Letters 2, 35 (1963).
43 R.E. Hanneman, M. D. Banus, and H. C. Gatos, J. Phys. Chem. Solids 25,293 (1964).
44 T. R. R. McDonald, R. Sand, and E. Gregory, J . Appl. Phys. 36,1498 (1965).
45 P. L. Smith, J. H. King, and H. A. Gebbie, in ”Physics and Chemistry of High Pressures.”
SOC. Chem. Ind., London, 1963.
46 H. G. Drickamer, in “Physics and Chemistry of High Pressures.” SOC. Chem. Ind., London,
1963.
340 ROBERT W. KEYES

TABLE 111
PARAMETERS
OF THE PHASETRANSITIONS
AND THE HIGH PRESSURE
PHASESOF
111-V SEMICONDUCTORS

Transition AV3b High pressure Superconducting

Substance pressureb (cm3/mole) crystal trans. temp.
(lo3 kg/cm2) structureb ( O K )

lnSb 22 1.6 8-Sn 1.87'

GaSb 90 5.2 8-Sn 4.2d
InAs 100 5.8 NaCl
AlSb 125 5.0 P-Sn 2.8'
InP 133 5.4
GaAs 240 5.5
Gap"

* It is worth noting that Minomura and Drickamer found no transition in G a P

to 550 x lo3 kg/cm*.
After J a m i e ~ o n . ~ ~
'Refs. 47, 54-56, 59. Another high pressure phase of InSb has = 4.2"K
(Ref. 50).
Ref. 51.
Ref. 60.
one another. A correlation between lattice parameter and transition pressure
of the 111-V compounds is shown in Fig. 6.
The high pressure phase diagram of InSb is actually far more complicated
than suggested by the simple picture of an or-Sn-fi-Sn type transition just

I 0

5 200
0
r
m
150

P
kz 50
a

LATTICE CONSTANT (1)

FIG.6. The transition pressures of the 111-V compounds (as in Table 111) plotted against zero
pressure lattice parameter. Most physical properties of the 111-V compounds show some cor-
relation with one another.
 5. EFFECTS OF HYDROSTATIC PRESSURE ON 111-V SEMICONDUCTORS 341

described. Other transitions occur, and several studies of the phase relation-
ships and structures have been It appears that there is a high
pressure phase of InSb with the p-Sn structure (InSb II), and it is relatively
easy to produce InSb I1 by quenching from high p r e s s ~ r e . ~ ’ A , ~dis-
~.~~
cussion of the many studies of the properties of InSb I1 and its alloys with
p-Sn that have been carried out is beyond the scope of this work. There is
also an orthorhombic phase, a phase InSb 111, which is formed at high tem-
perature and pressure, and still another phase above 80 kbar.;!3*47-50The
occurrence of these phases seems to be somewhat sensitive to the details of
the experiment ; some of them may be metastable.
The electrical resistivity of the 111-V compounds decreases by orders of
magnitude at the transition.23932~43~4s*46~51~53
The high pressure p-Sn phases
are metallic. Like P-Sn, the high pressure phases of InSb, AlSb, and GaSb
are superconducting.23~32~43.45.46*47-~51~53-60 It has proved possible to
study the high pressure forms of InSb and GaSb at atmospheric pressure
by applying high pressure, allowing the transition to take place, quenching
the high pressure apparatus to some low temperature, as 77”K, then releasing
the pressure. The samples remain in the metastable high pressure phase for
long times if they are kept at low temperature. The transition temperatures
of the high pressure phases are also shown in Table 111.

VIII. Elastic Properties

The volume of the 111-V compounds decreases with increasing pressure.
The dependence of the volume on pressure is quantitatively described by the
bulk modulus B, defined by B = - V(dP/dV),. The bulk modulus and the
shear elastic constants of several 111-V compounds have been measured by
ultrasonic methods. The bulk modulus turns out to have a value of about

47 J. S. Kasper and H. Brandhorst, J . Chem. Phys. 41, 3768 (1964).

48 J. E. Martin and P. L. Smith, Brit. J . Appl. Phys. 16, 495 (1965).
49 D. B. McWhan and M. Marezio, J . Chem. Phys. 45, 2508 (1966).

’O M. D. Banus and M. C. Lavine, J . Appl. Phys. 38,2042 (1967).

” A. J. Darnell and W. F. Libby, Phys. Rev. 135, A1453 (1964).
5 2 M. D. Banus, L. B. Farrell, and A. J. Strauss, J . Appl. Phys. 36, 2186 (1965).

53 S. Minomura, B. Okai, H. Nagasaki, and S. Tanuma, Phys. Letters 21, 272 (1966).
5 4 H. E. Bommel, A. J. Darnell, W. F. Libby, and B. R. Tittman, Science 139, 1301 (1963).

’’ S. Geller, D. B. McWhan, and G. W. Hull, Jr., Science 140, 62 (1963).

5 6 L. F. Stromberg and C. A. Swenson, Phys. Rev. 134, A21 (1964).

’’ D. B. McWhan, G. W. Hull, Jr., T. R. R. McDonald, and E. Gregory, Sciencel47,1441(1965).

’* M. D. Banus, S. N. Vernon, and H. C. Gatos, J . Appl. Phys. 36,864 (1965).
5 9 B. R. Tittman, A. J. Darnell, H. E. Bommel, and W. F. Libby, Phys. Reu. 135, A1460 (1964).
6 o J. Wittig, Science 155, 685 (1967).
342 ROBERT W . KEYES

B = 1.2q2/aO4,where q is the electronic charge and a, is the lattice constant,

for all of the 111-V semiconductors.61
The elastic properties of GaAs have been investigated in greater
Drabble and Brammer62 and McSkimin et have investigated the
pressure dependence of the elastic constants of GaAs. Their results are
presented in Table IV. Since there is a strong similarity between the elastic

TABLE 1V
THE ELASTIC
CONSTANTS
OF GaAs AND THEIRPRESSURE
DEPENDENCE

GaAsb GaAsC.d Gee

Ba.J 0.747 0.749 0.744

c8a. J 0.326 0.326 0.402
c44 0.594 0.595 0.668
dB/dP 4.61 4.73 4.76
dc'ldP 0.1 0.3 0.4
dcddp 1.1 1.8 1.4

In terms of the ordinary elastic constants,

+
B = ( c I I 2c,,),3 and c' = (c,, - c I z )2.
After McSkimin et
After Drabble and Bramrner.62
dValues of B , c', and c44 have also been reported by
Bateman et d 6 U and Garland and Park.65
After McSkimin and A n d r e a t ~ h ~ and
~.~'
In units of 10" dynes cm*.

properties of the 111-V and group IV semiconductors,61 the same elastic

constants of which has nearly the same lattice parameter
as GaAs, are also presented for comparison.
61 R. W. Keyes, J . Appl. Phys. 33,3371 (1962) This paper also contains references to the original
measurements of the elastic constants.
J. R.Drabble and A. J. Brammer, Solid State Commun. 4,467 (1966).
63 H. J. McSkimin, A. Jayaraman, and P. Andreatch, Jr., J . Appl. Phys. 38, 2362 (1967).
64 T. B. Bateman, H. J. McSkimin, and J. M. Whelan, J. Appl. Phys. 30, 544 (1959).
65 C. W. Garland and K. C. Park, J . Appl. Phys. 33,759 (1962).
66 H. J. McSkimin and P. Andreatch, Jr., J . Appl. Phys. 34,561 (1963).
67 H. J. McSkimin and P. Andreatch, Jr., J . A p p l . Phys. 35, 3312 (1964).
bs J. J. Hall, Bull. Am. Phys. Soc. 10,43 (1965), and to be published.