..

FLUORESCENCE OF GRADED- BAND-GAP.

and

R. Stille, Phys. Status Solidi 36, K71 (1969).

J. Biter and F. Williams, J. Luminescence 3, 395

5W.

(1ev1).

8E. T. Handelman and W. Kaiser, J. Appl. Phys. 35,

351e (1e64).
'H. H. Woodbury and R. B. Hall, Phys. Rev. 157, 641
(1e6v).
H. Kato, M. Yokozawa, and S. Takayanagi, Japan.
J. Appl. Phys. 4, 1019 (1965).
9J. M. Stanley, J. Chem. Phys. 24, 1279 (1956).
L. C. Greene and C. R. Geesner, J. Appl. Phys. 38,
3662 (1967).
'W. H. Strehlow, J. Appl. Phys. 40, 2928 (1969).
N. I. Vitrikhovskii and I. B. Mizetskaya, Fiz. Tverd.
Tela 1, 397 (1959} [Sov. Phys. Solid State 1, 358 (1959}].
~SA. J. Eroles and A. L. Friedberg, J. Am. Ceram.
Soc. 48, 223 (1965).
~4Y. S. Park and D. C. Reynolds, Phys. Rev. 132,
2450 (1963).
~
F. L. Pedrotti, Ph. D. thesis (University of Cincinnati,
1962) (unpublished); see D. C. Reynolds, C. W. Litton,
and T. C. Collins, Phys. Status Solidi 12, 3 (1965).

PHYSIC AL REVIEW B

VOLUME 5,

"E. T. Handelman and D. G. Thomas, J. Phys. Chem.

Solids 26, 1261 {1965).
D. C. Reynolds, C. W. Litton, and T. C. Collins,
Phys. Rev. 156, 881 (1967).
C. E. Hurwitz, II-VI Semiconducting Compounds
(Benjamin, New York, 1967), p. 682.
S. Ibuki and A. Ohso,
Phys. Chem. Solids 27,

J.

1753 (1966).

J. Berkowitz
J. Berkowitz

and

J. R.

Marquart,

J. Chem.

Phys.

39, 2v5 (1963).

and W. A. Chupka, J. Chem. Phys. 48,

5743 {1968).
~L. S. Brooks, J. Am. Chem. Soc. 74, 227 (1952).
P. Goldfinger and M. Jeunehomme, Trans. Faraday
Soc. 59, 2851 (1963).
P. G. Shewmon, Diffusion in Solids (McGraw-Hill,
New York, 1963), p. 14.
25R. B. Parsons, W. Wardzynski, and A. D. Yoffe,
Proc. Roy. Soc. (London) A262, 120 (1961).
6C. E. Bleil and I. Broser,
Phys. Chem. Solids
25, 11 (1964).

J.

NU

15 F EBRUARY 1972

MB ER 4

Interlayer Bonding and the Lattice Vibrations of P-GaSe

T. J. dieting* and J. L. Verble
Naval Research Laboratory, Washington, D.
(Received 29 September 1971)

C. 20390

The lattice vibrations of the layer compound P-GaSe have been investigated by means of infrared and Raman experiments. Ref lectivity Ineasurements for Eic over the range 1754100
cm have shown one infrared-active mode at 213. 9 cm" . Six Raman lines have been observed
at 19.1, 60. 1, 134.6, 213. 1, 249, and 307. 8 cm . A group-theoretical analysis of the lattice
vibrations, which shows the origin of the conjugate modes in layer compounds, is presented.
Electrostatic as well as van der Waals coupling between the layers is indicated by the large
localized effective charge obtained from the infrared measurements.

I. INTRODUCTION

Layer compounds are characterized by highly

anisotropic bonding forces and structurally identical layers. The forces between the layers are
known to be weak by comparison with the forces
within the layers. One therefore expects that the
interlayer coupling will have a small effect upon
the vibrational frequencies of the lattice. A special case of some importance arises when the
primitive unit cell contains two layers and there
is an inversion center between the layers. Then
the normal modes occur in pairs that are either
symmetric or antisymmetric with respect to inversion. These so-called conjugate modes can be
easily studied, provided that they are optically
active, by means of a combination of infrared and
Raman experiments.
Such experiments'
have recently been carried
out for the layer compounds MoS2, As2SS, and
AsSe3, and the conjugate optical modes have been

observed to be nearly degenerate in energy. The

hexagonal layer compound Mo82 has only one pair
of conjugate modes that are optically active: the
Ej infrared-active and the 8+, Haman-active pair.
A frequency difference of =1 cm was previously
reported by the authors for these two vibrations.
For As28, and As2Sehowever, several pairs of
conjugate modes are optically active; Zallen
et a/. ' have observed frequency splittings as
large as 6 cm ' between conjugate pairs.
In this paper we present infrared and Raman
data on another semiconducting layer compound of
wide interest, GaSe. In the previously mentioned
investigations it was assumed that the interlayer
forces were primarily of the van der %aals type.
This is a common assumption for layer compounds
and one which clearly needs justification.
Indeed,
we shall propose that the interlayer interaction in
GaSe contains an ionic or Coulomb contribution.
The principal evidence for this is the large localized effective charge which has been determined

T.

J.

J. I .

WIE TING AND

from the present infrared measurements.

The
value of the charge is in reasonable agreement
with the ionic charge required by the bonding
scheme of Fischer and Brebner. '
In Sec. II we describe the crystal structure and
present a group-theoretical analysis of the vibrational modes of GaSe; The correlation method of
group theory is used to relate the vibrational
modes of an isolated layer to those of the crystal.
This analysis allows the irreducible representations of the modes to be assigned to specific sets
of displacement vectors.
In Sec. III the experimental infrared and Raman
results are given, and the frequencies of the modes
are assigned to the displacement vectors of Sec.
II. The infrared ref lectivity obtained for E i c is
significantly different from that reported by I eung

TABLE

I.

rep.

properties

acous tie al

BXlS

2g

BXlS

infrared

BXlS

B2g

inactive

BXls

BXlS

Ag

n, +o,

+~,

Ag

~Raman
e~

Each layer of GaSe is structurally identical and

is composed of single planes of selenium atoms on
either side of a double plane of gallium atoms.
Figure I illustrates the coordination of the gallium
and selenium atoms in a single layer. The coordination numbers of the gallium and selenium atoms are
four and three, respectively. Within a layer the
crystal bonding is thought to be primarily covalent.
The fact that mechanical cleavage occurs easily
along the basal plane indicates that the bonding

inactive

c axis

Haman

BXls

BXlS

(cm

~)

237. 0

134. 6
307. 8

Bf,

inactive

E~u

acoustical

basal plane

3QP

Haman

basal plane

19.1

infrared

basal plane

213. 9

3gp

Raman

basal plane

213. 1

inactive

basal plane

Tg j Ty

$g

XX

&

Tg) Ty
xx

pV

&

1
1

Haman

basal plane

inactive

basal plane

Raman

basal plane

E(
2

AND GROUP THEORY

Direction of
vibration

inactive

lattice vibrations.
II. CRYSTAL STRUCTURE

lattice vibrations of P-GaSe.

Activity

A2

Sec. IV the GaSe data are interpreted interms

of the nature of the interlayer interactions, and

the effects of ionic bonding are discussed. It is
predicted that long-range electrostatic forces will
be important in force-model calculations of the

Long-wavelength

Trans.

et al. '
In

VEHBI E

E~e

60. 1
249

~See Ref. 5,

between the layers is relatively weak.

Three crystallographically distinct polytypes of

GaSe have been reported: The p and e structures
have two-layer hexagonal stacking s'equences,
whereas the y structure has a three-layer rhombohedral stacking sequence. ' Carter (of this laboratory) has shown by means of x-ray diffraction
that the GaSe Bridgman-grown crystal used in this
investigation has the hexagonal P structure.
The
GaS'
that
is
similar
to
and
has
the
structure
of
P
space group D,(PG~/mme). Two layers and four
molecular units are contained within the primitive
unit cell. Thus, 24 normal modes are allowed.
The normal vibrations of GaSe decompose into
irreducible representations at the Brillouin-zone

center as follows:

I'= 2A. ~+ 2A. gg+ 28'+ 282g+ 2E)

+ 2+ ~ + 2Egg + 2E 2.

FIG. 1. The coordination of the gallium and selenium

atoms in a single layer of GaSe. The gallium atoms are
represented by the black spheres.

Table I gives the transformation properties of the

representations.
Since the representations of the
acoustical modes must transform as T, T, , or
T these modes are represented by Aaand the
doubly degenerate E& . In addition. there are two
infrared-active modes of A2and Ej symmetry
and six Haman-active modes of A. ] E&g and Epg
The infrared- and Haman-active modes
symmetry.
are mutually exclusive because of the inversion
center between the layers. The remaining modes

INTERLAYER BONDING
Ga (C~)

LAYER (Dqh)

AND

THE LATTICE VIBRATIONS OF.

III. INFRARED

CRYSTAL (Deh)

Se (C
Ai

Ai

Eiu

1475

AND RAMAN MEASUREMENTS

A. Reflectance and Transmittance

Aq
Ai

..

Near-normal-incidence
measurements of the
reflectance and transmittance of a large Bridgmangrown crystal'0 (1. 5&&1.0-cm surface area) were
made at room temperature using a Perkin-Elmer
model No. 301 spectroghotometer.
No measurements were made for E c, because the crystal
was too thin (0. 067 cm). The experimental techniques employed were identical to those used in an
earlier study and will not be discussed here. The
range of the measurements was 175 4100 cm '.
Figure 4 shows the ref lectivity of P-GaSe in the
region below 450 cm, where the crystal was optically opaque. Above 450 cm ' the ref lectivity
was calculated from the equation '
II

Eig

Ep

FIG. 2. Correlation diagram for the irreducible representations of the site groups, the point group of an isolated
layer, and the crystal factor group of P-GaSe.

1+2'
are optically inactive.
In order to assign the representations to specific
sets of atomic displacements, we have used the
correlation method of group theory. ' Figure 2
shows the correlations among the representations
for the site groups, the point group of an isolated
layer, and the crystal factor group. An important
feature of the correlation diagram is that each of
the irreducible representations for the isolated
layer divides into two pairs of representations for
the crystal. Each pair consists of an odd and even
representation, and we therefore refer to the modes
which they represent as conjugate modes. The
correlation diagram indicates further that the gallium and selenium atoms vibrate in all of the normal modes of the crystal.
The assignments of representations to sets of
atomic displacements can now be carried out.
These are shown in Fig. 3. Odd modes are shown
in the top row of the figure, and even modes are
shown in the bottom row. Conjugate pairs are
therefore grouped vertically. Because of the inversion center between the layers, the conjugate
modes differ from each other by an interlayer
phase shift of 180'. Moreover, the conjugates of
the acoustical modes (Amand E,) are optical
modes (Bz and Ez, ) in which entire layers vibrate
rigidly out of phase with their neighbors. We
shall refer to this class of optical modes as
rigid-layer modes.
belonging to the
The A&and Erepresentations
infrared modes are assigned to the sets of atomic
displacements shown in Fig. 3, because these are
the only antisymmetric modes which generate a
net electric-dipole moment within the unit cell.
The remaining assignments of the representations
are unambiguous, apart from the superscripts on
which have no physical sigthe representations,
nific ance.

g~ + T2

2(2-R)
4R(2 -f~.)
')')
(t ~ mz. -~'+T.

are the measured reflectance and

Between 1250 and 4100 cm ', the
high-frequency dielectric constant is 6. 71+0. 1,
and the index of refraction for the ordinary ray

where

and T

transmittance.

is 2. 59+0. 02.
The curve shown in Fig. 4 represents a leastsquares fit to the ref lectivity data. In generating
this curve the well-known Lorentzian-oscillator
The dispersion parameters of
model was used.
the model are as follows: the high-frequency dielectric constant e the oscillator strength p,
the damping constant y, and the resonance frequency of the oscillator ~0. Table II gives the
values of the parameters obtained from the leastsquares fit to the measured ref lectivity. Note that
the high-frequency dielectric constant for the
least-squares fit agrees with that determined from
reflectance and transmittance measurements in

oo-

6
6

o-

6'

Aau

oEIu

61

o-

o-

B~g

E~g

bI
I

6
6

Aau

6
6

B~g

o6i
o-" q~
o-

" o-

'6

EIu

BIu

o-
o-

E~g

0Eau

o-

fb

"o-

Blu

Eau

o-

bl
(p

AIg

0E Ig

6
A'

oE'

FIG. 3. Displacement vectors and representations for

the long-wavelength vibrational modes of P-GaSe.

T.
I

90
80
70
60
50

J.

WIE TING AND

I

J.

L.

VE RB LE
I

P-GOSe
o

experiment

oscillator

FIG. 4. Ref lectivity of P-GaSe

at room temperature for E~c.
The solid curve represents a leastsquares fit to the ref lectivity data.

model

~0

50

20
IO
0
l

200

50

250
WAVE

the 1250 4100-cm

500
NUMBER

(cm

region.

Sachs Teller relation:

4 P

6E
&o

v To

where co is the low-frequency

for

Elc.

dielectric constant

The infrared ref lectivity of GaSe was previously

measured by Leung et a/. They reported one pair
of infrared-active modes, which is consistent with
the hexagonal P structure.
Their data are given in
Tables I and II. The dispersion parameters determined by the method of interference fringes were
regarded by these authors as more accurate than
those obtained from their ref lectivity measurements. However, the values which we have obtained are substantially different, particularly the

TABLE II. Dispersion parameters

450

~)

The last column of Table II shows the longitudinal optical-phonon frequency v (in units of
cm '), which was calculated from the Lyddane&Lo

400

550

value of the transverse optical-phonon frequency

Leung et al . reported variations in the revyo
f lectivity of 10/g from sample to sample, due to
surface preparation, and this may account for the
differences in the high-frequency dielectric constant, as well as the oscillator strength and damping constant. Qn the other hand, we observed no
frequency dependence of the ref lectivity above
1250 cm, where dispersion in the index of refraction should be negligible and the condition of
the surface should be important.
We did not attempt to polish or cleave the natural surface of
the GaSe sample. The natural surface appeared
visually to be in excellent condition.
The dispersion parameters of Table II can be
used to determine the localized effective charge
on the gallium and selenium atoms. Huang's
classical theory' of effective charge applies primarily to diatomic crystals which have tetrahedral site symmetry. In this case the local ef-

for the E infrared-active

mode of P-GaSe.
V TO

Present work

Lorentz

6. 73

oscillator

(+ 0. 1)

Reflectance and
transmittance

6. 71
(+ 0. 1)

Lorentz
Leung et

al.

oscillator
Inter ferenc e
fr lnges

See Ref. 5.

8. 4

VLo

(cm-')

(cm

~)

0. 224
0. 02)

0. 0125

213. 9

254. 7

(+

(+ 0. 001)

(+ 1)

(+ 5)

0. 143

0. 0087

230. 7

254. 2

230. 7

264. 6

0. 187

INTERLAYER BQNDING

AND

THE LA TTIC E VIB RA TIQN S

fective field has a simple form, and the Szigeti

charge can be written as

where e* is the effective charge, e is the electronic

charge, c is the speed of light, M is the reduced
mass of the ion pair, and N is the number of ion
pairs per unit volume. Since P-GaSe is a complex
anisotropic crystal, we can obtain only an approximate measure of the localized charge from
Eq. (4). The most important source of error
comes from the local-field factor 3/(e+ 2), which
may be appreciably different for GaSe. However,
if we assume that Eq. (4) is approximately correct, we obtain an effective charge of 0. 74e.
Leung et al. 's data from interference fringes
(Table II) give an effective charge of 0. 68e.
B.

Raman Scattering

The first-order Raman spectrum of P-GaSe was

obtained using an argon-ion laser, a double monochromator, photon-counting electronics, and
backscatter geometry. Six Raman lines" were
observed with 5145-A laser light of about 500-mW
The unanalyzed spectrum is shown in
intensity.

Fig. 5.
Since the GaSe crystal was too thin to prepare
and polish a surface parallel to the c axis, light
scattering was measured only from the basal
plane (xy plane). For normal incidence and scattering [z(xx)z or z(xy)Z], the polarization properties of the Raman lines at 19. 1, 134. 6, 213. 1,
and 307. 8 crn ' matched the transformation properties of the A&, and E3, representations of Table
I. The lines at 60. 1 and 249 cm ' were either very
weak or absent. For grazing incidence, in which
components of the incident electric vector were
along z as well as x or y, the lines at 60. 1 and
We there249 cm ' were greatly strengthened.
fore assign these two frequencies to the E&, repThe line at 249 cm ' remained weak
resentations.
and relatively broad under all conditions of ex-

citation.
Although there are two Raman frequencies for
each irreducible representation, the following considerations permit a unique determination of the
frequency for each set of displacement vectors
(see Fig. 3). We first note that the E~a, mode is
the conjugate of the infrared-active Eqmode and
that the frequencies of the E@, modes are very
different, 213. 1 as compared with 19.1 cm '. We
further note that the E@~. mode is a rigid-layer
mode. Now since the interlayer interaction in
GaSe is relatively weak, we shall assign the
19.9-cm frequency to the rigid-layer E@ mode,
and the 213. 1-cm ' frequency to the E2, mode.

The assignment of the A&, and E&, frequencies,

however, requires another kind of argument. In
the E~, normal mode (see Fig. 3) the restoring
force is primarily due to the gallium-gallium
bond, whereas in the E&, mode the gallium-selebonds are
nium as well as the gallium-gallium
involved. Thus we shall assign the higher frequency to the Ej, mode. The same argument
applies to the frequencies of the A&, modes. Table
I summarizes the frequency assignments of the
Raman-active modes.
IV. DISCUSSION OF INTERLAYER INTERACTION

In P-GaSe the E~and E'2, conjugate optical modes

are nearly degenerate in energy. Moreover, since
the acoustical-mode frequency is zero at the Brillouin-zone center, the frequencies of the E&

(acoustical) and E22, conjugate modes differ by

19.1 cm . These two experimental facts are related to the nature of the interlayer forces in
P-GaSe.
If we assume that the interlayer forces are exclusively of the van der Waals type, the symmetric
E2, mode will have a highex frequency than that of
the antisymmetric E&mode. The reason for this
is that the layers in the unit cell vibrate out of
phase in the symmetric mode (see Fig. 3), and
the additional van der Waals interaction between
the selenium atoms in adjacent layers will raise
the frequency of the E2, mode. The frequency of
the antisymmetric Eqmode, however, will not
be affected by the van der Waals interaction, because the layers vibrate in phase. The result
in this case is that v(E&) & v(E, ). A similar argument applies to the relative frequencies of the
Eqacoustical and E2, rigid-layer modes.
Using a simple model for the van der Waals interaction between the layers, we can estimate the increase in frequency of the E&~ mode. Itis well known
that two identical coupled oscillators have vibrational frequencies
given by Po and (vo+ &v )' 2, where
vo is the frequency of the isolated oscillator, and hv

is the coupling frequency, which depends only upon

the coupling force constant and the mass of the oscillators. The frequency vo represents the mode in
which the oscillators vibrate in phase, so that the
coupling force constant has no effectonthe frequency
of this mode. In the other mode, the oscillators
vibrate 180' out of phase. The coupling frequency
for P-GaSe, using this simple model, is the same
as the E3~ rigid-layer mode frequency, 19. 1 cm
Thus the frequency of the E~, mode is given by
(213. 92+19.1 ) '2= 214. 8 cm ~, and the calculated
difference v(E~, ) v (E~) =+0. 9 cm . Although
the experimental error is +1 cm ' for the conjugatemode frequencies, the important fact is that the
symmetric E3 mode was observed to have a louex
frequency than that of the antisymmetric E&mode

T.

1478
1.

J.

WIE TING AND

L.

VE RB LE

0
9

LLI

J.

.8

A, g
t

E2

p-GaSe

2g

FIG. 5. The unanalyzed Raman

spectrum of P-GaSe at room temperature.
I

E~g

50

100

150

200

WAVE NUMBER (cm

500

250

')

[observed difference v (E2, ) v (E&)= -0. 8 cm '].

It is improbable that the experimental error alone
can account for the observed difference in the conjugate-mode frequencies.
The interlayer interaction cannot therefore be exclusively of the van
der Waals type.
Another kind of interlayer force for GaSe is
suggested by the bonding scheme of Fischer and
Brebner. ' Their scheme assumes an electron
pair for each of the bonding atoms. If during
bonding one electron is transferred from the
selenium to the gallium atoms, the hybridized
orbitals of the Ga ' and Se' ions are tetrahedral
sp' and trigonal p', respectively. These configurations agree with the coordination numbers of
the gallium and selenium atoms. Moreover, the
Szigeti charge for GaSe, calculated in Sec. III,
is approximately equal to the one electron required by the bonding scheme. Thus the longrange Coulomb forces between the ions constitute
an electrostatic interaction between the layers.
Additional indirect evidence of the electrostatic interaction comes from the size of the van
der Waals radius for the selenium atoms. If the
selenium 4t) orbitals are used in the covalent
bonds to the gallium atoms, then the van der Waals
interaction between the selenium atoms in GaSe is
primarily due to the 4s electrons. Since these
are closer to the nucleus than the 4& electrons,
the interlayer distance between the selenium atoms
should be smaller than twice the van der Waals
radius. The actual interlayer distance (4. 04 A)
is slightly larger than twice the van der Waals
radius given by Pauling" (2x 2. 00 A). This dif*National Res earch Council Research Associate.
~J. L. Verble and T. J. Wieting, Phys. Rev. Letters

ference can be qualitatively explained by a Coulomb

repulsion between the layers. By contrast, in
distance across the gap is
MoS& the sulfur-sulfur
3. 37 A, which is appreciably less than twice the
Pauling van der Waals radius (2x1. 85 A). Using
the authors' previous measurements
on MoS~ and
Eq. (4), we find that the effective charge (for both
E J. c and E c) is 0. lie. Consequently, the electrostatic interaction between the layers is considerably smaller than that in GaSe. Finally,
since the van der Waals interaction in MoS2 is
primarily caused by the 3s, rather than 3p,
electrons, a reduction of the interlayer van der
Waals gap is to be expected.
In conclusion, the arguments presented here
suggest that long-range Coulomb forces are a
significant part of the lattice dynamics of GaSe.
Moreover, they represent the first evidence of
electrostatic interactions in layer compounds.
Thus a simple force model for GaSe, based on
nearest-neighbor interactions within a single
layer, such as that applied to MoS2, will not be
adequate. The success of this model for MoS2
appears to be directly related to the small value
of the effective charge, which implies that the
Coulomb forces are negligible.
A more complete
understanding of the lattice dynamics of GaSe
must await further experimental and theoretical
investigations.
tl

ACKNOWLEDGMENT

The authors wish to thank M. Schlueter for providing the GaSe crystal used in this investigation.
25, 362 0.970).

T.

J. Wieting

and

J. L.

Verble, Phys. Rev. B 3, 4286

INTERLAYER BONDING

AND

THE LATTICE VIBRATIONS OF

(1971).
R. Zallen, M. L. Slade, and A. T. Ward, Phys. Rev.
B 3, 4257 (1971).
G. Fischer and J. L. Brebner, J. Phys. Chem. Solids
23, 1363 (1962).
P. C. Leung, G. Andermann, W. G. Spitzer, and
C. A. Mead, J. Phys. Chem. Solids 27, 849 (1966).
6F. Jellinek and H. Hahn, Z. Naturforsch. 16b, 713
(1961).
R. W. G. Wyckoff, Crystal Structures (Interscience,
New York, 1965), 2nd ed. , Vol. 1, p. 145.
D. F. Hornig, J. Chem. Phys. 16, 1063 (1948); E.
B. Wilson, Jr. , J. C. Decius, and P. C. Cross, Molecular Vibrations (McGraw-Hill, New York, 1955), Appendix
X, pp. 312340.
In previous papers we have used the term "quasiacoustical" instead of "rigid-layer. " However, thelatter
term is perhaps clearer and more descriptive, since in

PHYSIC AL REVIEW B

Experimental

the long-wavelength limit there is no relative displacement

of the atoms within the layers.
The GaSe crystal was grown by
P. Voitchovsky of
the Ecole Polytechnique Fdddral de Lausanne, Switzerland.
I H. O. McMahon.
, J. Opt. Soc. Am. 40, 376 (1950).
~~M. Born and K. Huang, Dynamical Theory of Crystal
I.attices (Oxford U. P. , Oxford, England, 1968), Sec. 9.
G. B. Wright and A. Mooradian [Bull. Am. Phys.
Soc. 11, 812 (1966)] have observed Baman lines in GaSe
at 59. 6, 133.8, 209. 5, 253. 8, and 308. 6 cm ~. However,
no polarization properties were given, and the low-frequency
mode at 19. 1 cm ~ was not reported.
~4K. R. Symon, Mechanics (Addison-Wesley,
Beading,

J.

Mass. , 1957), p. 165.

L.

Pauling,

The Nature of the Chemical Bond (Cornell

U. P. , Ithaca, New York, 1960), p. 257.

~6R. A. Bromley, Phil. Mag. 23, 1417 (1971).

15 F EBRUARY 1972

VOLUME 5, NUMB ER 4

Observation

1479

of Wannier Levels in Semi-Insulating Gallium Arsenide

Robert

University

VV.

Koss

of &ermont, Burlington,

V'ermont

and

L.
Norwegian

M. Lambert*

Institute of Technology, Trondheim,

(Received 3 August 1971)

Norway

Optical absorption in an electric field has been of increased interest in recent years since
Callaway predicted that the Wannier levels may be observable in direct-transition semiconductors such as GaAs. In this work, such levels have been observed for the first time and found
to be in substantial agreement with the Callaway theory.

INTRODUCTION

This paper reports on an experimental investigation of the effect of a uniform external electric
field on optical absorption in semi-insulating GaAs.
Experimental data were obtained from room temperature to 24 'K for electric fields up to 1. 6x 10~
V/cm. The existence of Wannier levels was
clearly evident at 24 'K and agreed well with the
Callaway theory.
The direct-transition absorption coefficient
predicted by Callaway' using Kane functions was
given as
478K/ P

27Tg

I
g
7t'5'P

p.i'
flC pC

x =

qp

b.h w=

where
~

i'aK'/P'",

5 K

+E~ k~

(2)

To increase the value of qp by 1, it is necessary

to decrease the photon energy by

f=&p

2e'

louin zone along a principal lattice direction of the

is the electric field force, p, is the
applied field,
is the interband-moreduced effective mass, p
mentum matrix element, $ is the photon pola. rization vector, and n is the index of refraction.
The lower limit of the summation is given by
jp, where jp is dependent upon the photon energy
A~, and is the next integer greater than qp, where
qp is given by

=2vF/@',

and where A, (x) is the usual Airy function,

the photon frequency, E is the width of the

~ is
Bril-

2'/K .

Thus, when n is plotted as a function of increasing

photon energy for a given electric field, the result is a monotonically increasing staircase. The
width of each step is proportional to the electric
field as given by Eq. (3).
For small, uniform electric fields, theory pre-