Some Electrical and Optical Properties of ZnSe

M. Aven, D. T. F. Marple, and B. Segall

Citation: Journal of Applied Physics 32, 2261 (1961); doi: 10.1063/1.1777056

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 JOURNAL OF APPLIED PHYSICS SUPPLEMENT
Some Electrical and Optical Properties of ZnSe
M. AVEN, D. T. F. MARPLE, AND B. SEGALL
General Electric Research Laboratory, Schenectady, New York
Single crystals of ZnSe have been prepared by the vapor growth
technique and optical and electrical measurements on these
crystals are reported. Analysis of the reststrahlen reflection peak
gives 0.026 ev for the transverse optical phonon energy. The
longitudinal optical phonon energy is 0.031 ev as calculated from
the transverse phonon energy, the static dielectric constant,
Ea=8.1±0.3, and the high-frequency dielectric constant,
E",=5.75±0.1. The effective ionic charge calculated from the
Szigetti formula is 0.7±0.1. Exciton absorption peaks associated
with the valence and conduction bands in the vicinity of r were
observed at liquid hydrogen temperature with the principal peak
at 2.81±0.01 ev. The exciton reduced mass 0.1 ma combined with
the room temperature e1ectron-to-hole mobility ratio of 12, ob-
INTRODUCTION
P AST work on ZnSe has been mainly concerned with
its photoluminescent! and photoconductive2 prop-
erties. Recently several workers3 •4 have reported on the
synthesis of large single crystals of ZnSe. Larson,
Pedrotti, and Reynolds" as well as Halsted and Aven 6
have reported on the edge emission. Marple, Segall, and
Aven4 have described exciton absorption and infrared
reflection spectra.
The present paper is an extension of the work de-
scribed in reference 4. Optical studies now include inves-
tigation and partial interpretation of the optical con-
stants at energies higher than the optical band gap, and
observations of absorption bands on the high-energy
side of the reststrahlen absorption. The electrical work
to be reported is a preliminary investigation of the
electron and hole transport properties.
SAMPLE PREPARATION
ZnSe crystals were grown by the vapor growth
technique first reported by Greene, Reynolds, Czyzak,
and Baker7 and modified by Piper and Polich. 8 The
starting material was G.E. Chemical Products Plant
ZnSe powder which was first sintered in the presence of
excess Se in a hydrogen atmosphere. The sintered
material was then passed at the rate of approximately
0.2 mm/hr through a furnace heated to about 13S0°C,
which sublimed the ZnSe to the cold end of the growing
tube. The product was usually a boule of several cm3
1 R. E. Shrader, S. Lasof, and H. W. Leverenz, Solid Lumines-
cent Materials, Cornell University Symposium (John Wiley &
Sons, Inc., New York, 1946), pp. 215-257.
2 R. H. Bube and E. L. Lind, Phys. Rev. 110, 1040 (1958).
3 A. G. Fisher, Bull. Am. Phys. Soc. 6, 17 (1961).
4 D. T. F. Marple, B. Segall, and M. Aven, Bull. Am. Phys.
Soc. 6, 19 (1961).
I; O. W. Larson, L. S. Pedrotti, and D. C. Reynolds, Bul!. Am.
Phys. Soc. 6, 111 (1961).
• R. E. Halsted and M. Aven, Bull. Am. Phys. Soc. 6, 312
(1961).
7 L. C. Greene, D. C. Reynolds, S. J. Czyzak, and W. M. Baker,
J. Chern. Phys. 29, 1375 (1958).
8 W. W. Piper and S. Polich, J. App!. Phys. 32, 1278 (1961).
2261
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TO VOL. 32. NO. 10 OCTOBER. 1961
tained by preliminary transport measurements on n- and p-type
ZnSe gives tentative values of 0.1 ma and 0.6 ma for the electron
and hole masses, respectively.
Reflectance was determined by various methods in the range
0.025 to 14.5 ev photon energy and was analyzed by the Kronig-
Kramers inversion method to obtain the optical constants in the
1 to 10 ev range. A number of peaks appear in the imaginary part
of the dielectric constant.
The first set of peaks, 2.7 and 3.15 ev, are believed to be due to
exciton and interband transitions at r with a spin-orbit valence
band splitting of 0.45 ev. The second set of peaks, 4.75 and 5.1 ev,
are tentatively assigned to transitions at L with a spin-orbit split-
ting of 0.35 ev. Other peaks are observed at higher energies.
containing single crystal regions of a tenth to one cm3 •
Doped crystals were grown by adding the impurity to
the ZnSe powder prior to the sintering. Native imper-
fections were introduced, when desired, by firing the
crystals in Se or Zn. Sample bars approximately
1 cm long and 4 mm2 in cross-sectional area were cut
from the boules described above. Prior to electroding
the bars were chemically polished in hot concentrated
N aOH. The electrode material was In for the n-type
and In-Ag alloy for the p-type samples. Various sizes
and shapes of cleaved or polished crystals, depending
on the type of measurement and the spectral range,
were used in the optical work.
EXPERIMENTAL
Figure 1 shows the reflectance of ZnSe at room tem-
perature in the range 0.026 to 14.5 ev. Data included
here were obtained on a variety of crystals by several
different methods. In the region 0.026 to 0.05 ev meas-
urements were made on thick mechanically polished
sections cut from three different boules. Conventional
arrangements were used with a double-pass CsI prism
monochromator. In the 0.05 to 2.5 ev range the reflect-
ance given in Fig. 1 was calculated from the refractive
index. In the 1.8 to 2.5 ev range the index was calculated
from refraction produced by a ZnSe prism. Interference
fringes were observed in transmission through a S.3S,u
thick mechanically polished crystal in the range 0.4 to
2.4 ev with a double-pass CaF 2 prism spectrometer9 and
in a 114,u thick mechanically polished crystal with a
prism-grating spectrometer in the range 0.04 to 0.5 ev.
Matching the dispersion and magnitude of the index in
the overlapping regions and the reflectance directly
measured at 0.04 ev made possible a unique assignment
of interference orders in the analysis of the fringe data,
and hence a determination of both the index and the
crystal thicknesses.
Reflectance in the 2.5 to 3.8 ev range was twice
9 The optical arrangement was similar to the equipment de-
scribed by W. W. Piper, D. T. F. Marple, and P. D. Johnson,
Phys. Rev. 110, 323 (1958).
 2262 AVEN, MARPLE,
measured on a cleaved face of a single crystal, first a
few hours after cleaving and again after about 500-hr
exposure to still air. The equipment described in refer-
ence (9) was slightly modified for these measurements,
and a freshly evaporated Al mirror was used for a cali-
bration standard.lO No systematic differences in the two
measurements were found, and the average values are
given in Fig. 1.
Reflectance in the 3.8 to 14.5 ev range was measured
with a vacuum ultraviolet monochromatorll •12 on three
crystals. Two of these were measured a few hours after
cleaving and the third after about 800-hr exposure to
air. This last crystal was remeasured after chemical
polishing with NaOH.13 With the possible exception of
the region above 10 ev, no systematic differences were
found between these four surfaces, and the average
reflectance at each energy for the group, normalized to
match the absolute value found at 3.8 ev, is shown in
Fig. 1. The angle of incidence in all the reflection meas-
urements was less than 15 deg, and the results were
analyzed with the theory for normal incidence.
It is quite difficult to estimate the possible systematic
errors in the reflectance measurements in Fig. 1 espe-
cially at energies of 2.6 ev and more. Aside from possible
systematic errors connected with the condition of the
sample surface, the absolute reflectance near 2.6 ev is
believed to be correct within ±5% of the value stated,
with increasing possible systematic error up to ± 15%
beyond 7 ev. Random errors, due to detector noise for
example, would influence the shape of small details in
the curve, and are believed to be about ±0.OO5 in the
reflectance.
Transmission through three mechanically polished
samples cut from two different boules, with thicknesses
14.1, 114, and 2590 JJ. was measured with the double-
pass CsI prism spectrometer. Figure 2 shows the ab-
sorption coefficient in the range 0.031 to 0.08 ev as
calculated from these data. Corrections for reflection
loss were made with the results shown in Fig. 1. Widely
spaced interference fringes were observed in the thinnest
crystal, and although the results for the absorption peak
at 0.037 ev, are qualitatively reliable, they are less
accurate than the rest due to the difficulties in the
analysis of the fringes.
Optical properties in the absorption edge region, 2.6
to 2.9 ev received further study at room temperature
and near liquid hydrogen temperature. Results for the
absorption coefficient are shown in Fig. 3. Transmission
was measured on two mechanically polished crystals,
one 4.1 and the other 5.35 JJ. thick, for energies where
the absorption coefficient was less than about 2X 104
10 G. Hass, J. Opt. Soc. Am. 45, 945 (1955).
11 P. D. Johnson, J. Opt. Soc. Am. 42, 278 (1952).
12 The same procedure, with almost the same numerical value
was used for Ge. See H. R. Philipp and E. A. Taft Phys Rev
113, 1002 (1959). ' .
.13 The. mec~~nically polished crystal was immersed for one
mm,:,te m bOllmg 50% NaOH, followed by a rinse in briskly
flowmg tap water at 70°C followed by a rinse in distilled water.
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AND SEGALL
o.9
o. 8 f FIG. 1. Reflectance of
ZnSe for near-normal inci-
dence as a function of
o.7
photon energy at room
o. 6 temperature.
o. 5
o.4
o. 3 /1/\
/ v If'
o. 2
~
t-
/~
O. I
I/V
o
0.01 Q02 0.05 0.1 I 2 10 20
PHOTON ENERGY ev
cm-l . The optical constants also were measured by
reflection of polarized light at 80° angle of incidence. 14
Crystals used in these measurements had reflecting
faces about 6X8 mm, were about 2 mm thick and were
cemented to copper plates which could be cooled by a
cryostat. For the low-temperature measurements the
crystal was entirely enclosed in a metal-and-glass shield
also cooled by the cryostat. No changes in the optical
constants were observed during a period of eight hours
near liquid hydrogen temperature. Two cleaved crystal
faces and two chemically polished surfaces were studied
at low temperatures, but only the data for one crystal
was included in Fig. 3. The other crystals gave qualita-
tively similar results, but at low temperature the large
absorption peak was shifted by up to 0.01 ev from the
results presented here. The cause of this shift is not
known, but is possibly associated with strains or im-
purities in the crystals. Both the transmission and
reflection data in Fig. 3 were obtained on sections of the
same boule. The sharp structure shown in Fig. 3 was
entirely absent in mechanically polished. crystals.
:Measurements of transport properties in ZnSe are at
present in a preliminary stage. Such measurements are
complicated by the tendency of ZnSe (as well as most
other wide band-gap II-VI compounds) to compensate
the intentionally added donor or acceptor impurities
through formation of native imperfections, vacancies or
interstitials. An additional complication in p-type sul-
fides and selenides of zinc and cadmium arises from the
relatively large hole ionization energy, between 0.5 and
1.2 ev in these materials. The Hall effect apparatus
built for these measurements covered the temperature
range from room temperature up to about 600°C, and
operated on currents between 10-3 and 10-11 amp. The
measurements were performed by applying a dc poten-
tial, usually of the order of 0.1 v, across the long
dimension of the crystal. The current through the
crystal was ascertained by measuring the potential drop
across a standard resistor in series with the crystal.
The potential drop across the crystal and the Hall
. voltage were measured by two sets of appropriately
14 Apparatus and techniques described by S. Roberts, Phys.
Rev. 114, 104 (1959); 118, 1509 (1960).
 ELECTRICAL AND OPTICAL PROPERTIES OF ZnSe 2263

TABLE I. Mobilities and carrier concentrations for doped WAVELENGTH ANGSTROMS

and un doped ZnSe. 4700 4650 4600 4550 4500 4450 4400 4350 4300
n:' ...
..11-- I ~~~mi6l.,
Carrier

Material (OC)
Mobility
2
Temp. range (cm /v-sec)
concentration
(em- 3 )
Electrons Holes 27°C 200°C
0

2. 5
.
°
6
300 -I(
23°1(

300 OK }
} REFLECTION OF
POLARIZED RADIATION
- l-
I- :1I-ITr.~=:~:~NI

TRANSMISSION

ZnSe:Cu 200-400 11 1010

0
• 23·K

ZnSe:Cu, Se-fired 130-260 16 1011

ZnSe, Se-fired 200-400 15 1010
ZnSe:Ga 27-400 80 106 .5
ZnSe:Ga, Zn-fired 27 150 1016 n'2
ZnSe, Zn-fired 27-250 260 1016 0 J..
I~ (
located electrodes on the faces of the crystal. The
5

L,#
°V
Y
. .,, II
. .J
2.64 2.66 2.68 2.70 2.80 2.86
measurements were performed with an Applied Physics PHOTON ENERGY,.,

Corporation vibrating reed electrometer. Magnetic

fields between 5 and 6 kgauss were used.
Although measurements were made at a number of
different temperatures, the limited range covered does
not allow a reliable mobility-temperature relationship
to be established at this time. Table I lists the average
mobilities in the temperature range covered for three
types of samples for each conductivity type. The carrier
concentrations are given for room temperature for the
n-type samples. The p-type samples had too high resis-
tivity for reproducible Hall measurements at room
temperature, and therefore the carrier concentrations
for these samples are given for 200°C.
DISCUSSION
The reststrahlen reflection peak at 0.026 ev was fitted
with the classical theory for a single resonance absorp-
~ energy with the Lyddane-Sachs-Teller formula 16 is
I~
I
I ~
I
FIG. 3. Absorption coefficient a for ZnSe in the absorption edge
region as a function of photon energy.
tion,t5 ignoring the small reflection anomaly at 0.037 ev
which is associated with the absorption peak at about
the same energy. The static dielectric constant was
found to be 8.1±0.3 from capacitance measurements on
a single-crystal wafer about 0.015 cm thick and 1.5 em
in diameter. Analysis of the refractive index data gave
5.75±0.1 for the high-frequency dielectric constant.
With these constants inserted in the equations at the
outset the data could be fitted within the scatter in the
data with a resonance energy of 0.026 ev. The absorp-
tion coefficient as calculated from the reflection is
included in Fig. 2 and agrees satisfactorily with the
transmission results where they overlap. The largest
absorption peak is due to transverse optical phonons at
or near the center of the Brillouin zone. The longitu-
dinal phonon energy calculated from the above resonance
0.031 ev, in agreement with the structure observed in
luminescence at energies near the absorption edge by
HalstedP

103
? I
I
~ The effective ionic charge sZ has been discussed by
Szigetti 18 and Callen19 among others. With the dielectric
I

I
I
I
I
V 0
constants and reststrahlen frequency reported above
the Szigetti formula gives sZ = O. 70. From the stand-
point of effective charge ZnSe i3 intermediate in
~
u
.;, 10 2
J "ionicity" compared to the other "fourth-row" com-

\
pounds, as sZ for CuBr and GaAs are 1.00 and 0.43,
d
I
~ respectively.'8,20
We believe that the series of weaker absorption peaks
I
seen in Fig. 2 are due at least in part to multiple
10 I
o CALCULATED FROM phonon absorption processes involving both the optical
\
r\~
REFLECTION
o d= 14.IJl
o d' 114 Jl 10 For a convenient summary see T. S. Moss, Optical Properties
6 d' 2590Jl of Semiconductors (Butterworth Scientific Publications Ltd.,
I I London, 1959), pp. 15-22.
I
A: 16 R. H. Lyddane, R. G. Sachs, and E. Teller, Phys. Rev. 59,
673 (1941).
o ~ ~ ~ ~ ~ ~ ~ ~ 17 R. E. Halsted (private communication).
PHOTON ENERGY IV 18 B. Szigetti, Trans. Faraday Soc. 45, 155 (1949).
19 H. B. Callen, Phys. Rev. 76, 1394 (1949).
FIG. 2. Absorption coefficient a for ZnSe in the infrared region 20 G. Picus, E. Burstein, B. W. Henvis, and M. Hass, J.
as a function of photon energy at room temperature. Phys. Chem. Solids 8, 282 (1959).

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 2264 AVEN,
II
0 cally it is expected to be about i as strong.
9
S A- V ~\ 11\
7
6 ~
(n2~ V II IL \ - - 2nk
5 II \ / ' "\ \ temperature range covered the dominant mobility-
4
'- /-..... ~
3
2
71
V,n
~
\
\ln L 2
0
1
r k )
1
~20 1 2 4 5 6
PHOTON ENERGY e.
"-V
FIG. 4. Real and imaginary parts of the dielectric constant,
(n2 -k 2 ) and 2nk respectively, for ZnSe as a function of photon
energy at room t~mperature. The refractive inde~ n a~d extinction
coefficient k were calculated from the results III Fig. 1 by the
Kronig-Kramers inversion.
and acoustical branches of the phonon spectrum. A
spectrum qualitatively similar to Fig. 2 has been ob-
served in InSb,21 GaP22 and other materials. However,
some of the structure seen in Fig. 2 may possibly be due
to impurity absorption. Further analysis of the results
is in progress.
A consistent quantitative interpretation of the low
temperature absorption shown in Fig. 3 is obtained by
the assumption that the large peak is due to weakly
bound direct excitons formed in the ground state and
that the small secondary peak23 is the first excited state.
The sharpness and strength indicate that the absorption
is a direct transition.
On the basis of our knowledge of the band structure
of the compound semiconductors, it is plausible to as-
sume that the smallest "vertical" gap is at r (i.e., at
k=O). Thus we believe that excitons are formed from
the conduction band and upper valence band which
have respectively24 r6 and rs symmetries at k=O. If the
degeneracy in the rs valence band is neglected,25 the
hydrogenic formula is correct in the limit of weak
binding. The spacing of the peaks gives (0.020±0.004)
ev for the exciton binding energy and (0.1O±0.03) mo
for the exciton reduced mass. The oscillator strength
for the ground state excitons calculated from the ab-
sorption and the refractive index (not presented here)
is about 3 X 10-3 in satisfactory agreement with rough
theoretical estimates. The first excited state is roughly
21 S. J. Fray, F. A. Johnson, and R. H. Jones, Proc. Phys. Soc.
(London) 76, 939 (1960).
22 D. A. Kleinman and W. G. Spitzer, Phys. Rev. 118, 110
(1960).
23 Observations of reflectance at normal incidence made near
liquid hydrogen temperature on one cleaved crystal with spectral
resolution of 0.8 A confirm the existence of this second peak and
give a more accurate measurement of the peak spacing than is
shown in Fig. 3. The width of both peaks at half-maximum ab-
sorption coefficient is 4± 1.5 A.
24 The notation employed here is given in G. Dresselhaus Phys.
Rev. 100, 580 (1955).
26 This degeneracy leads to errors which are probably small
compared to the experimental uncertainty in the line spacing.
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MARPLE, AND SEGALL
a factor of ten weaker in oscillator strength. Theoreti-
It is possible to obtain an estimate of the effective
masses of electrons and holes from the exciton reduced
t--~
mass given above and the mobility ratio obtained from
the transport measurements. Assuming that in the
limiting mechanism is scattering by longitudinal optical
phonons, the ratio of the hole and electron masses is
given by26 mh/me= (JJ.e/JJ.h)i. By using the averages for
1-""'\
the mobility values in Table I for both electrons and
~
10
holes, the above equation in conjunction with the
exciton reduced mass of 0.1 mo yields approximately
0.1 mo for the effective mass of electrons and 0.6 mo for
the effective mass of holes. These assignments have to
be regarded as tentative at this time, subject to revision
after more exhaustive transport measurements and
after elucidation of the scattering mechanisms.
In this connection it is worth noting that according
to the carrier concentration figures in Table I, native
imperfections have a strong influence on the position of
the Fermi level. ZnSe :Ga, for example, is but weakly
n type, probably because most of the Ga donors are
compensated by Zn vacancies. ZnSe fired in Zn,
which treatment is expected to produce either selenium
vacancies or interstitial zinc, however, is strongly n type
even without the addition of chemical donor impurities.
In p-type samples this effect is less pronounced, both
ZnSe :Cu and Se-fired ZnSe having about equal carrier
concentrations.
Figure 4 shows the optical constants, expressed as
the real and imaginary parts of the dielectric constant,
for the energy range 1 to 10 ev, as calculated from the
room temperature reflectance, Fig. 1, by the Kramers-
Kronig inversion procedure. 27 In this analysis the reflect-
ance at energies higher than 14.5 ev was extrapolated
assuming12 that d(logR)t/ d (loghv) = - 2.21 in order to
bring the phase angle to zero in the transparent region
between 0.5 and 2.5 ev.
The small absorption peak at 2.70 ev calculated by
the Kramers-Kronig inversion is in satisfactory agree-
ment with the absorption for room temperature given
in Fig. 3. It is interpreted as exciton absorption and the
onset of direct transitions at r. The bump at 3.15 ev in
the imaginary part of the dielectric constant Fig. 4 is
thought to be due to excitons formed from the "split-
off", r7 valence band and the r6 conduction band, and
to direct transitions between the bands. That the life-
time of these excitons is appreciably shorter than the
lower-energy ones results from the fact that they can
undergo autoionization. The reflectance peak associated
with this absorption has also been observed at 23°K. At
this temperature it is considerably sharper, with peak
26 H. Ehrenrei!,:h, J. Phys. Chern. Solids 8, 130 (1959).
27 For an example and summary of the literature, see W. G.
Spitzer and D. A. Kleinman, Phys. Rev. 121, 1324 (1961), or
reference 12. We wish to thank D. S. Story who programmed and
performed most of the calculations on an IBM 1620 computer.
 ELECTRICAL AND OPTICAL PROPERTIES OF ZnSe 2265

reflection at 3.22 ev and half-width very roughly 0.04
ev. From the energy difference for the two absorptions
at room temperature as evaluated from Fig. 4, one
obtains O.4S± 0.04 ev for the splitting of the valence
band at r due to spin-orbit interaction.
We suggest that the absorption peaks in Fig. 4 at
4.75 and 5.10 ev are due to transitions between the two
valence band states and the conduction band at LCi.e.,
k= 271"/ a(-U,~)]' The valence band splitting at L due
to spin-orbit interaction is theoretically expected to be
about i of that at r. Within the experimental error the
separation of the two peaks, 0.35±0.08 ev, is in accord
with this prediction.
One may speculate that the absorption peak at 6.4
ev is due to transitions between the valence and con-
duction bands in the vicinity of XCi.e., k= 271"/ a (1,0,0)]'
This ordering of the different direct-transition band
gaps suggested for ZnSe is the same as that suggested
for Ge by Phillips.28 The relative magnitude of the
absorption at 4.7S and 6.4 ev and the width of the peak
at 6.4 ev are comparable to the corresponding structure
observed in GeP We believe that interpretation of the
structure above 6.4 ev, as well as confirmation of the
assignment of the lower energy structure, will be greatly
aided by improved calculations of the band structure
of II-VI compounds, and by more accurate optical data.
ACKNOWLEDGMENTS
We wish to thank H. R. Philipp and E. A. Taft for
assistance in obtaining the reflectance data in the 3.8
to 14.5 ev energy range, and for advice on the Kronig-
Kramers inversion calculations, and Henry Ehrenreich
for stimulating discussions.
28 J. C. Phillips, J. Phys. Chern. Solids 12, 208 (1960).

JOURNAL OF APPLIED PHYSICS SUPPLEMENT TO VOL. 32, NO. 10 OCTOBER, 1961

Band Structure of HgSe and HgSe-HgTe Alloys

T. C. HARMAN AND A. J. STRAUSS
Lincoln Laboratory,* Massachusetts Institute of Technology, Lexington 73, Jfassachusetts

A detailed analysis of Hall coefficient data obtained at temperatures between 77° and 350 0 K has been
made for HgSe and HgSeo.5Teo.5 samples containing excess donor concentrations up to 1019 em-a. On the
basis of previous magnetoresistance, Seebeck coefficient, and reflectivity data, a spherically symmetric non-
quadratic conduction band exhibiting the E(k) dependence described by Kane was adopted in making the
analysis. Calculations based on a conventional two-band model failed to give quantitative agreement with
experiment, but good agreement was obtained on the basis of a model in which the conduction band and one
valence band overlap in energy. Therefore the materials are semimetals rather than semiconductors. The
best fit to the data was obtained with an overlap energy of 0.07 ev for both HgSe and HgSeO.5Teo.5, with
hole density-of-states masses of 0.17 /no and 0.30 /no, respectively. With increasing carrier concentration,
the optical absorption edge for heavily doped HgSe exhibits a shift to higher energies which is characteristic
of n-type materials with low electron effective masses. Qualitatively, the optical data are consistent with a
semimetal band model rather than with a semiconductor model, since the interband absorption edge ap-
parently occurs at photon energies less than the Fermi energy.

INTRODUCTION ev, without specifying the nature of the experimental

T HE II-VI compounds HgSe and HgTe, which
crystallize in the zinc-blende structure, form a
continuous series of pseudo binary solid solutions.
Values of 0.01-0.02 ev for the energy gap of HgTe
have been obtained by several authors1- s who analyzed
the variation of Hall coefficient with temperature on
the basis of a simple two-band semiconductor model.
Zhuze 6 has reported the energy gap of HgSe to be 0.12
* Operated with support from the U. S. Army, Navy, and Air
Force.
1 I. M. Tsidilkovski, Zhur. Tekh. Fiz. (USSR) 27,1744 (1957).
2 T. C. Harman, M. J. Logan, and H. L. Goering, J. Phys.
Chern. Solids 7, 228 (1958).
3 R. O. Carlson, Phys. Rev. 111, 476 (1958).
4 J. Black, S. M. Ku, and H. T. Minden, J. Electrochem. Soc.
105, 723 (1958).
5 W. D. Lawson, S. Nielsen, E. H. Putley, and A. S. Young, J.
Phys. Chern. Solids 9, 325 (1959).
6 V. P. Zhuze, Zhur. Tekh. Fiz. (USSR) 25, 2079 (1955).
data or the band model employed, while Goodman 7 has
predicted a gap of 0.7 ev for HgSe on theoretical
grounds. No energy gap values for HgSe-HgTe alloys
have been reported.
In the present investigation, the variation of Hall
coefficient and resistivity with temperature has been
determined experimentally for samples of HgSe and the
following alloys: HgSeo.75Teo.25, HgSeo.5Teo.5, and
HgSeO.25TeO.75' A detailed analysis has been made of the
Hall coefficient data for HgSe and HgSeO.6Teo.5 samples
varying widely in net donor concentration. It has not
been possible to explain these data on the basis of a
simple two-band model. Good agreement with experi-
ment is obtained, however, with a band model in which
the conduction band and one valence band overlap
7 C. H. L. Goodman, Proc. Phys. Soc. (London) B67, 258
(1954).

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