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Some Electrical and Optical Properties of Znse: To) Ip: 80.111.243.8 On: Tue, 22 Apr 2014 10:41:46
Some Electrical and Optical Properties of Znse: To) Ip: 80.111.243.8 On: Tue, 22 Apr 2014 10:41:46
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JOURNAL OF APPLIED PHYSICS SUPPLEMENT TO VOL. 32. NO. 10 OCTOBER. 1961
Single crystals of ZnSe have been prepared by the vapor growth tained by preliminary transport measurements on n- and p-type
technique and optical and electrical measurements on these ZnSe gives tentative values of 0.1 ma and 0.6 ma for the electron
crystals are reported. Analysis of the reststrahlen reflection peak and hole masses, respectively.
gives 0.026 ev for the transverse optical phonon energy. The Reflectance was determined by various methods in the range
longitudinal optical phonon energy is 0.031 ev as calculated from 0.025 to 14.5 ev photon energy and was analyzed by the Kronig-
the transverse phonon energy, the static dielectric constant, Kramers inversion method to obtain the optical constants in the
Ea=8.1±0.3, and the high-frequency dielectric constant, 1 to 10 ev range. A number of peaks appear in the imaginary part
E",=5.75±0.1. The effective ionic charge calculated from the of the dielectric constant.
Szigetti formula is 0.7±0.1. Exciton absorption peaks associated The first set of peaks, 2.7 and 3.15 ev, are believed to be due to
with the valence and conduction bands in the vicinity of r were exciton and interband transitions at r with a spin-orbit valence
observed at liquid hydrogen temperature with the principal peak band splitting of 0.45 ev. The second set of peaks, 4.75 and 5.1 ev,
at 2.81±0.01 ev. The exciton reduced mass 0.1 ma combined with are tentatively assigned to transitions at L with a spin-orbit split-
the room temperature e1ectron-to-hole mobility ratio of 12, ob- ting of 0.35 ev. Other peaks are observed at higher energies.
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ELECTRICAL AND OPTICAL PROPERTIES OF ZnSe 2263
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
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,.,
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, MARPLE, AND SEGALL
V,n
~
\
\ln L 2
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
0
1
r k )
1-""'\
the mobility values in Table I for both electrons and
1
~20 1 2 4 5 6
PHOTON ENERGY e.
"-V ~
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
FIG. 4. Real and imaginary parts of the dielectric constant, the effective mass of holes. These assignments have to
(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 be regarded as tentative at this time, subject to revision
coefficient k were calculated from the results III Fig. 1 by the after more exhaustive transport measurements and
Kronig-Kramers inversion.
after elucidation of the scattering mechanisms.
In this connection it is worth noting that according
and acoustical branches of the phonon spectrum. A to the carrier concentration figures in Table I, native
spectrum qualitatively similar to Fig. 2 has been ob- imperfections have a strong influence on the position of
served in InSb,21 GaP22 and other materials. However, the Fermi level. ZnSe :Ga, for example, is but weakly
some of the structure seen in Fig. 2 may possibly be due n type, probably because most of the Ga donors are
to impurity absorption. Further analysis of the results compensated by Zn vacancies. ZnSe fired in Zn,
is in progress. which treatment is expected to produce either selenium
A consistent quantitative interpretation of the low vacancies or interstitial zinc, however, is strongly n type
temperature absorption shown in Fig. 3 is obtained by even without the addition of chemical donor impurities.
the assumption that the large peak is due to weakly In p-type samples this effect is less pronounced, both
bound direct excitons formed in the ground state and ZnSe :Cu and Se-fired ZnSe having about equal carrier
that the small secondary peak23 is the first excited state. concentrations.
The sharpness and strength indicate that the absorption Figure 4 shows the optical constants, expressed as
is a direct transition. the real and imaginary parts of the dielectric constant,
On the basis of our knowledge of the band structure for the energy range 1 to 10 ev, as calculated from the
of the compound semiconductors, it is plausible to as- room temperature reflectance, Fig. 1, by the Kramers-
sume that the smallest "vertical" gap is at r (i.e., at Kronig inversion procedure. 27 In this analysis the reflect-
k=O). Thus we believe that excitons are formed from ance at energies higher than 14.5 ev was extrapolated
the conduction band and upper valence band which assuming12 that d(logR)t/ d (loghv) = - 2.21 in order to
have respectively24 r6 and rs symmetries at k=O. If the bring the phase angle to zero in the transparent region
degeneracy in the rs valence band is neglected,25 the between 0.5 and 2.5 ev.
hydrogenic formula is correct in the limit of weak The small absorption peak at 2.70 ev calculated by
binding. The spacing of the peaks gives (0.020±0.004) the Kramers-Kronig inversion is in satisfactory agree-
ev for the exciton binding energy and (0.1O±0.03) mo ment with the absorption for room temperature given
for the exciton reduced mass. The oscillator strength in Fig. 3. It is interpreted as exciton absorption and the
for the ground state excitons calculated from the ab- onset of direct transitions at r. The bump at 3.15 ev in
sorption and the refractive index (not presented here) the imaginary part of the dielectric constant Fig. 4 is
is about 3 X 10-3 in satisfactory agreement with rough thought to be due to excitons formed from the "split-
theoretical estimates. The first excited state is roughly off", r7 valence band and the r6 conduction band, and
to direct transitions between the bands. That the life-
21 S. J. Fray, F. A. Johnson, and R. H. Jones, Proc. Phys. Soc.
(London) 76, 939 (1960). time of these excitons is appreciably shorter than the
22 D. A. Kleinman and W. G. Spitzer, Phys. Rev. 118, 110 lower-energy ones results from the fact that they can
(1960).
23 Observations of reflectance at normal incidence made near
undergo autoionization. The reflectance peak associated
liquid hydrogen temperature on one cleaved crystal with spectral with this absorption has also been observed at 23°K. At
resolution of 0.8 A confirm the existence of this second peak and this temperature it is considerably sharper, with peak
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. 26 H. Ehrenrei!,:h, J. Phys. Chern. Solids 8, 130 (1959).
24 The notation employed here is given in G. Dresselhaus Phys. 27 For an example and summary of the literature, see W. G.
Rev. 100, 580 (1955). Spitzer and D. A. Kleinman, Phys. Rev. 121, 1324 (1961), or
26 This degeneracy leads to errors which are probably small reference 12. We wish to thank D. S. Story who programmed and
compared to the experimental uncertainty in the line spacing. performed most of the calculations on an IBM 1620 computer.
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ELECTRICAL AND OPTICAL PROPERTIES OF ZnSe 2265
reflection at 3.22 ev and half-width very roughly 0.04 for Ge by Phillips.28 The relative magnitude of the
ev. From the energy difference for the two absorptions absorption at 4.7S and 6.4 ev and the width of the peak
at room temperature as evaluated from Fig. 4, one at 6.4 ev are comparable to the corresponding structure
obtains O.4S± 0.04 ev for the splitting of the valence observed in GeP We believe that interpretation of the
band at r due to spin-orbit interaction. structure above 6.4 ev, as well as confirmation of the
We suggest that the absorption peaks in Fig. 4 at assignment of the lower energy structure, will be greatly
4.75 and 5.10 ev are due to transitions between the two aided by improved calculations of the band structure
valence band states and the conduction band at LCi.e., of II-VI compounds, and by more accurate optical data.
k= 271"/ a(-U,~)]' The valence band splitting at L due
to spin-orbit interaction is theoretically expected to be ACKNOWLEDGMENTS
about i of that at r. Within the experimental error the
separation of the two peaks, 0.35±0.08 ev, is in accord We wish to thank H. R. Philipp and E. A. Taft for
with this prediction. assistance in obtaining the reflectance data in the 3.8
One may speculate that the absorption peak at 6.4 to 14.5 ev energy range, and for advice on the Kronig-
ev is due to transitions between the valence and con- Kramers inversion calculations, and Henry Ehrenreich
duction bands in the vicinity of XCi.e., k= 271"/ a (1,0,0)]' for stimulating discussions.
This ordering of the different direct-transition band
gaps suggested for ZnSe is the same as that suggested 28 J. C. Phillips, J. Phys. Chern. Solids 12, 208 (1960).
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.
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