Effect of thermal annealing on electrical and photoelectrical properties of n-InSb
InSb wafers of n-type conductivity were annealed at 300, 370, and 400 °C for 30 min in an open tube system under a flowing argon ambient. The conductivity type conversion is revealed for the first time in samples with the electron concentration ~1.0•10¹⁴ cm⁻³ for all annealing temperatures. Experime...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
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| Zitieren: | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb / S.V. Stariy, A.V. Sukach, V.V. Tetyorkin, V.O. Yukhymchuk, T.R. Stara // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 105-109. — Бібліогр.: 20 назв. — англ. |
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| author | Stariy, S.V. Sukach, A.V. Tetyorkin, V.V. Yukhymchuk, V.O. Stara, T.R. |
| author_facet | Stariy, S.V. Sukach, A.V. Tetyorkin, V.V. Yukhymchuk, V.O. Stara, T.R. |
| citation_txt | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb / S.V. Stariy, A.V. Sukach, V.V. Tetyorkin, V.O. Yukhymchuk, T.R. Stara // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 105-109. — Бібліогр.: 20 назв. — англ. |
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| container_title | Semiconductor Physics Quantum Electronics & Optoelectronics |
| description | InSb wafers of n-type conductivity were annealed at 300, 370, and 400 °C for 30 min in an open tube system under a flowing argon ambient. The conductivity type conversion is revealed for the first time in samples with the electron concentration ~1.0•10¹⁴ cm⁻³ for all annealing temperatures. Experimental evidences have been obtained that this phenomenon has a bulk character. In annealed samples, the spectral response exhibits a pronounced increase in the short-wave region. The effect of annealing on the electrical and photoelectrical properties of n-InSb has been explained by the formation of InSb antisites.
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| first_indexed | 2026-03-21T19:35:27Z |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 105-109.
doi: https://doi.org/10.15407/spqeo20.01.105
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
105
PACS 61.72.Cc, 07.57.Kp
Effect of thermal annealing on electrical and photoelectrical
properties of n-InSb
S.V. Stariy, A.V. Sukach, V.V. Tetyorkin, V.O. Yukhymchuk, T.R. Stara
V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, Ukraine
Phone (38 044) 525-54-61, e-mail: teterkin@isp.kiev.ua
Abstract. InSb wafers of n-type conductivity were annealed at 300, 370 and 400 °C for
30 min in an open tube system under flowing argon ambient. The conductivity type
conversion are revealed for the first time in samples with the electron concentration
~1.0·1014 cm–3 for all annealing temperatures. Experimental evidences have been
obtained that this phenomenon has a bulk character. In annealed samples the spectral
response exhibits pronounced increase in the short-wave region. The effect of annealing
on electrical and photoelectrical properties of n-InSb has been explained by formation of
InSb antisites.
Keywords: InSb, thermal annealing, conductivity type conversion, native defects,
indium antisites.
Manuscript received 14.11.16; revised version received 24.01.17; accepted for
publication 01.03.17; published online 05.04.17.
1. Introduction
In semiconductor technology, initial wafers of
semiconductor material are usually doped by diffusion
or ion implantation of impurity atoms. The doped
semiconductors are subjected to thermal annealing to
reduce a number of diffusion or implantation damages,
as well as to activate implanted ions. The conventional
long-term furnace annealing and rapid thermal annealing
(RTA) processes are used for this purpose. Both
processes have their own advantages and disadvantages.
For instance, the furnace annealing results in dopant
profile broadening as well as evaporation of volatile
component in AIIIBV and AIIBIV semiconductors. To
suppress the loss of volatile components, capsulation
layers are usually deposited onto the surface of samples.
The RTA seems to be more suitable for the processing of
implanted semiconductors, because it offers the
advantage of fast removing the implantation damages
together with the less dopant profile broadening. At the
same time, there are indications that the implanted
AIIIBV materials suffer from defects generated during
RTA [1]. As to InSb, it has been pointed out that the
stoichiometry of InSb in the surface region can be
destroyed by any annealing treatment at temperatures
exceeding 350 °C [2]. The RTA of Be implanted wafers
at temperatures higher than 350 °C show deficiency of
Sb in the subsurface layer [3]. Taking into account the
discrepant data on the annealing processes in InSb, the
aim of this work was to study the effect of furnace
annealing on electrical and photoelectrical properties of
InSb wafers as well as to clarify the nature of defects
generated by the annealing.
2. Experimental details
The samples for electrical and photoelectrical mea-
surements were cut from InSb (111) wafers of n-type
conductivity with the thickness close to 500 μm. The
etch pits density in the wafers was less than 102 cm–2. An
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 105-109.
doi: https://doi.org/10.15407/spqeo20.01.105
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
106
open tube system was used for the annealing of InSb
wafers in a flowing argon atmosphere at the
temperatures 300, 370 and 400 °C for 30 min. No
capsulation layers were deposited onto the surface of
samples. Electrical parameters of samples were obtained
from the Hall effect and specific resistance
measurements in the magnetic field 0.3 kOe. The
electron concentration in the reference samples was
close to 1.0·1014 cm–3 at 77 K. The photoconductivity
response and photoelectromagnetic effect (PEM)
measurements were carried out using the standard
technique with low-frequency modulation of radiation.
A weak signal condition δn, δp << n, p was fulfilled,
where δn and δp are the concentration of non-
equilibrium electrons and holes. The surfaces of samples
were mechanically polished and chemically etched
directly before measurements. The spectral distribution
of infrared radiation source (Globar) was determined
using a calibrated pyroelectric sensor. The photocurrent
spectra were measured in samples of p-type conductivity
doped for comparison.
3. Experimental results and discussion
The most important result of the furnace annealing is the
conductivity type conversion from an n-type to a p-type
observed at all annealing temperatures. Typical
temperature dependences of carrier concentration in the
reference (unannealed) and annealed samples are shown
in Fig. 1. As seen, in the annealed samples the hole
concentration increases with the annealing temperature
increase from 300 up to 370 °C and remains practically
unchanged at higher annealing temperatures. The hole
mobility exhibits slight increase in the whole range of
annealing temperatures, but its magnitude is several
times lower in comparison with the values published in
the literature [4] for p-type materials of high quality
(Fig. 2).
Fig. 3 shows the photocurrent spectra measured at
77 K. In the reference sample, the spectrum has the
typical shape for InSb single crystals, namely: the
photocurrent rises rapidly in the long-wave region,
reaches a peak value at the wavelengths λp ≈
5.3…5.4 µm and saturates in the short-wave region.
Note that the peak wavelength λp exceeds the
wavelength value λg = hc/Eg, which corresponds to the
energy gap Eg. The photocurrent saturates at the short
wavelengths with the magnitude that depends on the
surface treatment. For comparison, experimental
measurements were carried out for the surfaces etched in
CP4A and HBr+Br2 solutions (Fig. 3, curves 1 and 2,
respectively). By fitting the calculated and experimental
data, the surface recombination velocity of 7·103 and
1.4·104 cm/s was estimated for CP4A and HBr+Br2
solutions, accordingly. Similar values were obtained
earlier for InSb of n-type conductivity [4]. The details of
the photocurrent calculation in n-InSb are given in
Appendix. The important result was obtained for the
annealed sample of p-type conductivity (Fig. 4, curve 3).
As seen, in contrast with the reference sample the
photocurrent exhibited a marked increase in the short-
wave region. Note that this dependence was observed in
the annealed sample only. In the samples of p-type
conductivity doped in a conventional manner, photo-
current spectra had a shape similar to that shown in
Fig. 3 for n-InSb.
Fig. 1. Temperature dependences of electron and hole
concentration in the reference sample of n-type conductivity
(1) and annealed samples (2-4) of p-type conductivity. The
arrow marks the temperature of p-to-n transition.
2 4 6 8 10 12 14
103
104
105
μ,
c
m
2 / V
s
1000/T, K-1
300
370
400
n-type
Fig. 2. Carrier mobility vs temperature in the reference and
annealed samples. The designations are the same as in Fig. 1.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 105-109.
doi: https://doi.org/10.15407/spqeo20.01.105
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
107
Fig. 3. Photocurrent per incident photon spectra in the
reference (1, 2) and annealed at 300 °C (3) samples measured
at 77 K. The solid line represents the calculated spectrum. The
surface is etched in CP4A (1, 3) and HBr+Br2 (3) solutions.
In Fig. 4, the field dependences of PEM in InSb
samples of n- and p-type conductivities are shown.
Surface of the samples was etched in CP4A solution. In
the reference sample of n-InSb, PEM linearly depends
on the magnetic field B up to 12 kOe. Due to low
mobility of minority carriers (holes), the condition of
strong magnetic field µpH/c > 1 is not reached in this
case. By contrast, in the annealed sample of p-type
conductivity the field dependence of current IPME(H)
deviates from linearity at a relatively low magnetic field
(H = 1.5 kOe), indicating that the condition μnH/c >> 1
is reached for electrons. From the slope of IPME(H)
dependence, the electron mobility value was estimated to
be 8·104 cm2/V·s at 77 K.
In relation with the experimental data, several
remarks should be made. The conductivity type
conversion seems to be a bulk phenomenon. At least,
this conclusion was made for the investigated sample
annealed at the lowest temperature. To prove it, the sheet
resistance and thermoEMF was repeatedly measured in
the sample thinned by chemical etching up to the
thickness of ~100 µm. Obviously, there is no doubt that
this conclusion remains valid for higher annealing
temperatures. To interpret experimental data correctly,
there is a need to consider the nature as well as evolution
of native defects caused by thermal treatment.
Unfortunately, there are very few experimental studies
of native defects in bulk crystals and epilayers of InSb
[5-8]. At the same time, comprehensive theoretical
investigations were recently published in the literature
[9-11]. However, when comparing theoretical and
experimental data, difficulties arise due to the fact that
theoretical calculations were made for the thermal
equilibrium conditions, which cannot be entirely realized
in the annealing process. Thus, it is difficult to predict a
particular type of defects that can be realized in an
annealing process. In further analysis, experimental data
and theoretical models developed for the annealed GaAs
were also taken into account [12-14].
Since the investigated samples were not
encapsulated, the surface decomposition and preferential
evaporation of volatile component (Sb) from the surface
can occur [15]. Experimentally, in the investigated
samples an excess Sb at the surface has been detected by
Raman scattering measurements. Fig. 5 shows the room
temperature Raman spectra measured in the reference
and annealed samples. To prevent their heating during
measurements, the low-intensity laser excitation at the
wavelength 532 nm was used. As seen, in the initial
sample the spectrum consists of the bulk TO and LO
peaks at 178 and 187 cm–1, respectively, whereas in the
annealed samples two additional peaks at 115.5 and
155 cm–1 arose. These peaks can be attributed to Eg and
A1g modes of crystalline Sb [15].
Obviously, evaporation and segregation of Sb at the
surface results in formation of vacancies at the anion
sub-lattice. Beside vacancies, the most important native
point defects in A3B5 semiconductors are interstitials,
antisites and antisite pairs. The formation energies,
densities, atomic and electronic structures of grown-in
defects were theoretically analyzed in bulk crystals
under thermal equilibrium condition [9-11]. Different
charge states of these defects were modeled as a function
of the Fermi level. So, the impact of different growth
conditions on the formation energies was taken into
account. In InSb, possible acceptor defects are InSb
antisites and In vacancies. Generally, InSb antisites can
be neutral, singly and doubly negatively charged defects
[11]. Accordingly, SbIn antisites can be neutral, singly
and doubly negatively charged ones. However, the small
band gap of InSb limits formation of many charged
defects. Thus, only the neutral and –1 charge states for
InSb and the +1 and neutral charge states for SbIn are
possible [11]. SbIn antisites are more stable than the InSb
ones under Sb-rich condition, whereas under In-rich
condition InSb antisites are favored over SbIn. Due to the
difference in formation energies between the two
antisites is not large, both defects should be observed.
The antisite pairs InSb-SbIn are assumed to be neutral
[11]. The formation energies for InSb and SbIn antisites
under stoichiometric condition are estimated to be 1.46
and 1.29 eV, respectively [11]. The formation energies
of In and Sb vacancies for the same condition are 2.57
and 1.69 eV, accordingly [10]. Large difference between
the energies implies that antisite defects dominate over
vacancies under stoichiometric conditions, when the
Fermi level is Eg /2. However, under different growth
and doping conditions, vacancy energies can be lower
than those for antisites, and the dominant intrinsic defect
type may change.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 105-109.
doi: https://doi.org/10.15407/spqeo20.01.105
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
108
Fig. 4. Field dependences of photoelectromagnetic effect in the
reference (1) and annealed at 300 °C (2) samples measured at
77 K.
Fig. 5. Room temperature Raman spectra in the reference (1)
and annealed at 300 and 400 °C samples (curves 2 and 3,
respectively).
The p-type conversion called the thermal
conversion in GaAs subjected to RTA or furnace
annealing is known for many years [12-14]. Several
models of this phenomenon have been proposed in
literature, but today the most reasonable one is formation
of GaAs antisites [12-14]. It is clear from the above
analysis that Sb vacancies cannot be responsible for
conductivity type conversion due to their donor-like
nature. Similarly to that in GaAs, it can be assumed that
InSb antisites are mainly responsible for this phenomenon
in the annealed InSb. Together with In vacancies and
residual acceptors, they determine the hole concentration
in the annealed samples. If this assumption is true, it
means that Sb vacancies are not stable with respect to
formation of InSb antisites. Since the energy states of InSb
antisites are not known, the hole concentration at 77 K in
the annealed samples may be regarded as a lower limit
for the density of InSb antisites.
The important question is the spatial distribution of
native defects in the annealed samples. The
concentration of InSb antisites near the surface can be
considerably larger in comparison with the bulk one due
to several reasons. Obviously, the most simple reason is
the evaporation of Sb atoms from the surface. Another
possibility of the surface enrichment with native defects
has been pointed out by Höglund et al. [9]. Using the
density-functional theory, they showed that the higher
concentration of defects at the surface can be related to a
lower formation energy as compared to that of bulk
defects. The increased concentration of negatively
charged defects induces the band bending at the surface.
Beside these reasons, the band bending can arise due to
the Fermi pinning at the top of the valence band by the
surface states related to InSb antisites. In any case, the
band bending results in formation of an accumulation
layer as well as suppression of minority carrier
recombination. The appropriate model of photocon-
ductivity in semiconductors with the surface band
bending has been developed in [16]. The consequence of
this is the observed increase in the photocurrent in the
annealed samples of InSb.
4. Conclusions
The conductivity type conversion was observed in n-
InSb subjected the furnace annealing at temperatures
300, 370 and 400 °C for 30 min. The samples with the
unencapsulated surface were used for annealing.
Vacancies generated due to evaporation and segregation
of volatile component (Sb) are assumed to be unstable
with respect to formation of InSb antsites, which are
acceptors in InSb. Antisite defects are more easily
generated at the surface, which results in the band
bending and formation of an accumulation layer. It leads
to suppression of recombination of minority carriers
(electrons) at the surface and to increase of
photoresponse in the annealed samples. The density of
antisites has been estimated to be of the order of
(2…4)·1014 cm–3.
Appendix
Early results of experimental and theoretical
investigations of photoconductivity in InSb were
summarized in a number of monographs [17-20]. Below,
we will follow Smith [18]. The continuity equation for
the optically generated minority carriers (holes) is
expressed as
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2017. V. 20, N 1. P. 105-109.
doi: https://doi.org/10.15407/spqeo20.01.105
© 2017, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
109
( )xp
dx
pdD
p
α−ℜ=
τ
δ−δ exp2
2
, (A1)
where
.)1( ω−ηα=ℜ hRI (A2)
Here, I is the light intensity, Rs – surface reflection
coefficient, η – quantum efficiency, D – ambipolar
diffusion coefficient. Other symbols have their usual
meanings. The solution to equation (A1) for a thick
sample (d >> L) is given by
( )
1
)(exp
exp 22 −α
α−ℜτ
−−=δ
L
x
LxAp p , (A3)
where the constant A can be found from the boundary
condition
.psD dx
pd δ=δ
(A4)
The concentration of excess holes is
.
1
2
22
⎥
⎥
⎦
⎤
⎢
⎢
⎣
⎡
−
τ+
τ+α
−α
τℜ
=δ α−− xL
x
p
pp ee
sL
sL
L
p (A5)
In the above equations, transport of excess carriers
is governed by ambipolar diffusion and drift. Since in
this case the condition n >> p is fulfilled, the ambipolar
diffusion coefficient and mobility are defined by holes.
The spectral dependences of the absorption coefficient is
approximated by the expressions [20]
( ) 800109.1 2/14 +−ν×=α gEh (A6)
for λ < λg and
⎟⎟
⎠
⎞
⎜⎜
⎝
⎛ −ν
=α kT
Eh gexp8001 (A7)
for λ > λg. An appropriate expression for the temperature
dependence of the band gap is taken from [4]. The
calculated photocurrent is shown in Fig. 3.
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|
| id | nasplib_isofts_kiev_ua-123456789-214905 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2026-03-21T19:35:27Z |
| publishDate | 2017 |
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| spelling | Stariy, S.V. Sukach, A.V. Tetyorkin, V.V. Yukhymchuk, V.O. Stara, T.R. 2026-03-03T11:02:35Z 2017 Effect of thermal annealing on electrical and photoelectrical properties of n-InSb / S.V. Stariy, A.V. Sukach, V.V. Tetyorkin, V.O. Yukhymchuk, T.R. Stara // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2017. — Т. 20, № 1. — С. 105-109. — Бібліогр.: 20 назв. — англ. 1560-8034 PACS: 61.72.Cc, 07.57.Kp https://nasplib.isofts.kiev.ua/handle/123456789/214905 https://doi.org/10.15407/spqeo20.01.105 InSb wafers of n-type conductivity were annealed at 300, 370, and 400 °C for 30 min in an open tube system under a flowing argon ambient. The conductivity type conversion is revealed for the first time in samples with the electron concentration ~1.0•10¹⁴ cm⁻³ for all annealing temperatures. Experimental evidences have been obtained that this phenomenon has a bulk character. In annealed samples, the spectral response exhibits a pronounced increase in the short-wave region. The effect of annealing on the electrical and photoelectrical properties of n-InSb has been explained by the formation of InSb antisites. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Effect of thermal annealing on electrical and photoelectrical properties of n-InSb Article published earlier |
| spellingShingle | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb Stariy, S.V. Sukach, A.V. Tetyorkin, V.V. Yukhymchuk, V.O. Stara, T.R. |
| title | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb |
| title_full | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb |
| title_fullStr | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb |
| title_full_unstemmed | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb |
| title_short | Effect of thermal annealing on electrical and photoelectrical properties of n-InSb |
| title_sort | effect of thermal annealing on electrical and photoelectrical properties of n-insb |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/214905 |
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