Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions
The chemical etching of Ві₂Те₃ and n-(Ві₂Те₃)₀.₉(Sb₂Te₃)₀.₀₅(Sb₂Se₃)0.05 and p- (Bi₂Te₃)₀.₂₅(Sb₂Te₃)₀.₇₂(Sb₂Se₃)₀.₀₃ crystals of solid solutions with HNO₃–HCl etchant compositions was investigated. The dependences of dissolution rate of these semiconductors on etchant composition, stirring, te...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2011
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| Назва видання: | Semiconductor Physics Quantum Electronics & Optoelectronics |
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| Цитувати: | Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions / I.I. Pavlovich, Z.F. Tomashik, I.B. Stratiychuk, V.M. Tomashik, O.A. Savchuk, A.S. Kravtsova // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 2. — С. 200-202. — Бібліогр.: 8 назв. — англ. |
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irk-123456789-1177192017-05-27T03:03:14Z Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions Pavlovich, I.I. Tomashik, Z.F. Stratiychuk, I.B. Tomashik, V.M. Savchuk, O.A. Kravtsova, A.S. The chemical etching of Ві₂Те₃ and n-(Ві₂Те₃)₀.₉(Sb₂Te₃)₀.₀₅(Sb₂Se₃)0.05 and p- (Bi₂Te₃)₀.₂₅(Sb₂Te₃)₀.₇₂(Sb₂Se₃)₀.₀₃ crystals of solid solutions with HNO₃–HCl etchant compositions was investigated. The dependences of dissolution rate of these semiconductors on etchant composition, stirring, temperature and their shelf-time storage have been studied. It was shown that the process of dissolution of the investigated materials in the polishing solutions HNO₃–HCl is limited by the diffusion stages. 2011 Article Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions / I.I. Pavlovich, Z.F. Tomashik, I.B. Stratiychuk, V.M. Tomashik, O.A. Savchuk, A.S. Kravtsova // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 2. — С. 200-202. — Бібліогр.: 8 назв. — англ. 1560-8034 PACS 77.84.Bw, 81.65.Cf, Ps http://dspace.nbuv.gov.ua/handle/123456789/117719 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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The chemical etching of Ві₂Те₃ and n-(Ві₂Те₃)₀.₉(Sb₂Te₃)₀.₀₅(Sb₂Se₃)0.05 and p-
(Bi₂Te₃)₀.₂₅(Sb₂Te₃)₀.₇₂(Sb₂Se₃)₀.₀₃ crystals of solid solutions with HNO₃–HCl etchant
compositions was investigated. The dependences of dissolution rate of these
semiconductors on etchant composition, stirring, temperature and their shelf-time storage
have been studied. It was shown that the process of dissolution of the investigated
materials in the polishing solutions HNO₃–HCl is limited by the diffusion stages. |
| format |
Article |
| author |
Pavlovich, I.I. Tomashik, Z.F. Stratiychuk, I.B. Tomashik, V.M. Savchuk, O.A. Kravtsova, A.S. |
| spellingShingle |
Pavlovich, I.I. Tomashik, Z.F. Stratiychuk, I.B. Tomashik, V.M. Savchuk, O.A. Kravtsova, A.S. Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Pavlovich, I.I. Tomashik, Z.F. Stratiychuk, I.B. Tomashik, V.M. Savchuk, O.A. Kravtsova, A.S. |
| author_sort |
Pavlovich, I.I. |
| title |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions |
| title_short |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions |
| title_full |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions |
| title_fullStr |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions |
| title_full_unstemmed |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions |
| title_sort |
chemical-dynamic polishing of semiconductor materials based on bi and sb chalcogenides by using hno₃–hcl solutions |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2011 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/117719 |
| citation_txt |
Chemical-dynamic polishing of semiconductor materials based on Bi and Sb chalcogenides by using HNO₃–HCl solutions / I.I. Pavlovich, Z.F. Tomashik, I.B. Stratiychuk, V.M. Tomashik, O.A. Savchuk, A.S. Kravtsova // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 2. — С. 200-202. — Бібліогр.: 8 назв. — англ. |
| series |
Semiconductor Physics Quantum Electronics & Optoelectronics |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 2. P. 200-202.
PACS 77.84.Bw, 81.65.Cf, Ps
Chemical-dynamic polishing of semiconductor materials
based on Bi and Sb chalcogenides by using HNO3–HCl solutions
I.I. Pavlovich, Z.F. Tomashik, I.B. Stratiychuk, V.M. Tomashik, O.A. Savchuk, A.S. Kravtsova
V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine,
41, prospect Nauky, 03028 Kyiv, Ukraine, Phone: 38 (044) 525-57-55, e-mail: tomashyk@isp.kiev.ua
Abstract. The chemical etching of Ві2Те3 and n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 and p-
(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 crystals of solid solutions with HNO3–HCl etchant
compositions was investigated. The dependences of dissolution rate of these
semiconductors on etchant composition, stirring, temperature and their shelf-time storage
have been studied. It was shown that the process of dissolution of the investigated
materials in the polishing solutions HNO3–HCl is limited by the diffusion stages.
Keywords: chemical etching, etchant, solid solutions, bismuth telluride, etching rate,
chemical-dynamic polishing.
Manuscript received 14.10.10; accepted for publication 16.03.11; published online 30.06.11.
1. Introduction
Solid solutions based on Bi and Sb chalcogenides are
highly efficient thermoelectric materials for low-
temperature zone (T < 220 K) [1]. Currently, these
materials have no alternative both in thermoeffectivity in
this temperature range and in terms of their practical use
for production of thermoelectric energy converters. In
making the devices based on semiconductor materials
the problem of getting high quality of surface at the final
stage of chemical treatment remains one of the topical
ones in the modern semiconductor materials science [2].
In practice, to prepare surface with a needed quality,
usually used is chemical-dynamic polishing (CDP) in
specially selected etching compositions [3].
Thus, for the chemical treatment of Ві2Те3, the
authors [4] used I2 solution in methanol, as the result
they got triangular etching pits on the surface, which
density was . For etchant preparation, they have
mixed iodine with HCl and heated to 60 ºC, cooled to
room temperature and then added other components of
etchant. After etching, the samples were washed in HCl,
water and dried up in air flow. Rinsing in HCl helps to
eliminate from the sample surfaces bismuth compounds
and I
26 cm10 −
2, insoluble in water, which can precipitate on
crystals. Then samples were washed with ethanol (at
finish rinsing, we can also use methanol, because it is a
good solvent of residual iodine). For the chemical
treatment of Ві2Те3, authors [5] have used solutions of
(2HNO3 + 1HCl + 6H2O) or (10 ml HNO3 + 10 ml HCl
+ 40 ml H2O + 1 g I2) for 1-2 min. After etching in the
first solution, the samples were washed with water and
in the second one by ethanol and dried by filter paper.
As a result, in both cases hexagonal etching pits were
formed on the surface. When etching Ві2Те3 with 30%
HNO3, hexagonal etching pits were obtained on the
surface of wafers, and in [6], for chemical polishing
Ві2Те3, hot solution of dilute “aqua regia” has been used.
The object of this work is investigation of chemical
etching the Ві2Те3 crystals as well as n-
(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 and p-
(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 solid solutions with
HNO3–HCl etching compositions, determination of
concentration limits for polishing solutions, ascertaining
the influence of aging processes in etchants on the
etching rate and quality of polishing, optimization of
etching compositions and chemical treatment modes to
use them in producing materials for making operation
elements of devices.
2. Experimental
To investigate semiconductor dissolution, ascertain the
character of corresponding reactions and determine
limiting stages of the process, we have used the method
of rotating disk and appropriate device for its practical
implementation – installation for CDP [7]. The crystals
of Ві2Те3 as well as n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05
and p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 solid solutions
were grown using vertical growth zone melting of the
components. For the investigation, we cut from the
ingots the wafers with dimensions (∼5×7×1.5 cm), which
were abraded by aqueous suspension of M10, M5 and
M1 abrasive powder one after another. After each stage
of wafer treatment – cutting, abrading, mechanical and
chemical-mechanical polishing interoperable cleaning
was performed to eliminate various contaminations from
the surface. Physical or mechanical contaminations
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
200
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 2. P. 200-202.
(mote, abrasive, metallic materials, fibers and
semiconductor particles that are crumbled into small
pieces) were eliminated with warm water with addition
of surfactants. The final stage of treatment included
washing in distilled water, degreasing by ethanol or
acetone, then samples were dried up in air flow.
Mechanically polished surface of crystalline
samples are stable in time, but it is not structurally
perfect, and therefore, before researching, the layer with
a thickness of 80-100 μm was eliminated from it with
etchant of the same composition, in which the process of
chemical treatment was subsequently performed.
Samples were stuck by their operation surface to glass
substrates by using picein and placed on the disk of CDP
installation. The dissolution rate of crystals was
measured by the difference in the sample thickness
before and after the etching process by using the watch
indicator 1MIGP to within ±0.5 μm. Etching time was
chosen so that the process was shot by one of at least 10-
15 μm of material.
To prepare etching compounds, we used 70% HNO3
and 36.6% HCl. Etching compositions were prepared
directly before use, then they were hold up for 80-
120 min. After completion of etching process, the samples
were quickly bereaved from etching composition and
immediately washed several times with deionized water
and in ultrasonic bath for 5 min at 20 °C for surface
cleaning from etchant residues, then dried up in air flow.
The surface microstructures obtained after etching
were photographed using the universal stage microscope
ZEISS JENATECH INSPECTION with a digital
camcorder possessing magnifications between 25× to
1600×.
3. Results and discussions
Investigation of chemical dissolution Ві2Те3,
n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 and
p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 were performed
within the concentration range 10-100 vol.% HNO3 to
HCl at T = 293 K and the disk rotation speed
. Concentration dependences of the etching
rate (v
1min86 −=γ
etch) of these crystals in the HNO3–HCl solutions are
shown in Fig. 1. As seen from the figure, with increasing
the amount of HNO3 in HCl the dissolution rate of Ві2Те3
increases from 1.7 to 23 μm/min, for n-type material –
from 1 to 88 μm/min and for p-type material – from 0.3 to
71 μm/min, while the corresponding curve is
characterized by two peaks at different ratio etching
components. Depending on the volume ratio of
components [HNO3]:[HCl], we can assume the following
course of these reactions in the etching solution:
10HCl + 4HNO3 = 6H2O + 2HNО2 +
+ 5Cl2 + 2ClNO(peak 1, [HCl]/[HNO3]=2.7:1), (1)
HCl + HNO3 = ClNO2 + H2O
(peak 2, [HCl]/[HNO3]=1:2). (2)
0 10 20 30 40 50 60 70 80 90 100
0
10
20
30
40
50
60
70
80
90
100
v,
µ
m
/m
in
c, vol.% HNO3
1
2
3
Fig. 1. Concentration dependences of the etching rate for
Ві2Те3 (1), n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 (2) and p-
(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 (3) in the solutions of the
HNO3–HCl system (T = 293 K, γ = 86 min–1).
The results of metallographic analysis of the
samples surface obtained by etching Ві2Те3, n- and p-
type conductivity semiconductors designed by polishing
etchants, showed the possibility to use them for CDP of
thermoelectric materials surface.
In order to study the processes that occur by
dissolution of the investigated semiconductor materials
in etching compositions of HNO3–HCl system, we
performed kinetic research and plotted the dependences
of the dissolution rate (v) in the coordinates
( ) at T = 293 K as well as of the
etchant temperature in the coordinates
2/11 −− γ−v
1min12036 −<γ<
Tv /1ln − in
polishing solution of 55 vol. % HNO3 in HCl. As seen
from Fig. 2a, for all the investigated materials the
suitable lines can be extrapolated to the origin, which
indicates a diffusion mechanism of dissolution inherent
to these materials. Investigation of temperature
dependences of the dissolution rate of the mentioned
above materials in the same etching solution (Fig. 2b)
revealed that the apparent activation energy did not
exceed Ea = 30 kJ/mol in all the cases [8]. This confirms
the conclusion that the limiting stage of the process of
dissolution of these materials is diffusion.
For technological purposes, it is important
information about the stability of etching solutions,
which means the influence of the storage duration on
such basic things as the etching rate, polishing ability
and others. To establish this influence, we carried out the
research of etching rate changes observed for Ві2Те3 and
solid solutions based on it in the etching composition of
55 vol.% HNO3–HCl, which were aged for 2, 24, 48, 72
and 96 hours at room temperature. As seen from Fig. 3,
with increasing duration of etchant aging, the dissolution
rates of investigated materials have been hardly changed.
It should be also noted that aging this etchant of HNO3–
HCl system for five days has no effect on the polishing
properties, so, these etchants can be used for chemical
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
201
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 2. P. 200-202.
polishing for a long time after their preparation, which is
another advantage of them. This should be considered in
practical use of the proposed etching compositions.
0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 0.17 0.18
0.04
0.06
0.08
0.10
0.12
0.14
0.16
v-1
, m
in
/μ
m
γ-1/2, min1/2
1
3
2
а
3.22 3.29 3.36 3.43 3.50 3.57 3.64
2.8
3.2
3.6
4.0
4.4
4.8
5.2
ln
v
, [
v,
μm
/m
in
]
103/Т, К-1
B
C
D
X
X
X
1
2
3
b
Fig. 2. Dependences of the etching rate for Ві2Те3 (1),
n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 (2) and
p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 (3) on the speed of disk
rotation (T = 293 K) (a) and temperature (γ = 86 min–1) (b) in
the solution containing 55 vol. % HNO3 to HCl.
0 10 20 30 40 50 60 70 80 90 100
0
10
20
30
40
50
60
70
80
90
100
v,
µ
m
/m
in
τ, h
1
2
3
Fig. 3. Dependences of the etching rate of Ві2Те3 (1),
n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 (2) and
p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 (3) on the shelf-time of
etchant containing 55 vol.% HNO3 to HCl (T = 293 K,
γ = 86 min–1).
Thus, the results of the experiments revealed that
all etchants HNO3–HCl in the concentration range
10-100 % HNO3 in HCl have a good polishing
properties for surface of thermoelectric materials Ві2Те3,
n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 and
p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03, characterized by a
low etching rate and can be used for CDP of these
materials.
4. Conclusions
We have investigated the dependences of the dissolution
rate of Ві2Те3 crystals as well as solid solutions
n-(Bi2Te3)0.9(Sb2Te3)0.05(Sb2Se3)0.05 and
p-(Bi2Te3)0.25(Sb2Te3)0.72(Sb2Se3)0.03 on the composition
of etchants HNO3–HCl, their stirring, temperature and
shelf-time storage. We showed that one can use
solutions containing (10-60, 80) vol.% HNO3 to HCl in
chemical polishing the above semiconductors. We have
found that the studied etchants are stable in time and
keep their polishing properties for five days after
preparation.
References
1. V.A. Kutasov, L.N. Lukyanova, P.P. Konstantinov,
High-effective thermoelectric materials n-
(Bi,Sb)2Te3 for the temperature below 200 K //
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393 (2000), in Russian.
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© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
202
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