State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type
The morphology and composition of Cd₁₋xZnxTe and Cd₁₋xMnxTe solid solutions surfaces after different types of surface treatment were investigated. Chemical etching of the surfaces and polishing by diamond pastes cause change of surface stoichiometry and ontamination of surface layer by carbon and e...
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Dremlyuzhenko, S.G. Zakharuk, Z.I. Rarenko, I.M. Srtebegev, V.M. Voloshchuk, A.G. Yurijchuk, I.M. 2017-05-28T17:27:45Z 2017-05-28T17:27:45Z 2004 State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type / S.G. Dremlyuzhenko, Z.I. Zakharuk, I.M. Rarenko, V.M. Srtebegev, A.G. Voloshchuk, I.M. Yurijchuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 1. — С. 52-55. — Бібліогр.: 9 назв. — англ. 1560-8034 PACS: 79.20.Rf; 79.60.Bm https://nasplib.isofts.kiev.ua/handle/123456789/118105 The morphology and composition of Cd₁₋xZnxTe and Cd₁₋xMnxTe solid solutions surfaces after different types of surface treatment were investigated. Chemical etching of the surfaces and polishing by diamond pastes cause change of surface stoichiometry and ontamination of surface layer by carbon and etchant components. Potentiometer studies were carried out to study the processes that take place on the interface "semiconductor-electrolyte". A prediction of phase composition of oxide films on Cd₁₋xZnxTe and Cd₁₋xMnxTe surfaces was made and a mechanism of their dissolution was determined. It was found that chemicomechanical polishing by alkaline colloidal silica compositions is an optimal surface treatment procedure. Chemico-mechanical polishing with this mixture gives a uniform surface without essential change of surface stoichiometry and fouling of the surface layer by etchant components. The financial support of the Civilian Research and Development Foundation (grant UP2-536) and the Science and Technology Center of Ukraine (grant №1440) is gratefully acknowledged. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type Article published earlier |
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State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type |
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State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type Dremlyuzhenko, S.G. Zakharuk, Z.I. Rarenko, I.M. Srtebegev, V.M. Voloshchuk, A.G. Yurijchuk, I.M. |
| title_short |
State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type |
| title_full |
State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type |
| title_fullStr |
State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type |
| title_full_unstemmed |
State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type |
| title_sort |
state of cd₁₋xznxte and cd₁₋xmnxte surface depending on treatment type |
| author |
Dremlyuzhenko, S.G. Zakharuk, Z.I. Rarenko, I.M. Srtebegev, V.M. Voloshchuk, A.G. Yurijchuk, I.M. |
| author_facet |
Dremlyuzhenko, S.G. Zakharuk, Z.I. Rarenko, I.M. Srtebegev, V.M. Voloshchuk, A.G. Yurijchuk, I.M. |
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2004 |
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English |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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Article |
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The morphology and composition of Cd₁₋xZnxTe and Cd₁₋xMnxTe solid solutions surfaces after different types of surface treatment were investigated. Chemical etching of the surfaces and polishing by diamond pastes cause change of surface stoichiometry and ontamination
of surface layer by carbon and etchant components. Potentiometer studies were carried out to study the processes that take place on the interface "semiconductor-electrolyte". A prediction of phase composition of oxide films on Cd₁₋xZnxTe and Cd₁₋xMnxTe surfaces was made and a mechanism of their dissolution was determined. It was found that chemicomechanical polishing by alkaline colloidal silica compositions is an optimal surface treatment procedure. Chemico-mechanical polishing with this mixture gives a uniform surface without essential change of surface stoichiometry and fouling of the surface layer by etchant components.
|
| issn |
1560-8034 |
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https://nasplib.isofts.kiev.ua/handle/123456789/118105 |
| citation_txt |
State of Cd₁₋xZnxTe and Cd₁₋xMnxTe surface depending on treatment type / S.G. Dremlyuzhenko, Z.I. Zakharuk, I.M. Rarenko, V.M. Srtebegev, A.G. Voloshchuk, I.M. Yurijchuk // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2004. — Т. 7, № 1. — С. 52-55. — Бібліогр.: 9 назв. — англ. |
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2025-11-24T23:40:09Z |
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| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics. 2004. V. 7, N 1. P. 52-55.
© 2004, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine52
PACS: 79.20.Rf; 79.60.Bm
State of Cd1�xZnxTe and Cd1�xMnxTe surface
depending on treatment type
S.G. Dremlyuzhenko, Z.I. Zakharuk, I.M. Rarenko, V.M. Srtebegev,
A.G. Voloshchuk, I.M. Yurijchuk
Chernivtsi National University, 2, Kotsyubynsky str., 58012 Chernivtsi, Ukraine
E-mail: microel@chnu.cv.ua, Phone.: +380 (372) 584875
Abstract. The morphology and composition of Cd1�xZnxTe and Cd1�xMnxTe solid solutions
surfaces after different types of surface treatment were investigated. Chemical etching of the
surfaces and polishing by diamond pastes cause change of surface stoichiometry and con-
tamination of surface layer by carbon and etchant components. Potentiometer studies were
carried out to study the processes that take place on the interface �semiconductor-electrolyte�.
A prediction of phase composition of oxide films on Cd1�xZnxTe and Cd1�xMnxTe surfaces
was made and a mechanism of their dissolution was determined. It was found that chemico-
mechanical polishing by alkaline colloidal silica compositions is an optimal surface treat-
ment procedure. Chemico-mechanical polishing with this mixture gives a uniform surface
without essential change of surface stoichiometry and fouling of the surface layer by etchant
components.
Keywords: Cd1�xZnxTe, Cd1�xMnxTe, semiconductor, surface, morphology, etchant.
Paper received 24.11.03; accepted for publication 30.03.04.
High-quality structure-perfect semiconductor surfaces
which are uniform on chemical composition and purity
are very important in production of semiconductor de-
vices . Polishing with an etchant is one of the most widely
used methods of semiconductor surface treatment. At
present the etchants on K2Cr2O7, CrO3 and bromine base
give the best results of surface polishing. But chemical
etching with K2Cr2O7 and CrO3 etchants results in con-
siderable enrichment of cadmium telluride surface by
chromium ions, which can be explained by high absorp-
tive ability of −2
72OCr ions on cadmium telluride surface
[1, 2]. Oxidation mechanisms of these etching processes
were not sufficiently studied.
The use of the etchants with bromine results in change
of surfaces stoichiometry and in enrichment of cadmium
telluride surface by bromine ions [3]. A formation of el-
ementary tellurium and tellurium dioxide islands was
observed in [4, 5]. An etching mechanism of CdTe sur-
face by etchants with bromine was studied in [5,6] were
the presence of elementary tellurium on the surface was
reported. So, the use of these etchants do not give a possi-
bility to obtain the surface with minimal contamination
with etchant elements. Further studies are needed to work
out an optimal surface treatment procedure which causes
minimal changes in crystals surface.
The purpose of the paper is to determine the etchants
composition and an optimal treatment procedure for the
Cd1�xZnxTe and Cd1�xMnxTe surfaces. Solution of the
problem is possible if only using wide spectra of chemico-
physical methods to study the mechanisms and kinetics
of the processes that take place at the interface �semicon-
ductor-electrolyte�.
The studies were carried out on the CdTe, Cd1-xZnxTe
(0.02 ≤ x < 0.2) and Cd1�xMnxTe (0.02 ≤ x < 0.55) single
crystals grown by the Bridgman technique. Cutting the
crystal into wafers was made by tungsten wire (∅ 0.2 mm)
with abrasive water suspension of ∅10 µm; mechanical
lapping � with free abrasives of ∅10 µm and ∅5 µm; me-
chanic polishing � with diamond pastes with grain size
less than 1 µm. The depth of structure changes has been
controlled using two-crystal X-ray spectrometer by sub-
sequent etching the wafers surface [7]. Local distribution
of structure defects of thin surface layers was studied by
X-ray method with the use of skew asymmetric diffrac-
tion geometry with a small critical angle of total internal
reflection [8]. The morphology and element composition
of the surfaces were studied by an electron raster micro-
scope and X-ray microanalyzer Camscan 4DV.
The studies were carried out after different types of
surface treatment: polishing with abrasive pastes; etch-
S.G. Dremlyuzhenko et al.: State of Cd1�xZnxTe and Cd1�xMnxTe surface depending ...
53SQO, 7(1), 2004
ing in etchant 1 (HNO3:H2O:K2Cr2O7) and etchant 2 (Br
(8 %): methanol); chemico-mechanical polishing. The
studies of the Cd1�xZnxTe and Cd1�xMnxTe surface com-
position after different treatments reveal the presence of
carbon and oxygen on the surface. The presence of car-
bon on the Cd1�xZnxTe and Cd1�xMnxTe surfaces can be
caused by: the contamination of the material by pirolytic
coating of quarts container in which the crystal was grown;
the chafing of carbon while cutting the samples by corun-
dum abrasive; the contamination while lapping and pol-
ishing with abrasive pastes; the contamination of the sur-
face while etching with chemical solutions and washing
in organic solvents. The removal of damaged layer after
mechanical polishing was achieved by long-term chemi-
cal treatment of the surface with polishing etchants. The
use of rather long etching time results in breakdown of
plainness and emergence of a relief (Fig. 1a, b). Besides,
in these samples the local micro inhomogeneities
(<100 µm) were revealed by the X-ray method. In
topograms, as a rule, they are surrounded by bright back-
ground, which testifies about the existence of tensions
around them. Using skew asymmetric X-ray topography
we have found that one part of these inhomogeneities are
humps and the other are pits. The roughness of the sur-
face is caused by different etching velocity of the matrix
and inclusions. The dimension of the inclusions is of
10÷50 µm (Fig. 1c). The studies of the element composi-
tion of the humps by X-ray microanalyzer have shown
that most of the humps have considerable content of tel-
lurium (Table 1). The presence of silicon, aluminium,
oxygen, iron, sulphur and others was also detected. Quan-
titative analysis of the matrix (beyond the inclusions) de-
tects the presence of non-uniformly distributed impurity
elements which concentration is up to 1 at. %. The pres-
ence of the impurities in the matrix changes the composi-
tion of the solid solution.
Chemical etching of the Cd1�xZnxTe and Cd1�xMnxTe
surfaces with bromine-methanol etchants enriches the sur-
face layer by bromine and oxygen into the depth of 13�
15 nm, so as in the case of cadmium telluride surface [3].
In order to determine an optimal composition of the
etchant it is necessary to study the processes that take
place in the system �CdTe�etchant�. Electro-potentio-
meter method is an effective tool for studying the proces-
ses on the interface �semiconductor�electrolyte� (�semi-
conductor�etchant�). One of the possible ways to carry
out electro-potentiometer investigation is to determine
the dependencies of equilibrium potential on pH (Pour-
baix diagram). An analysis of the Pourbaix diagram give
a possibility to make a reliable prediction of the phase
composition of oxide films on semiconductors surface and
to find out a mechanism of their solubility. The analysis
of the ϕ�pH diagram for the CdTe�H2O system shows
that region of thermodynamic stability of cadmium
telluride in solid phase spreads through whole studied
pH interval. A mechanism of corrosion processes in the
CdTe�H2O system and chemical forms of corrosion prod-
ucts are defined by the values of the oxidative potential
of the medium and pH [9]. Proposed procedure for ther-
modynamic prediction of possible redox reactions in the
CdTe�H2O system may also be used for an analysis of
more complex �semiconductor-electrolyte� systems.
Zinc component doesn�t considerably change (from
thermodynamic point of view) the possible oxidative pro-
cesses in the CdTe�H2O system, because cadmium and
zinc are chemically similar elements. More higher zinc
activity somewhat restrict the pH interval in which
Cd1�xZnxTe single crystal surface can be in active state.
In the �Cd1�xZnxTe�aqueous solution� system a forma-
tion of insoluble Zn(OH)2 phase, which passivate a semi-
conductor surface, is possible at pH = 6.13, whereas a
formation of Cd(OH)2 � at pH = 6.9. Zinc hydroxide is
thermodynamically stable in 6.13�12.37 pH interval
and dissolve at higher values of pH forming −
2HZnO and
−2
2ZnO ions.
Thermodynamic analysis of redox processes in the
Cd1�xMnxTe�H2O system is more complicated as com-
pared to the CdTe�H2O system. It is caused by the pres-
ence of manganese, which can be oxidized to Mn2+,
Mn3+, Mn4+, Mn6+ and Mn7+ forming soluble and in-
soluble in water compounds. Analysis of the literature
reveals more than 30 reactions by which manganese and
its components can be oxidized in aqueous solutions.
Calculations of the ϕ = f(pH) dependencies define the
Pourbaix diagram for the Mn�H2O system. Comparing
�equilibrium potential � pH� diagrams for the Mn�H2O
and the CdTe�H2O systems the prediction of thermody-
namic possible reactions in the Cd1�xMnxTe�H2O sys-
tems is given and an estimate of the chemical state of the
semiconductors surface in aqueous solutions with diffe-
rent pH is made.
In the high acidic medium (pH < � 0.37), all the com-
ponents (Cd, Mn, Te) dissolve and pass into the solution
in the form of Cd2+, Mn2+, Te4+ ions. It indicates on
uniform dissolution of the semiconductor and gives a pos-
sibility to predict (introducing special agents into the so-
lution) the possible effect of the Cd1�xMnxTe single crys-
tal surface etching. Mineral or organic acid substances,
which form stable complex compounds with above men-
tioned ions, can be used as a special agents. It is worth to
note that unlike the Mn2+/Mn and the Cd2+/Cd systems
the Te4+/Te system has a positive value of the standard
electrode potential ϕ° =0.568 V. So, taking into account
the high concentration of free surface electrons, the re-
duction of the Te4+ ions and the formation of the elemen-
tary tellurium phase on the Cd1�xMnxTe single crystals
surface is expected.
In the pH interval 0.37�5.45, the mechanism of cad-
mium and manganese components dissolution does not
change, and tellurium oxidizes forming dissoluble +
2HTeO .
However a small increase of the oxidizing potential of
the medium (for example, due to the dissolved O2) pro-
duces a conditions for extraction of low soluble H2TeO4
phase on the Cd1�xMnxTe surface. An increase of Te4+
and +
2HTeO ions concentrations in the Cd1�xMnxTe�H2O
system also makes for this process.
In low-acidic, neutral and low-alkaline solutions (pH
5.45�10.45) the Cd1�xMnxTe surface is passivated. It is
54
SQO, 7(1), 2004
S.G. Dremlyuzhenko et al.: State of Cd1�xZnxTe and Cd1�xMnxTe surface depending ...
caused by the formation of the oxide and hydroxide com-
pounds on the semiconductor surface. Calculated Gibbs
free energies of possible Cd1�xMnxTe oxidation products
have negative values and decrease in the row: CdO→
→TeO2→Cd(OH)2→Mn(OH)2. Taking into account the
ability of the CdO, TeO2, Cd(OH)2 to dissolve in alka-
line medium, it is possible to predict an enrichment of the
passivating films by Mn(OH)2 phase, which transforms
into Mn3O4 and Mn2O3 with an increase of the oxidative
potential. Further increase of pH activates dissolution
processes of the film: TeO2 completely dissolves at pH ≥
≥ 10.45; Cd(OH)2 � at pH ≥ 11.17; Mn(OH)2 � at pH ≥
≥ 11.45. Therefore, one can expect that in high-alkaline
medium (pH ≥ 11.45) the Cd1�xMnxTe surface is free from
oxides and hydroxides. Calculations show that cadmium,
manganese and tellurium oxidation is possible in this
conditions. In the result the soluble in water −
2HCdO ,
−
2HMnO and −2
3TeO ionic forms are produced.
The analysis of the Pourbaix diagram allows us to
conclude:
� dominant action of Te is caused by the fact that
the oxidation potential of the reactions, that take place
in �semiconductor-electrolyte� system with tellurium com-
ponent, is greater than the oxidation potentials of cad-
mium, manganese and zinc;
� according to the thermodynamic analysis a uni-
form dissolution from the surface takes place in acidic
mediums. Polishing etching is possible in the systems
which oxidation potential is not less than 0.416 V. The
most effective systems are etchants which contain the sol-
vent HNO3 as an oxidizer;
Fig. 1. Scanning electron microscope image of the Cd0.55Mn0.45Te surface: a) after mechanical lapping; b) after etching with bromine
methanol solutions; c) inclusions on the surface after etching with bromine methanol solutions; d) after chemico-mechanical polishing
with SiO2 colloidal solution.
a b
c d
S.G. Dremlyuzhenko et al.: State of Cd1�xZnxTe and Cd1�xMnxTe surface depending ...
55SQO, 7(1), 2004
� in highly alkaline mediums the substances which
electrode potential doesn�t exceed the potential of the
reaction Te + 6OH� = −2
3TeO + 6H+ + 4e (ϕ° = �0.57 V)
can serve as an oxidizer. There are many substances that
meet this condition, but the use of H2O2, taking into ac-
count the specificity of the medium (pH ≥ 11.45), is more
preferred because its decomposition products are reduced
in alkaline medium at potentials greater than �0.267 V.
These conclusions confirm the right choice of the
chemico-mechanical polishing with a solution which con-
sists of fine-dispersed SiO2, H2O2, NaOH, glycerin and
monoethanolamin [3] as a final treatment. This is due to
the fact that the SiO2 colloidal powder with 2�20 nm size
as an abrasive material doesn�t cause essential structural
distortion and its hydrophilic character allows to put
easily it into water medium and to obtain stable water
dispersions. The products of polishing are eliminated
from the surface due to high absorption ability of the
etchant, caused by large SiO2 colloidal powder surface
with active hydroxo-(OH) and amino-(NH2) groups. Be-
sides, in order to transfer an etching process into the dif-
fusive region and to remove roughness of the working
surface the glycerine is added to the solution. Glycerine
addition leads to a decrease of etching velocity and gives
a possibility to control and regulate effectively an etch-
ing process. Monoethanolamin fixes the dissolution prod-
ucts in the etchants volume.
Hence, chemico-mechanical polishing by colloidal
silica compositions does not contaminate the surface layer
with etchants components. Besides, this method causes a
minimal change of the Cd1�xZnxTe and Cd1-xMnxTe sur-
face stoichiometry as compared with chemical etching,
that was confirmed by investigation of the surface com-
position. An advantage of this method is also a possibil-
ity to obtain a surface free from local micro-inhomoge-
neities, that are formed on chemical etching (Fig. 1d).
Moreover, the chemico-mechanical polishing does not
brake down the plane-parallelism of the surface. Thus,
the use of the chemico-mechanical polishing with colloi-
dal silica compositions allows to obtain a surface, which
mostly satisfies the demands, which are required to the
optical devices surface.
Table 1. Composition of the matrix and inclusions (in at.%) of Cd1�xZnxTe (0,02 ≤≤≤≤≤ x < 0,2) and Cd1�xMnxTe surfaces after etching
with K2Cr2O7 solution (M � matrix; I � inclusions).
N Sample Cd Te Zn Mn Si Al Fe Cr Cl S Na O
1 CdZnTe (M) 44.8 49.5 4.97 0.69
2 CdZnTe (M) 44.6 49.6 5.03 0.41 0.11 0.24
3 CdMnTe (M) 45.9 50.2 3.01 0.18 0.32 0.13 0.22
4 CdMnTe (M) 46.7 49.7 2.88 0.34 0.19 0.22
5 CdZnTe (I) 19.0 38.7 1.25 35.3 2.49 2.8 0.38
6 CdZnTe (I) 8.66 34.0 0.48 37.1 12.7 0.12 3.48 1.24 0.24
7 CdMnTe (I) 12.8 15.1 1.5 17.0 7.16 0.92 19.1 15.3 11.0
8 CdMnTe (I) 34.4 35.6 3.58 12.2 2.8 2.65 8.67
Acknowledgements
The financial support of the Civilian Research and De-
velopment Foundation (grant UP2-536) and the Science
and Technology Center of Ukraine (grant ¹1440) is
gratefully acknowledged.
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