Role of an inert component in compositions with manganese(II) and manganese(IV) oxides in studying nonlinear effects in GaAs thermal oxidation

Article abstract of DOI:10.1134/S0036023610120077

GaAs thermal oxidation by mixtures containing manganese(II) and manganese(IV) oxides and gallium arsenide-inert components was studied.

Full text of DOI:10.1134/S0036023610120077

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 12, pp. 1857–1862. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © T.V. Kozhevnikova, P.K. Penskoi, V.F. Kostryukov, I.V. Kuznetsova, S.V. Kutsev, I.Ya. Mittova, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010,
Vol. 55, No. 12, pp. 1970–1975.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Role of an Inert Component in Compositions with Manganese(II)
and Manganese(IV) Oxides in Studying Nonlinear Effects
in GaAs Thermal Oxidation
T. V. Kozhevnikovaa, P. K. Penskoia, V. F. Kostryukova,
I. V. Kuznetsovab, S. V. Kutsevc, and I. Ya. Mittovaa
a Voronezh State University, Universitetsksya pl. 1, Voronezh, 394006 Russia
b Voronezh State Technological Academy, pr. Revolyutsii 19, Voronezh, 394622 Russia
c Institute of Physicochemical Problems of Ceramic Materials, Russian Academy of Sciences, Voronezh, Russia
Received October 8, 2009
Abstract—GaAs thermal oxidation by mixtures containing manganese(II) and manganese(IV) oxides and
gallium arsenideꢀinert components was studied.
DOI: 10.1134/S0036023610120077
III–V compound semiconductors, primarily, our understanding of the nature of nonlinear effects on
GaAs, are of paramount importance not only as canꢀ gallium arsenide thermal oxidation.
didate materials for various fields of advanced engiꢀ
neering but also as an important class of subjects of
solidꢀstate chemistry, thermodynamics, and heterogeꢀ
neous kinetics [1]. Studies into gallium arsenide therꢀ
mal oxidation under the action of binary activator
oxide compositions revealed nonadditivity of their
chemistimulating effect manifested as a nonlinear
dependence of the oxide layer thickness on GaAs on
the activator oxide composition [2]. The nonlinear
effects were shown to arise from interactions between
activators that generate additional links between them
[3] and spoil the linear independence of concurrent
reactions in the joint action of oxides.
Here, we study GaAs thermal oxidation under the
action of MnO and MnO2 activator oxides in compoꢀ
sitions with Ga2O3, Al2O3, and Y2O3 inert components.
EXPERIMENTAL
Samples to be oxidized were polished singleꢀcrystal
GaAs wafers (100) (AGChTsꢀ1 type). The activators
used were powdered MnO and MnO2 in variable comꢀ
positions with inert Ga2O3, Al2O3, and Y2O3 (pure for
analysis grade). Each oxide was mechanically ground
in an Arden vibrator for 15 min and weighed on an
analytical balance in an amount required for preparing
a set of compositions in 10ꢀmol % steps. An aliquot of
a set composition was stirred and placed in a quartz
container where the GaAs wafer to be oxidized served
as a cover (positioned at 10 mm from the activator surꢀ
face). The container was mounted inside a horizontal
quartz reactor preheated to the set temperature in a
An explicit relationship was found to exist between
the character of the nonlinear effect and the oxidation
state of the metal that forms one of the oxides of the
composition [3]. Therefore, there is natural interest to
studying gallium arsenide thermal oxidation under the
action of compositions comprising an inert compoꢀ
nent (which does not activate oxidation) and an actiꢀ
vator (which represents an oxide of the same element
resistor furnace. The process was performed at 530°C
in flowing oxygen (30 L/h) for 10–40 min using postꢀ
oxidation. Automated temperature control in a resisꢀ
tor furnace ensured a 2ꢀK temperature maintenance
accuracy.
in different oxidation states). Oxides of
d elements,
which have a wide spectrum of stable oxidation states,
are most suitable for this purpose. Manganese oxides
are promising for use as activators of gallium arsenide
Oxide film thicknesses on GaAs were determined
thermal oxidation for several reasons. First, mangaꢀ ellipsometrically (LEFꢀ3M) [4]. The composition of
nese forms derivatives where it has different oxidation oxide layers was determined using IR spectroscopy
numbers. Second, manganese oxides are efficient cheꢀ (SpecordꢀM80) [5] and electron probe microanalysis
mistimulators, and their individual and joint action on (EPMA; CamScan) [6]. Transformations in the actiꢀ
GaAs thermal oxidation has been studied [2, 3]. Third, vator compositions having an inert component were
the joint action of two oxides (manganese oxide with identified using thermogravimetry (PaulikꢀPaulikꢀ
an inert diluent) in variable compositions can reveal a Erdey Qꢀ1500D) [7] and Xꢀray powder diffraction
linear or additive effect of components on chemistimꢀ (DRONꢀ4) [8]. The sinterability of the compositions
ulated gallium arsenide oxidation, and it can enhance was ascertained as the change in the specific surface
1857

1858
KOZHEVNIKOVA et al.
Table 1. Powder Xꢀray diffraction data for individual oxides
and compositions with inert components in the course of
GaAs thermal oxidation at 530°C for 10 min
Thus, Xꢀray diffraction shows that activator oxides
and inert diluents are chemically inert to each other
under the experimental conditions.
Nonlinear effects have been discovered in an
experimental study of the kinetics of GaAs thermal
oxidation under the action of MnO2 and MnO compoꢀ
sitions with the Ga2O3 inert component. Addition of
Ga2O3 to either MnO2 or MnO strongly reduces the
oxide layer thickness gain rate via retarding the chemꢀ
istimulating effect of manganese(II) oxide, with a
minimum in the region of 40 mol % Ga2O3 (figure,
panel a). A further increase in the concentration of the
inert component in the composition decreases the
negative nonadditivity, and in the range 100–60%
Ga2O3 the oxide layer thickness is a linear function of
composition. Points on the Ga2O3 ordinate refer to
intrinsic GaAs oxidation in the absence of activators
under the specified conditions. Extrapolation of the
linear segment of the curves to the MnO2 or MnO
ordinate gives the same results as for GaAs oxidation
under the individual chemistimulating action of actiꢀ
vators; that is, the linear dependence is determined by
the oxide layer thickness obtained on GaAs under the
action of a chemistimulator and in the absence
thereof.
Sample
Phase
Ga2O3
Al2O3
Y2O3
β
ꢀGa2O3
ꢀAl2O3
Y2O3
γ
MnO2
MnO
MnO2, Mn2O3
MnO, MnO2, Mn2O3
(Ga2O3)0.8(MnO2)0.2
(Ga2O3)0.4(MnO2)0.6
(Al2O3)0.8(MnO2)0.2
(Al2O3)0.2(MnO2)0.8
(Y2O3)0.8(MnO2)0.2
(Y2O3)0.2(MnO2)0.8
(Ga2O3)0.8(MnO)0.2
(Ga2O3)0.4(MnO)0.6
(Al2O3)0.8(MnO)0.2
(Al2O3)0.2(MnO)0.8
(Y2O3)0.8(MnO)0.2
(Y2O3)0.2(MnO)0.8
β
ꢀGa2O3; MnO2, Mn2O3
β
ꢀGa2O3; MnO2, Mn2O3
γ
ꢀAl2O3; MnO2, Mn2O3, Mn3O4
γ
ꢀAl2O3; MnO2, Mn2O3, Mn3O4
Y2O3; MnO2, Mn2O3
Y2O3; MnO2, Mn2O3
β
ꢀGa2O3; MnO, MnO2, Mn2O3
β
ꢀGa2O3; MnO, MnO2, Mn2O3
γ
ꢀAl2O3; MnO, MnO2, Mn2O3
γ
ꢀAl2O3; MnO, MnO2, Mn2O3
Y2O3; MnO, MnO2, Mn2O3
Y2O3; MnO, MnO2, Mn2O3
To a certain degree, the general pattern of the oxide
layer thickness as a function of composition for the
Ga2O3–MnO and Ga2O3–MnO2 systems is analogous
to the data obtained earlier for the Ga2O3–Sb2O3 sysꢀ
tem [10]. There, an additive dependence was observed
when the second component was added to gallium
oxide, and for low Ga2O3 contents, the oxide film
thickness showed negative nonadditivity. Negative
nonadditivity at low levels of the inert component was
associated with the sintering of the chemistimulator.
The sintering of oxide powders depends on dispersity,
temperature, and activating additives. As regards the
effect of an oxide composition, the activating effect of
the second component on the sinterability of the first
component can play a considerable role.
Chemical activation during sintering is reduced to
doping with additives that either do or do not form a
liquid phase at the sintering temperature [12, 13].
The additives to Al2O3 that do not form a liquid
phase are categorized into three groups with respect to
their effects, as follows:
area determined by thermal nitrogen desorption (BET,
TRISTARꢀ3000) [9].
RESULTS AND DISCUSSION
In choosing inert components for oxide composiꢀ
tions, we were guided by the thermodynamic forbidꢀ
dance of transit oxygen transfer from Ga2O3, Al2O3,
and Y2O3 to the components of the semiconductor to
be oxidized [10, 11]. Blanks of intrinsic GaAs oxidaꢀ
tion in flowing oxygen and in the presence of inert
components showed the complete identity of the proꢀ
cess kinetics and the absence of aluminum and yttrium
traces in the resulting oxide layers (IRS and EPMA).
For checking inertness under our conditions, comꢀ
positions and individual oxides used in the experiꢀ
ments were annealed in air at 530°C for 10 min.
Annealed samples were characterized by powder Xꢀray
diffraction. The results are displayed in Table 1.
(i) additives activating sintering and simultaꢀ
neously enhancing coarsening, e.g., TiO2 and ZrO2 in
Xꢀray diffraction shows that manganese oxides
under our experimental conditions experience partial
Al2O3
;
(ii) additives activating sintering and slowing down
coarsening, e.g., MgO or BeO in Al2O3;
(iii) additives inhibiting sintering processes and
slowing down coarsening.
The effect of the first group of additives is the conꢀ
sequence of their dissolution in the system to be sinꢀ
tered to form a solid solution where the defect concenꢀ
tration responsible for diffusion mass transfer rate is
higher.
transformations (MnO
MnO2
Mn2O3 and
MnO2 Mn2O3), which coincides with the related
literature [12]. Inert components (Ga2O3, Al2O3, and
Y2O3) do not experience any changes during annealꢀ
ing. Common phases have not been detected upon
annealing. Noteworthy, in the presence of Al2O3, the
manganese oxidation state in MnO2 is reduced to
Mn3O4
.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 12 2010

ROLE OF AN INERT COMPONENT IN COMPOSITIONS
1859
The scenario of the effect of the second group is
similar to that of the first group. The reduction in
coarsening rate caused by these additives is due to the
influence of heterogeneous inclusions on grain
growth. Thus, the amount of the additive required for
this factor to come into play should exceed the solubilꢀ
ity limit at the sintering temperature.
d
, nm
(а)
250
200
150
100
50
The effect of the third group of additives is opposite
to the effect of the first group of additives.
As a result of this, the activator vaporization rate
decreases substantially, and its chemistimulating effect
weakens, which leads to a strong negative nonadditivꢀ
ity. This was also noted for Ga2O3–MnO2 and Ga2O3–
MnO compositions. However, the minimum deviation
of the oxide layer thickness versus composition plot is
slightly extended along the composition axis. A possiꢀ
ble reason for this is that MnO and МnО2 at elevated
temperatures are prone to dissociation (Table 1) [14].
It was noted earlier [10] that, in the absence of
chemical interactions between inert components and
the chemistimulator, the key role may belong to
nonchemical factors, specifically, sintering processes
influence the vaporization dynamics of oxides and
their chemistimulating efficiency. For the effect of
oxide compositions, the activating action of the secꢀ
ond component on the sintering of the first one can be
important. In this connection, we ascertained the sinꢀ
terability of compositions.
Specific surface area determinations for powdered
compositions and their components (Table 2) showed
that, for individual components and the linear oxidaꢀ
tion range under the action of Ga2O3–MnO and
Ga2O3–MnO2 compositions, the specific surface area
does not change considerably. In the negative nonadꢀ
ditivity region, the specific surface area shifts down
sharply.
1.0 0.8 0.6 0.4 0.2
0
0.2 0.4 0.6 0.8 1.0
MnO
3
Mole fraction
Ga O
MnO
d
2
2
, nm
Mole fraction
(b)
250
200
150
100
50
1.0 0.8 0.6 0.4 0.2
0
Al O
0.2 0.4 0.6 0.8 1.0
MnO
MnO
d
2
, nm
2 3
Mole fraction
Mole fraction
(c)
250
200
150
100
50
1.0 0.8 0.6 0.4 0.2
MnO
0
0.2 0.4 0.6 0.8 1.0
MnO
2
Mole fraction
Mole fraction
Y O
2
3
Oxide layer thickness on GaAs as a function of composiꢀ
tion of (a) Ga O –MnO and Ga O –MnO systems; (b)
Thus, in GaAs thermal oxidation under the action
of Ga2O3–MnO2 and Ga2O3–MnO compositions,
Ga2O3 additives strongly enhance sintering of the actiꢀ
vator, causing a negative effect on the activator vaporꢀ
ization dynamics and considerably reducing its chemꢀ
istimulating activity. When Al2O3 levels in the compoꢀ
sition are considerable, the dilution effect is such that
sintering of the activator decreases, the negative effect
weakens, and starting with 20 mol % Ga2O3, it acts as
an ordinary inert diluent, as its considerable levels
2
3
2
2 3
Al O –MnO and Al O –MnO systems; and (c) Y O –
2
3
2
2
2 3
2
3
2 3
MnO and Y O –MnO systems during oxidation in the
following protocol: 530
°С; time (min): (1) 10, (2) 20, (3)
30, and ( ) 40.
4
In the negative nonadditivity region, there is an
abrupt change in the specific surface area for mangaꢀ
nese(II) oxide compositions with Al2O3, as for Ga2O3–
make the sintering tendency of MnO2 and MnO disapꢀ MnO2 and Ga2O3–MnO systems (Table 2).
pear (Table 2).
For manganese(IV) oxide compositions with
The variation trend of the oxide layer thickness as a
Al2O3, there is a different situation. Oxidation for
function of composition for the Al2O3–МnО system,
10 min resulted in an additive oxide layer thickness
to a certain degree, is analogous to the effect of mixꢀ
versus composition curve over the entire range of comꢀ
positions (figure, panel b, curve 1). As the process time
tures of the Ga2O3–МnО system. Addition of Ga2O3 to
МnО weakens the chemistimulating effect of mangaꢀ
nese(II) oxide, and nonadditivity is found in the
region of 40 mol % Al2O3. As the Ga2O3 content of the
composition increases, this negative deviation
decreases, and the dependence is additive starting with
increases, the linear dependence holds in the range of
pure aluminum oxide (here, oxide layer thickness valꢀ
ues are similar to those for intrinsic GaAs oxidation) to
80 mol % MnO2. However, extrapolation of the linear
plot to the manganese dioxide ordinate gives underesꢀ
60 mol % Al2O3
.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 12 2010

1860
KOZHEVNIKOVA et al.
Table 2. Specific surface areas of activator oxide composiꢀ Table 3. Derivative thermal analysis data for oxides and their
compositions with inert components
Sample
Ga2O3
tions with inert components and their individual components
S0sp, m2/g
Ssp, m2/g
T
,
°
C
Thermal event
'
Sample
Ga2O3
Al2O3
Y2O3
8.6828
105.2572
9.1441
8.6656
104.5143
9.1394
–
–
–
–
Al2O3
Y2O3
–
–
MnO
MnO2
5.9488
5.8123
10.7831
10.7559
Endotherm
MnO2
618–675
300–480
480–567
618–675
480–567
567–618
618–675
300–480
480–567
300–480
480–567
300–480
480–567
(MnO2
Mn2O3)
*
Ga2O3–MnO2
9.0135
4.8548
Exotherm
(MnO MnO2)
(40%–60%)
Ga2O3–MnO2
(80%–20%)
MnO
8.8577
74.4893
29.8947
10.5846
9.9862
5.2622
6.3834
26.3578
48.7272
6.4372
8.0438
8.6735
74.1474
25.5636
10.3479
9.7583
2.2726
6.2052
25.3469
16.5837
6.3289
7.9563
Endotherm
(MnO2 Mn2O3)
Al2O3–MnO2
(80%–20%)
Ga2O3–MnO2
(50%–50%)
Endotherm
(MnO2 Mn2O3)
Al2O3–MnO2
(20%–80%)
Endotherm
(MnO2 Mn2O3)
Y2O3–MnO2
(20%–80%)
Al2O3–MnO2
(50%–50%)
Endotherm
(Mn2O3 Mn3O4)
Y2O3–MnO2
(80%–20%)
Y2O3–MnO2
(50%–50%)
Endotherm
MnO2 Mn2O3)
Ga2O3–MnO
(40%–60%)
Ga2O3–MnO
(80%–20%)
Exotherm
(MnO MnO2)
Ga2O3–MnO
(50%–50%)
Al2O3–MnO
(40%–60%)
Endotherm
(MnO2 Mn2O3)
Al2O3–MnO
(60%–40%)
Exotherm
(MnO MnO2)
Al2O3–MnO
(50%–50%)
Y2O3–MnO
(20%–80%)
Endotherm
(MnO2 Mn2O3)
Y2O3–MnO
(80%–20%)
Exotherm
(MnO MnO2)
Footnote: S0sp is the specific surface area of unannealed samples;
Ss' p is the specific surface area after 10ꢀmin annealing at 530°C.
* Hereafter, molar percent.
Y2O3–MnO
50%–50%)
Endotherm
(MnO2 Mn2O3)
endotherm at 567–618
that addition of aluminum oxide to MnO2 shifts the
temperature of transition to Mn2O3 by about 100
(Table 3), and the reduction in the manganese oxidaꢀ
tion state in the presence of Al2O3 is more complete
°C. Therefore, we may think
timates relative to the oxidation chemistimulated by
individual MnO2
.
°C
The results of thermogravimetric experiments
(Table 3) showed, for manganese dioxide, an endotꢀ
herm in the range 618–675°C with an attendant weight
loss corresponding to the conversion of MnO2 to
Mn2O3 (as probed by Xꢀray diffraction). For the
(
МnО2
Мn2О3
Мn3О4).
For the 20 mol % Al2O3 + 80 mol % MnO2 compoꢀ
40 mol % Al2O3 + 60 mol % MnO2 composition, there sition, sintering of the activator was noted along with
the formation of lowꢀactivity Mn3O4 (Table 2). Likely,
is an endotherm at 480–567°C with an attendant
weight loss. This endotherm is followed by another this brings about a stronger weakening of the chemisꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 12 2010

ROLE OF AN INERT COMPONENT IN COMPOSITIONS
1861
Table 4. Contents of activator elements (as probed by EPMA)
in oxide layers grown on GaAs in the presence of Ga2O3–
MnO2, Ga2O3–MnO, Al2O3–MnO2, Al2O3–MnO, Y2O3–
MnO2, and Y2O3–MnO compositions at 53°C for 40 min
timulating activity of the activator, and the thickness
versus composition plot deviates from the additive
line. For individual MnO2, Xꢀray diffraction detects
Mn2O3 in the initial mixture because of thermal dissoꢀ
ciation, in qualitative correlation with derivative therꢀ
mal analysis data (Table 3). Mn2O3 is the most active
Activator
Relative content
element in the of the activator in the
oxide layer,
at. %
initial composition
and oxide layer
oxide (its
= 40 Pa) [13]. In the presence of Al2O3,
p
O2
Composition
as shown by Xꢀray diffraction, MnO (
decomposes to Mn O ( = 5.33 mPa) [11]. Derivaꢀ
p
O2
= 5.33 Pa)
p
O2
2
Mn
Mn (comp.) : Mn (layer)
3
4
tive thermal analysis shows a twoꢀstep water loss at
lower temperatures (480–567 and 567–618 ), which
characterizes a deeper partial dissociation of MnO2
Mn2O3 Mn3O4. Accordingly, this effect must be
less pronounced at low Al2O3 levels, considerably
enhancing GaAs thermal oxidation.
For gallium arsenide oxidation activated by Y2O3–
MnO2 and Y2O3–MnO compositions, additive linear
plots are obtained over the entire ranges of composiꢀ
tions. The points on the Y2O3 ordinate refer to intrinsic
GaAs oxidation in the absence of activators; that is,
there is indeed a linear plot additively determined by
the oxide layer thickness obtained on GaAs in the
presence of the activator and in the absence thereof
(figure, panel c).
The results of the kinetic studies qualitatively corꢀ
relate with Xꢀray diffraction and thermoanalytical
data. Tables 2 and 3 demonstrate that in the presence
of chemically inert Y2O3, the MnO2 and MnO chemiꢀ
stimulators do not change the temperature range or
character of heatꢀinduced transitions.
MnO2
1.97
0.45
0.88
0.42
0.75
0.49
1.65
1.87
0.38
0.91
0.39
0.78
0.41
1.59
1 : 1
°С
(Ga2O3)0.8(MnO2)0.2
(Ga2O3)0.4(MnO2)0.6
(Al2O3)0.8(MnO2)0.2
(Al2O3)0.2(MnO2)0.8
(Y2O3)0.8(MnO2)0.2
(Y2O3)0.2(MnO2)0.8
MnO
0.20 : 0.23
0.60 : 0.45
0.20 : 0.21
0.80 : 0.38
0.20 : 0.24
0.80 : 0.83
1 : 1
(Ga2O3)0.8(MnO)0.2
(Ga2O3)0.4(MnO)0.6
(Al2O3)0.8(MnO)0.2
(Al2O3)0.2(MnO)0.8
(Y2O3)0.8(MnO)0.2
(Y2O3)0.2(MnO)0.8
0.20 : 0.20
0.60 : 0.48
0.20 : 0.20
0.60 : 0.41
0.20 : 0.21
0.80 : 0.83
ers were lower than in the composition containing
60 mol % MnO2
.
Further, determinations of the specific surface
areas for powder compositions and their components
(Table 2) showed that the surface area remains virtuꢀ
ally unchanged for individual manganese and yttrium
For (Al2O3)0.8(MnO2)0.2 and (Al2O3)0.2(MnO2)0.8
activator compositions and for 100 mol % MnO2 with
the manganese proportion in the initial mixture of
0.20 : 0.80 : 1, in the resulting oxide films, this proporꢀ
tion is 0.21 : 0.38 : 1. The minimum on the oxide layer
thickness versus composition plot (figure, panel c)
may be explained proceeding from this activator proꢀ
portion in the oxide layer. For example, for composiꢀ
tions having minimal manganese dioxide contents, the
activator proportions in the initial mixture and in the
resulting oxide layer are retained (the linear region).
As the manganese dioxide concentration in the comꢀ
position increases further, the manganese concentraꢀ
tion in the oxide layer becomes far lower than the
expectation (the nonlinear region). From Xꢀray difꢀ
fraction data (Table 1) for the Al2O3–MnO2 composiꢀ
tion, it follows that when the initial mixture contains a
minimal aluminum oxide amount, lowꢀactivity
Mn3O4 is formed. Inasmuch as Mn3O4 is a less strong
activator than MnO2 (which correlates with the vapor
oxides after 10ꢀmin annealing at 530°C. In MnO–
Y2O3 compositions, annealing does not noticeably
change the specific surface area; that is, the chemisꢀ
timulator does not sinter in the course of annealing.
Thus, we have discovered that the Y2O3 inert comꢀ
ponent does not change the activating effect of chemꢀ
istimulators on GaAs thermal oxidation. Use of
yttrium oxide as an inert component in compositions
with MnO2 and MnO activator oxides revealed a conꢀ
ceptual feasibility of linear and additive GaAs oxidaꢀ
tion under the action of twoꢀoxide compositions.
The discovered effects well correlate with the
EPMA elemental analyses of oxide layers (Table 4).
For compositions containing Ga2O3 (Al2O3) and manꢀ
ganese oxides, the relative content of the chemistimuꢀ
lator in the resulting oxide layers coincides with its
content in the initial compositions in the linear region
and differs from this in the nonadditivity region.
For aluminum oxide compositions, the
(Al2O3)0.4(MnO)0.6 composition has a higher mangaꢀ
nese content in the oxide layer compared to the initial
composition. Similar results were obtained for the galꢀ
pressure of Mn3O4 at 527
°C (
= 5.33 mPa) and
p
O2
MnO ( = 5.33 Pa)), its formation in a composition
p
2
O2
should decrease the manganese content of the oxide
layer.
For the compositions involving yttrium oxide, as
lium oxide systems: manganese contents in oxide layꢀ expected, the relative content of the activator element
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 12 2010

1862
KOZHEVNIKOVA et al.
4. S. I. Kol’tsov, V. K. Gromov, and R. R. Rachkovskii,
The Ellipsometric Method in Studying Solid Surfaces
(Nauka, Leningrad, 1983) [in Russian].
in the resulting oxide layers (Table 4) coincides with
that in the initial compositions over the entire range of
the compositions studied, and additivity is observed
here.
Thus, an inert component in activator oxide comꢀ
positions does not always lead to complete additivity in
the oxide layer thickness grown on GaAs as a function
of composition, although a linear dependence is
observed over a wide range of compositions.
5. K. Nakomoto, IR Spectra of Inorganic and Coordination
Compounds (Wiley, New York, 1988; Mir, Moscow,
1991).
6. J. Goldstein, D. Newbury, and P. Echlin, Scanning
Electron Miscoscopy and Xꢀray Microanalysis (Plenum,
New York, 1981; Mir, Moscow, 1984).
For the MnO–Y2O3 and MnO2–Y2O3 systems, this
additivity is observed over the entire range of the comꢀ
positions. For other systems, however, additional
nonchemical factors have been revealed to be responꢀ
sible for nonadditivity and nonlinear effects.
7. V. A. Logvinenko, F. Paulik, and I. Paulik, QuaiꢀEquiꢀ
librium Thermogravimetry in Contemporary Inorganic
Chemistry (Nauka, Novosibirsk, 1989) [in Russian].
8. Xꢀray Diffraction Data Cards (ASTM).
9. S. Gregg and K. Sing, Adsorption, Surface Area, and
Porosity (Academic Press, New York, 1982; Mir, Mosꢀ
cow, 1984).
ACKNOWLEDGMENTS
10. I. Ya. Mittova, S. I. Lopatin, V. R. Pshestanchik, et al.,
Zh. Neorg. Khim. 50 (10), 1599 (2005) [Russ. J. Inorg.
Chem. 50 (10), 1488 (2005)].
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 06ꢀ03ꢀ96338ꢀ
r_tsentr_a) and a Presidential Grant for Young Scienꢀ
tists (grant no. MKꢀ1347.2005.3).
11. P. K. Penskoi, V. F. Kostryukov, V. R. Pshestanchik, and
I. Ya. Mittova, Dokl. Akad. Nauk 414 (6), 765 (2007).
12. W. D. Kingeri, Introduction to Ceramics (Wiley, New
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RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 12 2010