Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions
Modelling the process to obtain vanadium dioxide in systems V – O – H – Na and V – O – H – S has been carried out using the program complex “Selector”. The latter is based on a computer method for thermodynamic analysis of equilibrium compositions. The dependences of the concentration of main compon...
Saved in:
| Published in: | Semiconductor Physics Quantum Electronics & Optoelectronics |
|---|---|
| Date: | 2011 |
| Main Authors: | , , , |
| Format: | Article |
| Language: | English |
| Published: |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2011
|
| Online Access: | https://nasplib.isofts.kiev.ua/handle/123456789/117608 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Cite this: | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions / I.M. Chernenko, O.P. Mysov, O.Yu. Oleinik, A.I. Ivon // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 1. — С. 51-54. — Бібліогр.: 17 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860078906053230592 |
|---|---|
| author | Chernenko, I.M. Mysov, O.P. Oleinik, O.Yu. Ivon, A.I. |
| author_facet | Chernenko, I.M. Mysov, O.P. Oleinik, O.Yu. Ivon, A.I. |
| citation_txt | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions / I.M. Chernenko, O.P. Mysov, O.Yu. Oleinik, A.I. Ivon // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 1. — С. 51-54. — Бібліогр.: 17 назв. — англ. |
| collection | DSpace DC |
| container_title | Semiconductor Physics Quantum Electronics & Optoelectronics |
| description | Modelling the process to obtain vanadium dioxide in systems V – O – H – Na and V – O – H – S has been carried out using the program complex “Selector”. The latter is based on a computer method for thermodynamic analysis of equilibrium compositions. The dependences of the concentration of main components in V – O – H – Na and V – O – H – S systems on hydrogen index pH as well as the dependence of the VO2 concentration on pressure in the system V – O – H – Na are given. The possibility to obtain vanadium dioxide in water solution of the systems involved has been estimated.
|
| first_indexed | 2025-12-07T17:15:10Z |
| format | Article |
| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 1. P. 51-54.
PACS 81.20.Ka
Computer simulation of vanadium dioxide semiconductor
phase formation in supersaturated solutions
I.M. Chernenko1, O.P. Mysov1, O.Yu. Oleinik1, A.I. Ivon2
1State Higher Educational Institution “Ukrainian State Chemical Technology University”
8, prospect Gagarina, 49005 Dnipropetrovsk, Ukraine
2Oles’ Gonchar Dnipropetrovsk National University,
72, prospect Gagarina, 49010 Dnipropetrovsk, Ukraine
Corresponding author e-mail: oleinik_o@ukr.net
Abstract. Modelling the process to obtain vanadium dioxide in systems V – O – H – Na
and V – O – H – S has been carried out using the program complex “Selector”. The latter
is based on a computer method for thermodynamic analysis of equilibrium compositions.
The dependences of the concentration of main components in V – O – H – Na and
V – O – H – S systems on hydrogen index pH as well as the dependence of the VO2
concentration on pressure in the system V – O – H – Na are given. The possibility to
obtain vanadium dioxide in water solution of the systems involved has been estimated.
Keywords: vanadium dioxide, phase transition, thermodynamical equilibrium,
concentration.
Manuscript received 10.06.10; accepted for publication 02.12.10; published online 28.02.11.
1. Introduction
Below the temperature of Tk = 68 °C, crystalline
vanadium dioxide (VO2) is a semiconductor with the
forbidden gap width close to 0.7 eV. Above Tk
temperature, VO2 changes into the metallic state due to
the 1st order phase transition (PT) “semiconductor –
metal” [1]. This transition is accompanied by a jump in
all the properties of VO2. The changes in electrical and
optical properties are of special interest for practical
applications. Thus, the specific resistivity of
monocrystalline vanadium dioxide changes by 104 times
within the range of ~3 °C around the phase transition
temperature. In temperature-sensitive resistors based on
VO2, it gives the temperature coefficient of resistance
increase up to ~80%/K at the phase-transition
temperatures. These values greatly exceed the
corresponding values in available commercial
thermoresistors.
PT-induced changes in optical parameters of
vanadium dioxide can be applied in photon crystals [2]
and in elements of laser optical tracts [3]. It has been
found that the phase transition in VO2 is accomplished
within a uniquely short period of time, viz. dozens of
femtoseconds [4].
However, the repeated temperature changes over
the range that includes the phase transition temperature
produce considerable mechanical stresses in the samples,
which may result in their cracking. This may shorten the
service life of electronic and optical elements based on
vanadium dioxide. The results of investigations [5] show
that the affects of mechanical stresses on VO2 sample
strengths can be reduced by decreasing geometrical
dimensions of vanadium dioxide crystals to the values of
less than one micrometer.
The common methods of crystalline vanadium
dioxide synthesis provide for producing crystals with
minimum averaged dimensions of the order of
millimeter units [6]. The most suitable methods for
obtaining particles of smaller sizes are the methods of
dispersion and condensation [7]. The chemical method
for liquid-phase condensation of VO2 particles in the
form of soles is the most acceptable technique for
synthesizing vanadium dioxide nanoparticles.
Preparation of nanodispersed particles by this method
involves the following steps: preparation of a solution of
several components possessing rather high solubility,
one of them being a vanadium-containing material;
initiating a chemical reaction in the solution, which
results in producing the required low-soluble vanadium
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
51
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 1. P. 51-54.
product; and extraction of the vanadium product from
the solution.
The most complicated tasks in the implementation
of the above method are: the proper selection of the
solution components, the choice of the required
technological conditions, the analysis of the chemical
composition of the final product, and its decomposition
into separate phase components. To practically select the
ways of employing this method for an assigned
particular product is inexpedient since it requires much
effort, cost and time, while the results are unpredictable.
The most efficient way to find the proper method of
synthesizing a required chemical compound is a
computer simulation of phase formation in the solution
chosen.
This study is aimed at the development of chemical
foundations for the synthesis of nanocrystalline
vanadium dioxide by using the condensation method.
This involves selecting the initial components and
defining the conditions for the most expedient liquid-
phase reaction on the base of computer simulation of
thermodynamic processes in supersaturated solutions.
To reach the targets, “Selector” software package
[8] was used, which is intended to minimize
thermodynamic potentials in chemical media.
The software package consists of a system of inter-
coordinated databases for thermodynamic data and the
bank of initial chemical compositions. “Selector”
program medium is based on a coordinated interaction of
functional and information block sets. The main of these
are: available calculation model database, calculation
model creation unit, reference data base, computation
unit, computation analysis unit, result presentation unit.
If necessary, the program can form a newly
required calculation model in case it is missed from the
available model base. The required calculation model is
then created using the list of specified allowed
equilibrium phases and dependent components, and
compositions of independent components.
The program provides several alternative models
that differ in thermodynamic potentials used. The
program calculations are performed with account of the
following six potentials: Helmholtz thermodynamic
potential, Gibbs thermodynamic potential, isochoric-
isentropic, isobaric-isentropic, isobaric-isenthalpic, and
isochoric-isenergetic potentials. The properties of the
prototype chemical system determine the choice of an
alternative model.
The software package allows calculations of full-,
metastable and intermediate chemical equilibrium phase
states in systems where aqueous solutions of various
electrolytes, gas mixtures, liquid and solid one- and
multicomponent phases may be present.
“Selector” program allows estimating the thermal
and pressure behavior of the chemical system
thermodynamic parameters. Activity coefficients of the
aqueous solution components in these systems are
estimated using the modified Debye-Hukkel equation in
the Helgeson version [9]. Calculations are performed
using thermodynamic properties of independent
components available in commonly used thermodynamic
databases [10, 11].
The productive algorithm of convex programming
was used to perform these calculations. The algorithm is
based on the method of internal points with one- and
two-side restraints on calculation values.
At the final stage of simulations, the calculation
result analysis module displays the results in the form of
tables; additionally, they may be displayed in a graphic
form.
In this study, the “Selector” software package was
used to select equilibrium phase states in aqueous
vanadium-containing media with the aim of determining
chemical conditions for vanadium dioxide phase
formation. Two chemical systems were studied: V – O –
H – S and V – O – H – Na. Both systems can be
implemented in reality as aqueous solutions of vanadium
pentoxide with addition of sulfate acid or sodium
hydroxide. They were chosen as prototype systems
proceeding from good solubility of vanadium pentoxide
(V2O5) in water (0.07 g vanadium pentoxide is dissolved
in 100 g of water at 25 °C). It should be noted that
vanadium dioxide is insoluble in water.
The equilibrium phase compositions in the systems
involved were obtained by minimization of the Gibbs
isobaric-isothermic potential. This appears to be the
most reasonable technique, since in this case, the
independent thermodynamic parameters would be the
temperature and pressure that under real process
conditions are set naturally by the environment.
The program calculations of phase formation were
performed using dependent components and constituents
of the thermodynamic system. The list includes 46
aqueous solution components, 22 gaseous medium
components and 22 solid phase components which can
potentially take part in the process of creating new
phases. The list of solid-phase components includes all
vanadium oxides with whole-numbered valence, and
most vanadates known so far. The list of aqueous
solution components comprises all possible simple
vanadium ions and complex ions including tetravalent
vanadium ions (oxyvanadyl VO2+) and pentavalent
vanadium VO4
3–, H2VO4
–, VO2
+ and others.
Simulation of phase formation in V – O – H – S
system was performed for a virtual chemical medium
consisting of vanadium pentoxide V2O5 0.055 mol, water
55.5 mol and sulfate acid H2SO4 0.25 mol, the sulfate
acid content varying from 0 to 0.25 mol by 0.01-mol
steps.
The results of the computer simulation of the phase
formation in V – O – H – S system indicate that the
system produces 11 components, their proportions
varying from to . According to their
chemical compositions, the components produced may
be separated into two groups: vanadium-containing and
sulfur-containing. The first group includes: neutral
phases V
-110 mol10-18
2O5, H3VO4, anions VO4
3–, H2VO4
–, HVO4
2–
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
52
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 1. P. 51-54.
and cations VO2+, VO2
+, VOOH+; the second group
comprises SO4
2– and H2SO4
– ions. Besides, the
thermodynamic system involved includes oxygen O2.
The ionic state of vanadium differs in vanadium-
containing components: V5+(V2O5, H3VO4, VO2
+, VO4
3–,
HVO4
2–), V4+ (VO2+), V3+ (VO+, VOH2+). It can be seen
that the most common components in the V – O – H – S
system solution are those with pentavalent vanadium.
These are: vanadium pentoxide, orthovanadate acid
H3VO4, ions of oxovanadium (V) – VO2
+; their presence
in acidic solutions agrees with the available publications
[12, 13]. The only tetravalent vanadium component is
the vanadyl ion VO2+.
The contents for most of solution components
depend on the proportion of sulfuric acid in the solution,
which determines the solution pH values. Fig. 1 shows
the concentrations of the V – O – H – S system main
components as a function of the solution pH value at the
temperature 25 °C. However, the solution components
obtained in concentrations less than 10–7 mol/l are not
shown in Fig. 1. The range of sulfuric acid contents of
the solution, used in the study, provided for the
vanadium ion concentration variations from 10–4 to
10–1 mol/l.
Fig. 1. The concentrations of V-O-H-S system main
components plotted against the solution pH value at the
temperature 25 °C.
Fig. 2. The concentrations of the V-O-H-Na system main
components plotted against the solution pH values at the
temperature 25 °C.
Fig. 3. VO2 concentrations plotted against pressure in
V – O – H – Na system.
The simulation results indicate that the number of
components in the prototype thermodynamic system
depends on the solution pH value. All the dependences
including those in Fig. 1 are monotonic decreasing or
increasing functions, their maximum content values
being determined by the solution pH value.
Vanadyl ions present in the prototype system
(maximum concentration 10–2 mol/l) make it perspective
for further developments.
The second chemical system used for the
simulation of vanadium dioxide phase formation was
V – O – H – Na system. For this purpose, the process of
vanadium pentoxide interaction with sodium hydroxide
(NaOH) in an aqueous solution was simulated. To
simulate the phase formation, a virtual medium was
used, containing vanadium pentoxide V2O5 0.055 mol,
water 55.5 mol, and sodium hydroxide varying from 0 to
0.24 mol, in 0.01 mol increments.
The simulation results indicate that the prototype
system contains 17 components. These include 7 neutral
components: V2O5, NaOH, Na2V2O6, H3VO4, VO2, O2,
H2; and 10 ionic components: H2VO4
–, HVO4
2–,
VOOH+, VON2+, VOH+, VO+, VO2+, VO2
+, VO4
3–, Na+.
The latter, except Na+, are vanadium-containing
components that contain vanadium in various valent
states. Among the neutral components, VO2 phase is
present, which is of special interest for the investigations
undertaken.
The component contents of the solution depend on
sodium hydroxide content, which determines the pH
values in a medium. The solution component
concentrations plotted against pH values are shown in
Fig. 2. Here, as a simplification, the components
obtained in concentrations above 10–8 mol/l are only
represented. In the representation coordinates used, the
functional dependences show different behavior: they
may decrease (V2O5, VO2+, VO2
+, H2VO4), increase
(NaOH, VO4
3–, Na+), or reach an extremum (Na2V2O6,
VO2, H3VO4, HVO4
2–, H2), which is determined by the
thermodynamic equilibrium conditions in the system.
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
53
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 1. P. 51-54.
The correctness of the performed computer
simulation is confirmed by the presence of a well-
studied sodium dimethavanadate Na2V2O6 [14] in the
prototype system, as well as VO2+ and VO2
+ ions
characteristic of aqueous solutions of vanadium
pentoxide [13], and complex ions of vanadium (V)
H2VO4
– and HVO4
2– described in [15]. This is also
confirmed by the uncharacteristic behavior of the
solution pH value that shows its minimum at NaOH
content of 0.11 mol. This peculiarity is caused by the
concentration dependence maximum formed in the
orthovanadate acid H3VO4 solution that naturally
decreases the pH value. It is significant that the above
concentration of sodium hydroxide results in a sharp
decrease of V2O5 phase content of the solution, which
indicates the total vanadium pentoxide dissociation.
The computer simulation results obtained show that
VO2 phase is present in the solution at pH = 6 to 11. Its
concentration is practically constant and the maximum
content of vanadium dioxide is 5.5⋅10–7 mol/l and occurs
at pH = 7.9. This phase may be most probably present in
the form of soles, which allows producing vanadium
dioxide in the form of nanoparticles. In the prototype
system, these particles may be probably found in an
amorphous state, thus an additional thermal treatment
may be required for their crystallization [16]. The
simulation of thermal and pressure behavior of the
vanadium dioxide phase concentrations obtained is
important for practical applications. This simulation of
VO2 content dependences on temperature in similar
systems indicates that within the temperature range 20 to
100 °C, vanadium dioxide concentrations show a slight
increase with temperature [17].
VO2 content dependences on pressure in
V – O – H – Na system, obtained using simulation by
means of the “Selector” software package, are shown in
Fig. 3. It is obvious that no essential changes of
vanadium dioxide content of the solution occur within
the range of 0.1 to 10 MPa.
References
1. A.A. Bugayev, B.M. Zakharchenya,
F.A. Chudnovsky, Metal-Semiconductor Phase
Transition and its Application. Nauka, Leningrad,
1979 (in Russian).
2. A.V. Akimov, A.V. Virchenko, V.G. Golubev,
A.A. Kaplyansky, D.A. Kurdyukov, A.B. Pevtsov,
A.V. Shcherbakov, Imaging the spectrum of Bragg
diffraction in composites opal-VO2 under action of
laser pulses // Fizika tverdogo tela, 45(2), p. 231-
234 (2003), in Russian.
3. O.B. Danilov, V.A. Klimov, O.P. Mikheyeva
A.I. Sidorov, S.A. Tul’sky, E.B. Shadrin, I.L.
Yachnev, Optical limitation of radiation in the
middle IR range in vanadium dioxide films //
Zhurnal tekhnich. fiziki, 73(1), p. 79-85 (2003), in
Russian.
4. A. Cavalleri, C. Toth, C.W. Siders, J.A. Squier,
F. Raksi, P. Forget, J.C. Kieffer, Femtosecond
structural dynamics in VO2 during an ultrafast
solid-solid phase transition // Phys. Rev. Lett.,
87(23), 237401-237404 (2001).
5. A.I. Ivon, Glass-ceramic materials based on the
component with phase transition metal-
semiconductor. Doctor Thesis. Dnipropetrovsk,
2008.
6. Patent of Ukraine No.40748А, Int. Cl. С01,
G31/02. The way to prepare vanadium dioxide /
A.I. Ivon, I.M. Chernenko, V.R. Kolbunov
(Ukraine); Dnipropetrovsk National University,
№99010384; Appl. from 26.01.99; Published
16.07.2001. Bulletin No.6.
7. Yu.G. Frolov, Colloidal Chemistry. Al’yans,
Moscow, 2004 (in Russian).
8. K.V. Chudnenko, Theory and software for
providing the method for minimization of
thermodynamic potentials to solve geochemical
tasks. Doctor Thesis. Irkutsk, published in Irkutsk
State Technological University, 2007 (in Russian).
9. H.C. Helgeson, D.H. Kirkham, G.C. Flowers,
Theoretical prediction of the thermodynamic
behavior of aqueous electrolytes at high pressures
and temperatures: IV. Calculation of activity
coefficients // Amer. J. Sci., 281, p. 1249-1516
(1981).
10. E.L. Shock and H.C. Helgeson, Calculation of the
thermodynamic and transport properties of aqueous
species at high pressures and temperatures:
Correlation algorithms for ionic species and
equation of state predictions to 5 kb and 1000 °C //
Geochim. Cosmochim. Acta, No.52, p. 2009-2036
(1988).
11. H. Yokokawa, Tables of thermodynamics properties
of inorganic compounds // J. National Chemical
Laboratory for industry, 83, p. 27-121 (1988).
12. A.S. Goncharenko, Electrochemistry of Vanadium
and its Compounds. Metallurgiya, Moscow, 1969
(in Russian).
13. V.N. Muzgin, L.B. Khamzina, V.L. Zolotavin,
I.Ya. Bezrukov, Analytical Chemistry of Vanadium.
Nauka, Moscow, 1981 (in Russian).
14. A.A. Fotiyev, B.V. Slobodin, M.Ya. Khodos,
Vanadates. Composition, Synthesis, Structure and
Properties. Nauka, Moscow, 1988 (in Russian).
15. Chemistry of pentavalent vanadium in water
solutions // Proc. Institute for Chemistry, Ural Sci.
Center, AS of USSR, No.24, Sverdlovsk, 1971 (in
Russian).
16. A.I. Gusev, A.A. Rempel’, Nanocrystalline
Materials. Fizmatlit, Moscow, 2001 (in Russian).
17. N.A. Shabanova, V.V. Popov, P.D. Sarkisov,
Chemistry and Technology of Nanodispersed
Oxides. Akademkniga, Moscow, 2006 (in Russian).
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
54
|
| id | nasplib_isofts_kiev_ua-123456789-117608 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2025-12-07T17:15:10Z |
| publishDate | 2011 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| record_format | dspace |
| spelling | Chernenko, I.M. Mysov, O.P. Oleinik, O.Yu. Ivon, A.I. 2017-05-25T16:48:43Z 2017-05-25T16:48:43Z 2011 Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions / I.M. Chernenko, O.P. Mysov, O.Yu. Oleinik, A.I. Ivon // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 1. — С. 51-54. — Бібліогр.: 17 назв. — англ. 1560-8034 PACS 81.20.Ka https://nasplib.isofts.kiev.ua/handle/123456789/117608 Modelling the process to obtain vanadium dioxide in systems V – O – H – Na and V – O – H – S has been carried out using the program complex “Selector”. The latter is based on a computer method for thermodynamic analysis of equilibrium compositions. The dependences of the concentration of main components in V – O – H – Na and V – O – H – S systems on hydrogen index pH as well as the dependence of the VO2 concentration on pressure in the system V – O – H – Na are given. The possibility to obtain vanadium dioxide in water solution of the systems involved has been estimated. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions Article published earlier |
| spellingShingle | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions Chernenko, I.M. Mysov, O.P. Oleinik, O.Yu. Ivon, A.I. |
| title | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| title_full | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| title_fullStr | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| title_full_unstemmed | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| title_short | Computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| title_sort | computer simulation of vanadium dioxide semiconductor phase formation in supersaturated solutions |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/117608 |
| work_keys_str_mv | AT chernenkoim computersimulationofvanadiumdioxidesemiconductorphaseformationinsupersaturatedsolutions AT mysovop computersimulationofvanadiumdioxidesemiconductorphaseformationinsupersaturatedsolutions AT oleinikoyu computersimulationofvanadiumdioxidesemiconductorphaseformationinsupersaturatedsolutions AT ivonai computersimulationofvanadiumdioxidesemiconductorphaseformationinsupersaturatedsolutions |