Научная статья на тему 'Nanoscale semiconductor and dielectric films and magnetic nanocrystals – new directions of development of the scientific school of Ya. A. Ugai “Solid state chemistry and semiconductors”. Review'

Nanoscale semiconductor and dielectric films and magnetic nanocrystals – new directions of development of the scientific school of Ya. A. Ugai “Solid state chemistry and semiconductors”. Review Текст научной статьи по специальности «Химические науки»

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Semiconductors / Dielectrics / Magnetic nanocrystals / Ferrites / Nanoscale films / Nanocrystals

Аннотация научной статьи по химическим наукам, автор научной работы — Irina Ya. Mittova, Boris V. Sladkopevtsev, Valentina O. Mittova

New directions of development of the scientific school of Yakov Aleksandrovich Ugai “Solid state chemistry and semiconductors” were considered for the direction “Study of semiconductors and nanostructured functional films based on them”, supervised by I. Ya. Mittova. The study of students and followers of the scientific school of Ya. A. Ugai cover materials science topics in the field of solid-state chemistry and inorganic and physical chemistry. At the present stage of research, the emphasis is being placed precisely on nanoscale objects, since in these objects the main mechanisms of modern solid-state chemistry are most clearly revealed: the methods of synthesis composition structure (degree of dispersion) properties. Under the guidance of Professor I. Ya. Mittova DSc (Chem.), research in two key areas is conducted: “Nanoscale semiconductor and dielectric films” and “Doped and undoped nanocrystalline ferrites”. In the first area, the problem of creating high-quality semiconductor and dielectric nanoscale films on AIIIBV by the effect reasonably selected chemostimulators on the process of thermal oxidation of semiconductors and/or directed modification of the composition and properties of the films. They present the specific results achieved to date, reflecting the positive effect of chemostimulators and modifiers on the rate of formation of dielectric and semiconductor films of the nanoscale thickness range and their functional characteristics, which are promising for practical applications. Nanomaterials based on yttrium and lanthanum orthoferrites with a perovskite structure have unique magnetic, optical, and catalytic properties. The use of various approaches to their synthesis and doping allowing to control the structure and properties in a wide range. In the field of magnetic nanocrystals under the supervision of Prof. I. Ya. Mittova studies of the effect of a doping impurity on the composition, structure, and properties of nanoparticles of yttrium and lanthanum orthoferrites by replacing the Y(La)3+ and Fe3+ cations are carried out. In the Socialist Republic of Vietnam one of the talented students of Prof. I. Ya. Mittova, Nguyen Anh Tien, performs studies in this area. To date, new methods for the synthesis of nanocrystals of doped and undoped ferrites, including ferrites of neodymium, praseodymium, holmium, etc. have been developed.

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Текст научной работы на тему «Nanoscale semiconductor and dielectric films and magnetic nanocrystals – new directions of development of the scientific school of Ya. A. Ugai “Solid state chemistry and semiconductors”. Review»

ISSN 1606-867Х (Print) ISSN 2687-0711 (Online)

Condensed Matter and Interphases

Kondensirovannye Sredy i Mezhfaznye Granitsy https://journals.vsu.ru/kcmf/

Review

Review article

https://doi.org/10.17308/kcmf.2021.23/3524

Nanoscale semiconductor and dielectric films and magnetic nanocrystals - new directions of development of the scientific school of Ya. A. Ugai "Solid state chemistry and semiconductors". Review

I. Ya. Mittova1, B. V. Sladkopevtsev1, V. O. Mittova2

1Voronezh State University,

1 Universitetskaya pl., Voronezh 394018, Russian Federation 2Voronezh State Medical University named after N. N. Burdenko, 12 Studencheskaya Street, Voronezh 394036, Russian Federation Abstract

New directions of development of the scientific school of Yakov Aleksandrovich Ugai "Solid state chemistry and semiconductors" were considered for the direction "Study of semiconductors and nanostructured functional films based on them", supervised by I. Ya. Mittova. The study of students and followers of the scientific school of Ya. A. Ugai cover materials science topics in the field of solid-state chemistry and inorganic and physical chemistry. At the present stage of research, the emphasis is being placed precisely on nanoscale objects, since in these objects the main mechanisms of modern solid-state chemistry are most clearly revealed: the methods of synthesis - composition - structure (degree of dispersion) - properties. Under the guidance of Professor I. Ya. Mittova DSc (Chem.), research in two key areas is conducted: "Nanoscale semiconductor and dielectric films" and "Doped and undoped nanocrystalline ferrites". In the first area, the problem of creating high-quality semiconductor and dielectric nanoscale films on AIIIBV by the effect reasonably selected chemostimulators on the process of thermal oxidation of semiconductors and/or directed modification of the composition and properties of the films. They present the specific results achieved to date, reflecting the positive effect of chemostimulators and modifiers on the rate of formation of dielectric and semiconductor films of the nanoscale thickness range and their functional characteristics, which are promising for practical applications.

Nanomaterials based on yttrium and lanthanum orthoferrites with a perovskite structure have unique magnetic, optical, and catalytic properties. The use of various approaches to their synthesis and doping allowing to control the structure and properties in a wide range. In the field of magnetic nanocrystals under the supervision of Prof. I. Ya. Mittova studies of the effect of a doping impurity on the composition, structure, and properties of nanoparticles of yttrium and lanthanum orthoferrites by replacing the Y(La)3+ and Fe3+ cations are carried out. In the Socialist Republic ofVietnam one of the talented students of Prof. I. Ya. Mittova, Nguyen Anh Tien, performs studies in this area. To date, new methods for the synthesis of nanocrystals of doped and undoped ferrites, including ferrites of neodymium, praseodymium, holmium, etc. have been developed.

Keywords: Semiconductors, Dielectrics, Magnetic nanocrystals, Ferrites, Nanoscale films, Nanocrystals Acknowledgements: the authors are grateful to Full Member of the Russian Academy of Sciences V. M. Ievlev for providing the opportunity for further creative development of research within the framework of the scientific school, for their support and assistance.

For citation: Mittova I. Ya., Sladkopevtsev B. V., Mittova V. O. Nanoscale semiconductor and dielectric films and magnetic nanocrystals - new directions of development of the scientific school of Ya. A. Ugai "Solid state chemistry and semiconductors". Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2021;23(3): 309-336. https://doi. org/10.17308/kcmf.2021.23/3524

Для цитирования: Миттова И. Я., Сладкопевцев Б. В., Миттова В. О. Наноразмерные полупроводниковые и диэлектрические пленки и магнитные нанокристаллы - новые направления развития научной школы Я. А. Угая «Химия твердого тела и полупроводников». Конденсированные среды и межфазные границы. 2021;23(3): 309-336. https://doi.org/10.17308/kcmf.2021.23/3524

И Irina Ya. Mittova, e-mail: imittova@mail.ru

© Mittova I. Ya., Sladkopevtsev В. V., Mittova V. 0., 2021

The content is available under Creative Commons Attribution 4.0 License.

1. Introduction

New research of the scientific school of Ya. A. Ugai "Solid state chemistry and semiconductors" [1] in the subdivision "Study of semiconductors and nanostructured functional films based on them", supervised by I. Ya. Mittova, are developing in a number of directions "in breadth and depth". They are performed by both the followers of Yakov Aleksandrovich's work and by the "students of followers", which is reflected in Table 1. In fact, we can talk about a deeper scientific continuity, since Yakov Aleksandrovich defended his Ph.D. thesis on the physical and chemical analysis of salt systems under the

Table 1. Defence of thesis

guidance of Prof. A. P. Palkin, who, in turn, was a student of Full Member of the Russian Academy of Sciences N. S. Kurnakov. The coverage of modern materials science topics in the field of solid-state chemistry and inorganic and physical chemistry as developed by students and followers of the scientific school of Ya. A. Ugai, his "scientific children, grandchildren, and greatgrandchildren" can be seen in Table 1. Here one cannot fail to mention one of the most talented, beloved, and successful students of Ya. A. Ugai, Evelina Domashevskaya. For many years she was the Head of the Department of Solid-State Physics and Nanostructures of Voronezh State

No. Thesis Full name of the applicant Title of dissertation Year of defence

1 2 3 4 5

Scientific ac visor/consultant Prof. I. Ya. Mittova

Natalia Ivanovna Ponomareva Formation of functional layers on semiconductors by

1 Doctorate chemical vapour deposition from organoelement 2004

compounds

Alexander Directed synthesis of lead telluride films doped with

2 Doctorate Mikhailovich Samoilov gallium and indium with the controlled content of impurity atoms and deviation from stoichiometry 2006

3 Doctorate Viktor Fedorovich Combined effect of chemostimulants on the thermal 2011

Kostryukov oxidation of gallium arsenide

Elena Viktorovna Tomina Chemically stimulated oxidation of GaAs and InP

4 Doctorate under the action of d-metals (Ni, Co, V), their oxides 2017

and oxide compositions

5 PhD Tatiana Alexandrovna Growth kinetics and some properties of doped oxide films on silicon 1983

Gadebskaya

Natalia Ivanovna Ponomareva Interaction of chlorides of elements of III, IV and V

6 PhD groups with the surface of silicon and gallium arsenide in an oxidizing atmosphere 1984

Victoria Interactions in Si-ExSy structures (E = In, Ge, Pb, Sb, Bi)

7 PhD Vladimirovna Pukhova and GaAs-ExSy(E = In, Pb, Sb) during their thermal oxidation 1986

8 PhD Vera Vasilievna Thermal oxidation of gallium arsenide and indium 1995

Sviridova phosphide in the presence of impurity oxides

9 PhD Irina Vladimiovna Phase formation processes in alumina ceramics 1995

Kuznetsova modified with oxides of copper, nickel and boron

10. Elena Viktorovna Tomina Thermal oxidation of gallium arsenide and indium

PhD phosphide with the participation of chlorides and oxochlorides of elements of groups IV - VI 1997

11 PhD Viktor Fedorovich Kostryukov Nonlinearity of the combined effect of lead, antimony and bismuth oxides on the thermal oxidation of gallium arsenide 2000

12 PhD Olga Anatolyevna Pinyaeva Chemostimulating effect of chromium derivatives on thermal oxidation of gallium arsenide 2001

I. Ya. Mittova et al. Review

End of Table 1

1 2 3 4 5

13 PhD Olga Vladimirovna Artamonova Synthesis of nanoceramic materials based on zirconium dioxide stabilized with indium oxide 2004

14 PhD Alexey Sergeevich Sukhochev Solid-phase interactions during the thermal oxidation of Me/GaAs and MeO/GaAs structures (Me = Fe, Co, Ni) 2006

15 PhD Irina Alexandrovna Donkareva Localization regions of interactions between activator oxides during the thermal oxidation of gallium arsenide 2006

16 PhD Petr Konstantinovich Penskoy Thermal oxidation of GaAs under the influence of Sb2O3, Bi2O3, MnO, MnO2 chemostimulant compositions with inert components Ga2O3, Al2O3, Y2O3 2009

17 PhD Nguyen Anh Tien Synthesis, structure and properties of La(Y)1xSr(Ca)xFeO3 (x = 0.0; 0.1; 0.2; 0.3) nanopowders 2009

Alexander Evolution of nanoscale film and island structures Me/

18 PhD Alexandrovich Lapenko InP (GaAs) and MexO/ InP (GaAs) (Me = V, Co) during thermal oxidation 2010

19 PhD Dinh Van Tac Sol-gel synthesis and properties of nanocrystalline ferrites based on Y2O3-Fe2O3 system 2012

20 PhD Boris Valdimirovich Sladkopevtsev Influence of the methods for the formation of VxO/InP structures on the features of their thermal oxidation 2013

and the composition of the films

21 PhD Alexey Alekseevich Samsonov Thermal oxidation of InP modified by deposited compositions of NiO+PbO, V2O5+PbO oxides 2013

22 PhD Maria Viktorovna Berezhnaya Effect of zinc and barium on the structure and properties of YFeO3 and LaFeO3-based nanopowders synthesized by the sol-gel method 2019

Scientific adviser prof. N. I. Ponomareva

Influence of an anolyte disinfectant solution on the

23 PhD Pavel Ivanovich Manelyak stability of geometric shapes of silicone imprints (joint supervision with DSc in Medical Sciences, Professor Edward Sarkisovich Kalivrajian, now deceased) 2009

24 PhD Elena Viktorovna Clinical and experimental substantiation of the use of an isoprene-styrene thermoplastic elastomer for basic removable laminar dentures 2009

Budakova (joint supervision with DSc in Medical Sciences, Professor Edward Sarkisovich Kalivrajian, now deceased)

25 PhD Tatiana Dmitrievna Poprygina Synthesis, structure, and properties of hydroxyapatite and the composites and coatings based on it 2012

Scientific adviser Prof. A. M. Samoilov

26 PhD Mikhail Konstantinovich Sharov Synthesis and properties of lead telluride films doped with gallium on silicon substrates 2000

27 PhD Sergey Vladimirovich Belenko One-step synthesis of gallium-doped PbTe/Si films with a specified composition and optimized functional parameters 2013

I. Ya. Mittova et al. Review

University, and now she is a professor of this department. The scientific school created by her "Atomic and electronic structure of solid state and nanostructures" is widely known not only in Russia, but also around the world. Undoubtedly, a great contribution in the formation of our scientific school was made by such outstanding students of Yakov Aleksandrovich as Associate Professor E. M. Averbakh (his first graduate student), professor V. Z. Anokhin, Associate Professors V. R. Pshestanchik and V. L. Gordin, who have unfortunately passed away. All of them laid the foundations for the study of objects that were new for that time, thin films of various functional purposes on semiconductors. New objects of research are mainly nanoscale, since in this area the main regularity of modern solid-state chemistry is most visibly and clearly manifested: synthesis method - composition - structure (degree of dispersion) - properties. This choice was due to the need to establish new fundamental laws of solid-state chemistry, the requirements of modern materials science, reflected in the current List of Critical Technologies (Technologies for the Production and Processing of Functional Nanomaterials) and the List of Priority Areas for the Development of Science, Technology and Engineering in the Russian Federation (Industry of Nanosystems).

2. Nanoscale semiconductors and dielectric films

Prospects for the development of all spheres of human activity are unambiguously associated with the improvement of microelectronic and nanoelectronic element bases. A variety of properties of AIIIBV type semiconductors determines their widespread use in devices for various technical purposes: for the production of the variety of optoelectronic devices in the infrared and visible ranges, high-speed electronic and powerful microwave devices [2].

One of the main tasks of the targeted formation of heterostructures on AIIIBV with the desired properties is the production of high-quality dielectric and semiconductor films of nanometer thickness and the improvement of the properties of the interfaces. The creation of high-quality heterostructures on AmBV by thermal oxidation is complicated by the mechanisms of

ongoing processes, due to the implementation of a negative communication channel between the stages of component-wise oxidation in the case of InP, the enrichment of films with unoxidized indium, and the segregation of arsenic in the elementary state at the inner interface of the heterostructure for GaAs [3]. Thermal oxidation of AIIIBV with the simultaneous action of interface modifiers and growing films, allowing to control their composition, nanostructure and properties, and chemostimulating agents promoting the accelerated formation of films with a decrease in the operating parameters of the process and blocking the negative communication channel of the intrinsic thermal oxidation of AmBV, allows achieving acceptable optical and electrophysical characteristics and to control the nanostructure of films, which is one of the factors determining their properties.

High-quality thermal oxide films on InP can be used in the development of highly efficient and cheap photoconverters of natural and linearly polarized radiation based on InP. Gallium arsenide, along with indium phosphide, is the most promising material for the production of next generation microwave integrated circuits [4].

The emergence of gallium arsenide microelectronics resulted in the creation of efficient and high-power injection lasers and LEDs in the wavelength range of 600-900 nm based on GaAs/GaAlAs heterostructures. Indium phosphide turned out to be a necessary component of more complex heteroepitaxial structures. As a result of these studies, InP technology arose and was rapidly developed, which currently constitutes a significant portion of micro- and optoelectronics. Laser diodes based on InP/ InGaPAs/InP are a key element of optoelectronics for fiber-optic communication, processing, data storage, etc., since they cover the ranges of the highest optical fibre transparency (wavelengths 1.3 and 1.55 ^m) [5]. In modern commercial and technical cable communications (intercomputer communications, long-distance telephony, local networks, etc.), these heterolasers are mainly used.

The energy parameters of the single-crystal phase of InP and GaAs are very close to the parameters of single-crystal silicon, which allows the manufacture of hybrid integrated electronics

I. Ya. Mittova et al. Review

devices compatible with silicon [6]. In addition to the production technology of microwave integrated circuits [4, 7, 8], heterostructures based on indium phosphide and gallium arsenide find many other applications, for example, as photodetectors [9, 10], in field-effect transistors based on Gatestacktechnology [11], memory cells [12], optoelectronic devices [13], in solar cells [14].

Wide-gap and optically transparent gallium phosphide is the main material for the creation of light-emitting diodes, photodetectors, photodetectors; it is promising for the development of high-temperature electronics devices capable of operating at temperatures significantly exceeding the reached limits of modern temperature sensors [15-17]. The unique optical properties of GaP single crystals are used to manufacture optical lenses and lenses for lasers [13]. However, any practical application of GaP requires the formation of various functional films (conductive, dielectric, antireflection, etc.) on its surface, which is undoubtedly associated with a number of technical difficulties. The use of gallium phosphide as waveguides and optical lenses for lasers is usually associated with the encapsulation of GaP single crystals in layers of a material with a lower refractive index (nGaP < 3.3), i.e., antireflection. Usually, AlGaP is used as the deposited material, which is well matched in lattice size with GaP [18].

Separately, it is necessary to highlight the areas of research associated with the formation of AIIIBV metal oxide semiconductor heterostructures by various methods. Among them are ZnO/InP heterostructures used to create optoelectronic devices and acoustic sensors [19, 20]; SnO2/InP with certain electrophysical properties, allowing their use as gas-sensitive sensors [21, 22]; multilayer heterostructures with a manganese dioxide layer with promising magnetic characteristics [23]. The range of synthesis methods used for such heterostructures is extremely wide: aerosol pyrolysis, molecular beam epitaxy, magnetron sputtering, CVD processes, etc. However, now, the idea of multipurpose control of the formation of functional nanoscale films on the surface of AIIIBV semiconductors by dopants remains practically unrealized. This approach allows fine adjustment of the kinetics and mechanism of the synthesis processes of these objects and the variation of their

composition, nanostructure, and, consequently, their properties within wide limits.

In the modern world, the demand for portable gas sensors is increasing due to the need for their widespread use in various branches of technology (for the prevention of explosions, fires) and for the control of environmental pollution. All these circumstances stimulated the development of research in the field of semiconductor gas sensors around the world. However, the study of the physical and chemical processes underlying the operation of sensors is still far from complete. Namely, the understanding of these processes allowed creating a new generation of highly efficient, reliable, and economical devices based on sensor elements. Among the materials studied, nanocrystalline tin dioxide has found the greatest practical application [24-27]. In addition to tin dioxide materials, other oxide materials are also studied (In2O3, ZnO, MoO3, Ga2O3), which may be of interest for creating chemical sensors. Indium oxide is characterized by its high sensitivity, fast response, a convenient range of resistance variation, and a sufficiently low temperature for detecting oxidizing and reducing gases in air [24]. The data [28, 29] and the results of studies [30] suggest that the decisive role in the exceptional sensory properties of In2O3 belongs to the high mobility of surface oxygen, which is characteristic for this oxide. There is an adsorption-competitive mechanism of the sensory response, which is associated with the displacement of oxygen from the surface with the subsequent adsorption of the detected gas molecules on the active sites of indium oxide. However, the low-dimensional structure of a single semiconducting metal oxide obtained by various methods does not solve the problem of selectivity and stability of the sensor material.

Therefore, it becomes necessary to alloy the oxide. It was shown in the study [24] that Fe2O3-In2O3 thin films exhibit maximum sensitivity to ozone at an operating temperature of 370 0C. In addition, the number of studies in which it was proposed to use multicomponent systems based on indium oxide with additives of other metal oxides ZnO - In2O3, MgO - In2O3, In2O3-SnO2 for the detection of chlorine in air is currently increasing [31, 32]. Attention is also paid to sensors based on copper oxide [33-35].

I. Ya. Mittova et al. Review

A significant disadvantage of the materials presented in the literature by various authors for the production of sensors is the high operating temperature (above 200 °C). This disadvantage can be offset by creating materials of mixed compositions [35].

The main direction of the development of our ideas, continuing the development of the considered section of the scientific school, is the use of chemostimulators and modifiers of the interface and growing films in the process of AIHBV oxidation for the control of the rate of their formation, composition, nanostructure, and properties [36-39]. The solution to the problem of creating high-quality semiconductor and dielectric films of nanometer scale thickness on A™BV is possible when changing the mechanism of thermal oxidation of these semiconductors from intrinsic to chemostimulated by influencing the process using reasonably selected chemostimulators and/or directed modification of the composition and properties of the films. The participation of chemostimulators in the oxidation process ensures the occurrence of new interface reactions with kinetically coupled and heterogeneous catalytic stages. In this case, the kinetic blocking of negative communication channels between the stages of oxidation of components AIII and BV due to the creation of new, positive channels with the participation of chemostimulators, the temperature and time of the synthesis process are reduced with a simultaneous modification of the composition and properties of functional films of nanometer thickness in the case of a chemostimulator with a modifying effect. We have previously shown [40-42] that the use of only modifiers of the inner interface and the films themselves already prevents the evaporation of the volatile component and degradation of the inner interface, reduce the density of surface states at the inner interface of the heterostructure, and control the structure and surface relief at the nanoscale. Naturally, the use of the combined action of a chemostimulator and a modifier is the most effective approach to solving this scientific problem. Based on many years of research, we have developed 2 methods for introducing a chemostimulator (modifier) into an oxidizing environment: directly in the process of thermal

oxidation of a semiconductor through the gas phase (method 1) and preliminary application to the surface, after which thermal oxidation of an already formed heterostructure occurs (method 2). At the same time, depending on the effect on the semiconductor surface, is the process of applying a chemostimulator (modifier), in the framework of method 2 we used two methods: method 1 (hard method) magnetron or vacuum-thermal deposition on the semiconductor surface and method 2 (soft method) of aerosol deposition or centrifugation. There is no noticeable effect on the semiconductor surface during the creation of the heterostructure using method 2 [43, 44].

The use of modifiers in combination with chemostimulators, in addition to blocking the diffusion of component A into the film in the unoxidized state and chemical bonding of component B at the inner interface, provides control over the growth rate, nanostructure, and properties of thermal oxide films and allows the development of new processes for the formation of functional nanosized dielectric and semiconductor films on AIIIBV semiconductors. The combined use of growth chemostimulators and modifiers is especially important in the formation of nanoscale films of a given thickness, when in the process of oxidation using only a chemostimulating agent due to the small thickness of the synthesized samples, the positive effect of the chemostimulator may not be fully realized [45, 46]. Chemostimulating and modifying agents can be introduced during the oxidation of semiconductors in one compound. In particular, with the chemical deposition of sulphides (PbS, Sb2S3, etc.) on the surface of semiconductors, during the oxidation of the formed heterostructures, the cation-forming element capable of the transit transfer of oxygen to the substrate components provides the rapid formation of the film by the catalytic or transit mechanism, partially performing the modifying function during its doping. The main modifying role is played by the anionic agent, influencing the characteristics of the internal interface, the composition, and, consequently, the characteristics of the films. The change in the composition of the films in the processes of oxidation of sulphide/semiconductor heterostructures according to the sulphide -

I. Ya. Mittova et al. Review

sulphate - oxosulphate - oxide scheme allows obtaining a whole spectrum of their different characteristics. The effectiveness of the effect of sulphur on the properties of the internal interface of a thermal oxide film with a semiconductor was demonstrated by preliminary treatment of the substrate surface in sulphur vapour [47, 48].

The use of complex compounds such as manganese and bismuth vanadate phosphates in the processes of chemically stimulated AIIIBV oxidation demonstrated a positive effect [49, 50], since manganese and bismuth oxides previously were demonstrated as effective chemostimulators of thermal oxidation of A™BV, in which the cation has a pronounced chemo-stimulating activity, and the anion can provide ready-made fragments of growing oxide films such as РО^" groups or groups that are isostructural to them.

The use of chemostimulators and/or modifiers is promising for the stepwise synthesis of nanoscale films on AIIIBV in combination with different types of activation of their action, heat treatment or pulsed photonic treatment, which expands the possibilities of controlling the rate of formation of films, their composition, structure, and properties [43, 44, 51].

Some of the specific results achieved to date reflecting the positive effect of chemostimulators and modifiers on the rate of formation of dielectric and semiconductor films of the nanoscale thickness range and their functional characteristics that have prospects for practical application are summarized in Table 2.

The main fundamental results achieved by the scientific group under the supervision of DSc in Chemistry, Professor I. Ya. Mittova, which includes DSc in Chemistry E. V. Tomina and V. F. Kostryukov, PhD in Chemistry B. V. Sladko-pevtsev and A. A. Samsonov, PhD students and students, are as follows:

1. The concept of the multifunctional effect of chemostimulators-modifiers, often in one compound and in a single process, was proposed. Schemes were also proposed for the mechanisms of thermal oxidation processes of AIIIBV under the influence of simple and complex compounds and their compositions as a physicochemical basis for the development of new processes for the formation of semiconductor and dielectric films on AIIIBV with a given growth rate and

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target characteristics. The specificity of catalytic processes in new nonequilibrium systems with solid-phase thin-film catalysts, reagents, and products has been revealed. The nature of the synergistic effects of the joint action of the chemostimulators deposited on the surface of AIIIBV semiconductors and modifiers of the processes of oxidation of heterostructures was established [36-38,52-55].

2. The nonlinear effects of the influence of binary compositions of oxide-chemostimulators on the formation of thin films on GaAs and InP were established and quantitatively interpreted using the concept of relative partial and integral thicknesses [39, 56-64].

3. The dependence of the nonlinear effect of the combined action of chemostimulators on the oxidation state of the element forming one of the oxides of the composition was revealed, both paired with the oxide of another element, and with the oxide of the same element, but in a different oxidation state [59, 65, 66].

4. The nature and spatial localization of binding stages under the combined action of chemostimulators on the thermal oxidation of GaAs and InP, responsible for the observed nonlinear effects, have been established [67-71].

5. The fundamental possibility of the additive effect of a composition of oxides, one of which is an inert component, on the process of thermal oxidation of GaAs has been proved [72-78].

6. The presence of a sensor signal for the presence of reducing gases in the atmosphere for of thin films synthesized on the surface of GaAs and InP by chemically stimulated thermal oxidation under the influence of both individual chemostimulating oxides and their compositions was established [79-82].

7. Methods for precision doping of thin films on the surface of GaAs and InP have been developed [81, 83, 84].

8. Methods were developed for the synthesis of nano-sized nanostructured oxide films on InP and GaAs using a V2O5 gel allowing to modify the surface of semiconductors under mild conditions, characterized by their efficiency and ease of implementation, variability of the composition, the thickness and morphology of deposited layers of oxide dopants over a wide range [43, 51, 85, 86].

Table 2. Multifunctionality of the action of chemostimulants and modifiers in the processes of synthesis of nanoscale films on AmBv

Characteristics of the object Oxidation mode, T, °C /1, min EAE, kj/mol Stage 1 / Stage 2 Oxidation mechanism Relative increase in film thickness compared to intrinsic oxidation (% or times) The composition of the films The result of the impact Resistivity (p), breakdown voltage (E) Properties of ^ the | synthesized ^ films £

Chemostimulant Semiconductor

o o

13 CL

tr>

13 1/1 tr>

CL

£L>

13 CL

5"

r+

fD —i T3 IT OJ

cn fD

O X fcl fD X n s T3

o

X X

T3 fT) tl

z

fT) *

-e-

OJ

w

X ^

fT) -1 T3 OJ X

NJ O NJ h-^ SJ l-M

l-M

O \D I

l-M l-M O

Modifiers

Method - introduction through the gas phase

A1P0. 4 InP 475-550/10-60 153 intrinsic 120% A1POa, InPO. 4' 4, modification

Method - surface application - hard methods

Sn02 InP 475-550/10-60 48 intrinsic - In(P03)3,P205, ln,03, SnO„ Sn,(POJ., modification p = 9.0-106 Ohm-cm semiconductor

Superposition modifier + moc ifier

SnOyinP + AÎPO, 4 InP 530/10-60 intrinsic - A1P04 InP04 Sn3(P04)2 ' modification p = 8.5-107 Ohm-cm semiconductor

Chemostimulants

Method - surface application - hard methods

Mn02 GaAs 450-550/10-60 95 transit up to 7.5 times Ga203,As205, Mn02 chemo-stimulation p = 1.2' 1010 Ohm-cm; E = 5.2-106V/cm dielectric

InP 450-550/10-60 180 transit up to 2.1 times ln,03, InP04, Mr^Oj, Mn02 chem-ostimulation p = 6.3-108 Ohm-cm; E = 7-106 V/cm dielectric

Superposition chemostimulant + modifier

Method - surface application - soft methods

BiPV, 0A x 1 —x 4 InP 490-570/5-60 51 transit-catalytic 62 - 248% BiV04, InP04 BiP04,V205 chemo-stimulation and modification

Mn3(PV1_ PÙ2 GaAs 490-550/5-60 156 transit up to 220% MnAs04, Mn_(V04).,, Mn_(P04).,, GaAs, GaAsO. chemo-stimulation and modification

TO

fT) <

Method - application to the surface and simultaneous introduction from the gas phase

MnOyinP+ Mn3(P04)2<d> InP 450-550/10-60 110 transit up to 240% In(P03)3, Mn,P,07, MnO, Mn,03, Mn3(P04\, MnPO 4 chemo-stimulation and modification p = 1.5-1010 Ohm-cm dielectric

Superposition of chemostimulant + inert component

Sb203+Y203 GaAs 530/10-40 transit 2-6 times Ga,03, As,03, 'sb2o; 3 chemo-stimulation p = 1.5-106 Ohmxcm Semiconductor with gas sensitivity

PbO + y2o3 InP 560/10-60 transit 2-4 times ln,03, InP04, PbO chemo-stimulation p = 1.5-106 Ohmxcm Semiconductor with gas sensitivity

Super position chemostimulant + chemostimulant

PbO + Bi203 GaAs 530/10-40 transit 2-4 times Ga203,As203, PbO, Bi203 chemo-stimulation p = MO6 Ohmxcm Semiconductor with gas sensitivity

sb2o3 + v2o5 GaAs 530/10-40 transit 3-6 times Ga203,As203, sb2o3)v2o5 chemo-stimulation p = MO6 Ohmxcm Semiconductor with gas sensitivity

PbO + v2o5 InP 560/10-60 transit 2-4 times ln,03, InP04, PbO,V2Os chemo-stimulation p = MO6 Ohmxcm Semiconductor with gas sensitivity

Standards

GaAs, standard-1 450-550/10-60 110 intrinsic - As, Ga,03, As.A - p = M05 Ohmxcm Semiconductor

InP, standard-2 450-550/10-60 270 intrinsic - In, ln,03, InPÖ. 4 - Ohmic conductivity Conductive

I. Ya. Mittova et al. Review

9. Studies of the chemically stimulated thermal oxidation of GaAs and InP have established the decisive influence of the physicochemical nature of the chemostimulator, the procedure and the method of its introduction into the system on the mechanism of the process. It was shown that the introduction of an oxide chemostimulator through the gas phase and its application by soft methods on the semiconductor surface causes the transit mechanism of oxidation. The application of compounds providing a renewable cyclicity of the process by rigid methods provides a synchronous catalytic mechanism for the process. Data on the dependence of the composition, thickness, and rate of formation of films, their morphology on the procedure and method of introducing various chemostimulators-modifiers into the system were obtained [46, 51, 86-90].

10. The high efficiency of the application of the spectral ellipsometry method for determination of the thickness and optical constants of nanoscale films of complex compositions, grown as a result of thermal oxidation of InP and GaAs under the influence of chemostimulators-modifiers was proved [81, 91-94].

11. It was found that magnetron sputtering is the optimal method for the formation of oxide heterostructures (V2O5, MnO2, etc.)/ semiconductor efficiently blocking the diffusion of unoxidised indium into the film during thermal oxidation in comparison with mild methods of modifying the semiconductor surface. Weakly absorbing films with a low content of unoxidised indium, no more than 1-2%, have been synthesized [89, 93].

12. Chemically stimulated oxidation of indium phosphide with a nanosized layer of bismuth vanadate phosphate on the surface led to a significant decrease in EAE (~ 50 kJ/mol) as compared to the intrinsic oxidation of InP (~ 270 kJ/mol), which indicates a significant chemostimulating effect of a complex chemostimulators on the thermal oxidation process of InP due to the decomposition of a complex chemostimulator-modifier with the formation of oxides-chemostimulators, as well as isostructural phosphate and vanadate fragments embedding in the forming film. The presence of V2O5 in films with a significant decrease in EAE and a large relative increase in the thickness of

the films throughout the entire process suggest the presence of the catalytic component of the oxidation mechanism [95]. The composition and optical properties of the films confirm the effective blocking of the diffusion of unoxidised indium into the forming films, which favourably affects their functional properties. The chemically stimulated oxidation of gallium arsenide with a nanosized layer of manganese vanadate phosphate on the surface proceeds by a transit mechanism as was evidenced by the EAE value of the process (about 150 kJ/mol), comparable by an order of magnitude with that of the reference oxidation of InP (~ 270 kJ/mol). According to the XRD results, a chemostimulator with a pronounced catalytic mechanism of action (V2O5), originally present in vanadate-phosphate was not revealed in films, which indicates the absence of a catalyst regeneration cycle: V2O5 ^VO2. Vanadate-phosphates of bismuth and manganese act simultaneously as both chemostimulators and modifiers of the thermal oxidation process, acting according to the transit mechanism for heterostructures on GaAs and according to transit-catalytic mechanism for heterostructures on InP, and leading to an acceleration of the process up to 220-248% (see Table 2). Thermal oxidation of InP with magnetron deposited nanoscale layers of the MnO2chemostimulator and the simultaneous introduction of a chemostimulator-modifier Mn3(PO4)2 through the gas phase led to an increase in the growth rate of the films up to 240% compared with the intrinsic oxidation of InP, the absence of under-oxidized indium in the films, the high content of a whole spectrum of phosphates (XRD, IRS, AES, USXES, SE), and, as a consequence, their dielectric characteristics (resistivity up to 1010 Ohm-cm, see Table 2).

The traditions established by the scientific school of Professor Yakov Aleksandrovich Ugai are continued by DSc in Chemistry, Professor A. M. Samoilov [96-101].

The main objectives of these studies are the investigation of the fundamental physicochemical properties of semiconductor systems with sensor properties and the improvement of methods for the directed synthesis of hetero- and nanostructures based on these materials for the achievement of optimal values of their functional parameters.

I. Ya. Mittova et al. Review

The focus of studies is on multicomponent narrow-bandgap AIVBVI semiconductors capable of efficiently detecting electromagnetic radiation in the terahertz and infrared regions of the spectrum [102-115], as well as wide-bandgap transparent metal oxides, which are promising for the creation of gas sensors and ultraviolet radiation sensors [116-129]. The study of these materials is currently carried out in several directions: the investigation of fundamental physicochemical properties, which are fundamental for the functioning of these systems as sensor materials [102, 103, 105, 109-112]; methods for the synthesis of PbTe thin films were optimized based on the data on the solubility of Ga and In in PbTe<Ga> and PbTe<In> with high sensitivity to IR radiation [104, 106, 111, 124, 125].

The obtained experimental data on the thermal stability and crystal structure of palladium (II) oxide allowed developing methods for the synthesis of nanostructures with different morphological organization, which demonstrated high sensitivity to toxic gases with oxidizing properties as well as good speed and stability of the sensory response over time [120-123]. The results of calculating the region of nonstoichiometry of nanocrystalline PdO films [127-129] in the future will allow finding the optimal conditions for the synthesis of nanostructures with high selectivity for detecting poisonous and explosive gases with oxidizing and reducing properties in atmospheric air [126].

The materials science traditions of the school were developed somewhat unexpectedly in the studies of DSc in Chemistry, Professor N. I. Ponomareva by the development of new methods for the synthesis of hydroxyapatite (HA) composites, allowing to obtain particles included in a biopolymer matrix. Since the properties of both HA itself and composites based on it depend on the particle size, the research task was to obtain nano-HA. It was shown that with the dropwise mixing of the reagents and the addition of alizarin red, promoting the formation of centres of induced crystallization, the rate of formation of stoichiometric HA in an aqueous solution increased by more than 100 times in comparison with the reference process. Synthesis of GA in a model body fluid (SBF) leads to the formation of type A carbonate hydroxyapatite corresponding

to the formula Ca10(P04)6(C03)05x(0H)2-x, where * < 2 (EPXMA, IRS), which was explained by the presence of a bicarbonate ion in SBF and carbon dioxide in the air [130, 131]. A method for the synthesis of nano-HA in drops of microemulsions prepared on the basis of toluene/octane and water with the addition of AOT as a surfactant has been developed, and it was shown that the particles had needle shape (length 10-20 nm and width 2-4 nm) and were covered with an amorphous shell. It was found that in the formation of HA composites with biopolymers, the determining factors are the presence of carboxyl, hydroxyl, and sulpho groups in the used biopolymers and the negative surface charge of the polymers. An excess of calcium ions increased the degree of binding of these organic components with HA and significantly increased the hardness of composites (up to 260 MN/m2) [132-134]. N. I. Ponomareva et al. Proposed a new economically viable method for the formation of bioactive coatings on the surface of titanium by the deposition of carbonate films from the solution with their subsequent transformation into phosphate and hydroxyapatite films [133-137]. The authors provided recommendations for the impregnation of HA with carbon implants [138, 139].

3. Doped and undoped nanocrystalline yttrium and lanthanum ferrites

The development of research in the field of semiconductor and dielectric films of the nanoscale thickness range by the followers of the scientific school of Ya. A. Ugai naturally spread to the area of magnetic nanocrystals. The increased interest in nanomaterials based on yttrium and lanthanum orthoferrites with a perovskite structure was caused by their unique magnetic, optical, and catalytic properties [140, 141] and the ability to control their structure and properties through doping over a wide range.

Among the methods for obtaining nanosized REE ferrites, the sol-gel method is widely used, allowing nanopowders with a narrow particle size distribution to be formed at relatively low temperatures using simple and inexpensive equipment. Variations ofthe sol-gel method include the polymer-gel process, in which the formation of a gel is achieved by introducing a water-soluble polymer into the initial solution followed by

I. Ya. Mittova et al. Review

evaporation, and the Pechini method (citrate-gel), which uses citric acid, ethylene glycol, or polyvinyl alcohol [142-144]. Hydrothermal treatment of precipitated yttrium and iron (III) hydroxides makes it possible to obtain single crystals of yttrium ferrite [145, 146], microcrystalline [147, 148] and nanocrystalline powders [147, 149, 150] by selecting the appropriate precursors, pH of the medium, and conditions of hydrothermal treatment. The mechanism of the formation of yttrium ferrite nanopowders under the conditions of glycine-nitrate combustion is described in [151, 152]. The synthesized particles are characterized by a rhombic and hexagonal structure with a particle size of 30 to 53 nm and 6 to 14 nm, respectively. It was found that the phase composition and average crystallite size are significantly influenced by the glycine/nitrate ratio, which determines the combustion temperature.

By the method of decomposition of alkoxide complexes, yttrium orthoferrite nanopowders are formed at a temperature of 680 °C and exhibit weak ferromagnetism [153]. One of the modern methods for the synthesis of ferrite nanocrystals is microwave synthesis. The method for the synthesis of vanadate and ferrite precipitation from a solution of precursors under the influence of microwave radiation is characterized by the simplicity of implementation, economy, and high synthesis rate. Microwave radiation stimulates the decomposition of salt precursors, the dehydration and synthesis of target products is due to the uniformity and high rate of microwave heating and acceleration of the processes of "nucleation" under the influence of "nonthermal" effects [154].

Effective absorption of microwave radiation requires the presence in the substance of either dipoles that can reorient and rotate under microwave action, or free charge carriers that can move when the microwave field is applied. Water molecules located in the crystal lattice of crystalline hydrates-precursors have a significant dipole moment. The decomposition of the used crystalline hydrates in a microwave field proceed to oxides, since the formation of an oxide product begins before the removal of all water contained in the system.

Compared to traditional heating methods, microwave heating has several undoubted

advantages: during microwave heating, the walls of the vessel are not heated, only the reaction mixture is heated. As a result of this: the reaction time was reduced (by 10-1000 times); directed activation of reacting molecules was carried out; there wee no side processes of destruction on the walls of the vessel, the overheating of the solvent above the boiling point was absent; the flow of energy stopped after the termination of the reaction [155, 156].

Microwave exposure followed by ultrasonic treatment of synthesized YFeO3 and BiFeO3 samples using sodium hydroxide as a precipitant allowed synthesizing chemically homogeneous nanopowders with a significant decrease in the energy intensity of the process. The resulting YFeO3 and BiFeO3 particles had a nearly spherical shape, they were characterized by a small size dispersion in the range of 20-100 nm [157, 158].

The change in the magnetic properties of doped ferrites was caused by several reasons: a change in the size and shape of particles, a distortion of the crystal lattice due to the difference in ionic radii, a change in the valence state of iron upon the introduction of a dopant, and the appearance of oxygen nonstoichiometry.

Studies of the effect of a doping impurity on the composition, structure, and properties of yttrium orthoferrite nanoparticles can be divided into two directions: substitution of the Y3+ and Fe3+ cation. We are working in both directions.

During the first stage of research, it was shown that the substitution of Y3+ by La3+ in yttrium ferrite nanopowders synthesized by coprecipitation led to an increase in magnetization from 0.041 A-m2/ kg for x = 0 to 0.231 A-m2/ kg for x = 0.4 and a decrease in the coercive force, which indicates a significant contribution of crystal lattice distortion in the formation of the magnetic properties of the material [159]. This effect was found even in the case of isovalent substitution, and in this case, it was due to the size factor.

The change in the magnetic properties in the case of heterovalent substitution was due not only to size factors, but also due to a change in the valence state of iron for compensation of the charge and the appearance of oxygen nonstoichiometry.

Data obtained by doping yttrium ferrite with some doubly charged cations are presented by

us in [160-162]. Sol-gel synthesis of Y1-xAxFeO3 samples (where A - Ca2+, Sr2+, Cd2+) is based on the processes of co-deposition of cations and annealing in a muffle furnace at a temperature of 750 °C for 1 h. Doping with Ca2+ and Cd2+ cations with ionic radius slightly exceeding the ionic radius of Y3+, led to a decrease in the particle size, specific magnetization, and coercive force. Decrease in Dav was explained by the appearance of internal stresses, limiting the growth of crystals [163]. Despite the deviation from Goldschmidt's rule [164], the substitution of Y3+ with strontium cations is possible and causes a significant increase in the coercive force from 3.98 kA/m (x = 0) up to 409.94 kA/m (x = 0.3), i.e. the formation of a new type of magnetic material, a hard magnetic ferromagnet.

It could be assumed that the doping of yttrium ferrite with barium cations would lead to a strong increase in the magnetic characteristics due to the incorporation of Ba2+ into position of Y3+ (since r(Ba2+)> r(Y3+) [165]), and the introduction of Zn2+ can change the magnetic properties both in the direction of decreasing (since zinc cations have a small radius) and increasing their value in the case of substitution of iron cations with Zn2+ ions. Indeed, in the studies of our team it was shown [165, 166] that the substitution of La3+ or Y3 cations in orthoferrites by doubly charged Zn2+ and Ва2 caused the distortion of the crystal lattice, a change in the valence state of iron, which, in turn, affects the strength of the exchange interaction and leads to a change in physicochemical properties, which expands the scope of the synthesized materials. Thus, nanocrystalline powders (1-х) YFeO3-d : xZn2+ and (1-x)LaFeO3-d : xZn2+, which are characterized by weak ferromagnetism, are promising materials for the production of devices requiring rapid re-magnetization of the sample with minimal energy consumption, for example, when creating transformer coils, and, nanopowders (1-x)YFeO3-d : xBa2+ and (1-х) LaFeO3-d : xBa2+ can be used to solve the problem of increasing the density of media for the magnetic recording of information, since they are magnetically hard materials. It was shown that the doping of nanocrystalline yttrium ferrite powders with zinc by coprecipitation followed by heat treatment causes a nonmonotonic

decrease in the crystallite size from 60 ± 6 nm x = 0 to 50 ± 4 nm x = 0.2 (XRD), contributes to an increase in the specific magnetization from 0.242 A m2/kg for x = 0 to 0.556 A m2/kg for x = 0.2 (in the field 1250 kA/m). The presence of ZnFe2O4 impurities in the samples led to an increase in the ferromagnetic character of the samples.

It was found that the developed technique for the synthesis [167] of (1-x)YFeO3-d : xBa2+ nanopowders led to the formation of particles with a size of 30 ± 2 nm for x = 0 to 55 ± 5 for x = 0.1 (XRD), characterised by the presence of a soft magnetic and magnetic hard sublattice within the same chemical phase.

In our studies [168], a method for the sol-gel synthesis of LaFeO3 using an aqueous solution of ammonia as a precipitant was demonstrated, lanthanum ferrite was doped with calcium and strontium. It was found that the introduction of Ca2+ into the ferrite lattice caused an increase in the average crystallite diameter from 30 nm for LaFeO3 up to 50 nm, in the case of Sr2+ it was up to 70 nm. Doping with calcium and strontium cations led to an increase in the coercive force and specific magnetization of the samples. The change in the magnetic properties of lanthanum ferrite upon doping with doubly charged cations was caused by the partial transition of Fe3+ in Fe4+, as well as distortion of the crystal lattice due to the difference in the ionic radii of La3+ and the dopant. With an equal content of Ca2+ and Sr2+ cations in the composition of the samples, the magnetic properties were different: H(La0JCaa3FeO3) < H(Laa7Sra3FeO3), a

/(Lac.7Ca0.3FeO3) > /(Lac.7Sr0.3FeO3).

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The complexity of the formation of lanthanum ferrite nanopowders doped with zinc and barium is due to the large difference in the ionic radii of lanthanum and the dopant introduced. However, despite the narrow homogeneity region, singlephase samples with a complex magnetic structure were obtained [169, 170]. The maximum degree of doping of lanthanum ferrite with zinc was xreal = 0.07. As the amount of the introduced dopant increased, the unit cell volume nonmonotonically increased from 240.634 A3 (x = 0) up to 242.245 A3 (x = 0.2) and the average crystallite size increased from 58 (x = 0) to 123 nm (x = 0.2), which was due to the incorporation of Zn ions2+ into the position of Fe3+, since r(Zn2+) > r(Fe3+). (1-x)LaFeO3-d : xZn2+

I. Ya. Mittova et al. Review

nanoparticles, depending on the composition, possess different types of magnetic ordering: antiferromagnetic and ferrimagnetic. The doping of YFeO3 nanopowders with Zn2+ cations with a radius of less than Y3+, should negatively affect the magnetization and coercive force. However, the formation of nanocrystals, characterized by a complex distribution of the doping cation was observed. The formation of particles with the structure "crystal core - amorphous shell" led to the arrangement of a part of the dopant ions in the form of an amorphous shell of zinc oxide. The increase in specific magnetization (1-x) YFeO d : xZn2+ with an increase in the amount

3-Ô

of Zn2+ was due to the reorientation of the magnetic moments of iron ions, as was observed in the study [171]. The distortion of the crystal lattice was insignificant, therefore, in this case, it did not significantly affect the properties. The enhancement of the ferromagnetic character of the material was also due to the presence of zinc ferrite in the spinel phase [166]

The introduction of Ba2+ cations into a LaFeO3 lattice in the position of La3+ caused an increase in the parameters of the crystal lattice and the average particle diameter from 25 (x = 0) up to 42 nm (x = 0.1). The maximum nominal doping level was x = 0.1 (XRD). The synthesized particles exhibited the properties of a hard magnetic ferromagnet with a wide hysteresis loop. The nonmonotonic change in the magnetic characteristics was due to the formation of a complex magnetic structure combining a hard magnetic and soft magnetic sublattice.

Thus, as in the case of yttrium ferrite, the doping of lanthanum ferrite with doubly charged barium and zinc cations led to the formation of materials exhibiting different magnetic properties, which allows using them for the production of information storage devices [165, 166, 169, 170]

Changes in the magnetic properties of yttrium ferrite upon doping with doubly charged cations were caused by several factors: first, due to the difference in ionic radii of Y3+ and dopant, distortion of the crystal lattice occurred and the particle size changed; secondly, such doping refers to heterovalent isomorphic transformations, which resulted in the formation of Fe4+ cations, i.e., a double exchange interaction of Fe3+-O2--

Fe4+ occurred, holes which were charge carriers in the transition from the Fe4+ ion to Fe3+ ion through the p-orbital of oxygen were generated [172]. It was shown in studies [159, 161] that upon the doping of lanthanum ferrite, an increase in the magnetization can be caused by similar reasons. The absence of such an interaction in perovskite Y1-xLaxFeO3 [159] explains its lower magnetization compared to Y1-xCdxFeO3 [161] with the same degree of substitution, since with an increase in the cadmium content, although the size of the resulting particles Y1-xCdxFeO3 decreased, their magnetization increased monotonically. Therefore, the compensation described above probably has a stronger effect on the magnetization than a change in particle size.

It should be noted that the data available in the literature on the effect of zinc on the size of nanocrystals and the magnetic properties of LaFeO3 nanopowders are very controversial. In studies [173, 174], the possibility to substitute La3+ cations with Zn2+ cations in lanthanum orthoferrite synthesized by the coprecipitation method was shown. A decrease in the crystal lattice volume with an increase in the dopant concentration led to an increase in the orthorhombic distortion of the LaFeO3 perovskite lattice, which caused an increase in magnetization.

In studies [175, 176], the results of the synthesis of LaFe1xZnxO3 nanopowders by the gel combustion method were presented, the mechanism of incorporation of the dopant and the effect on the magnetic structure of the material were described. The introduction of Zn2+ instead of Fe3+ led to the transformation of Fe3+ -Fe4+ and the formation of oxygen vacancies in the perovskite structure, which changed the angle and length of the Fe-O bonds. The structural analysis showed that zinc doping causes oxygen nonstoichiometry in the system. This can change the valence state of Fe3+ and hence the magnetization [176].

The doping of lanthanum ferrite with zinc, regardless of the preparation method and the position of the dopant in the perovskite lattice (in the position of La3+ or Fe3+) led to the formation of particles with a complex magnetic structure: an antiferromagnetic core - a ferromagnetic shell, as was evidenced by the shift of the hysteresis loop towards a negative field strength [174-176].

I. Ya. Mittova et al. Review

Due to the fact that the difference between the radii of La3+ - Zn2+ is much higher than that of Fe3+ - Zn2+, the substitution of iron cations by zinc is more likely. This was proved by us for (1-x)LaFeO3-d : xZn2+ nanopowders synthesized by co-deposition followed by annealing in a muffle furnace [170]. The substitution of some Fe3+ ions with Zn2+ ions led to the formation of a material with a complex magnetic structure. By controlling the amount of dopant introduced, it was possible to obtain materials with antiferromagnetic (for * = 0; 0.075; 0.15) or ferrimagnetic (x = 0.05; 0.1;

0.2) properties.

Lower specific magnetization for samples of yttrium ferrite doped with Zn2+, Cd2+, Ca2+, Sr2+, Ba2+ cations compared with (1-x)LaFeO3-g:xE2+, indicates a significant contribution of the effect of double exchange interaction on the magnetic properties of the material. The magnitude of the magnetization and coercive force of lanthanum ferrite nanopowders doped with doubly charged cations depends on the difference in ionic radii,

1.e., on the distortion of the crystal lattice. With an increase in the dopant content, the dependence of the magnetization on the particle size has not been established. Consequently, the above compensation and the structure factor seem to have a stronger effect on magnetization than a change in the particle size of the studied yttrium and lanthanum ferrites. The described results can be used to obtain composite materials [177, 178]. In addition, the detected inclusions of the ferromagnetic Fe2O3, BaFe2O4, ZnFe2O4 phases show that the synthesized samples are promising for creating granular structures [179, 180].

From the described above information, a complex mechanism for the incorporation of zinc into the lattices of yttrium and lanthanum ferrites can be proposed, and, based on the difference in atomic radii, it is most likely to be incorporated into the place of iron. However, as shown above, this statement is far from clear. Such transition elements as manganese and nickel should occupy positions of iron in the structure, since they are quite similar in their properties. The corresponding studies belong to the above-mentioned second direction. A significant increase in the magnetic parameters of YFeO3 nanoparticles was observed upon doping with magnetic ions Mn3+, as shown in [181]. It is

believed that the magnetic moment of the Mn3+ ion is higher than Fe3+ in oxides of the perovskite type, and this should be the reason for the increase in magnetic moments with an increase in the amount of dopant in YFe1-xMnxO3 [182]. In addition, the enhancement of antiferromagnetic ordering is due to distortions in the crystal lattice. In studies [183, 184] the results of doping of yttrium and lanthanum ferrite powders with nickel Ni2+ by successive precipitation using an aqueous solution of potassium hydroxide are presented [184]. The single-phase of YFe1-xNixO3 (x = 0-0.25) samples is achieved at a temperature of 800 °C for 1 h, respectively (XRD). With an increase in the content of the dopant Ni to x = 0.3 after annealing at 800 °C for 1 h, in addition to YFeO3, NiO and Y2O3 impurity phases are formed. With an increase in Ni2+ content in the YFeO3 lattice from x = 0.1 to 0.25, a decrease in the coercive force from 1332.6 to 887.9 Oe was observed, while the values of excess magnetization Mr and saturation magnetization Ms increased: from 1.8-10-1 up to 3.2-10-1 emu/g and 0.67 to 1.18 emu/g, respectively.

The introduction of Ni2+ cations into the LaFeO3 lattice in the position of Fe3+ causes a decrease in the parameters of the crystal lattice and a decrease in average particle diameter from 28.72 (x = 0) to 23.59 nm (x = 0.25). For LaFe1-xNixO3 samples with an increase in the content of Ni2+ dopant from x = 0 to 0.25, an increase in the coercive force from 42.53 Oe to 160.76 Oe was observed, while the values of excess magnetization Mr and saturation magnetization Ms decreased: from 1.0-10-2 up to 3.8-10-4 emu/g and from 0.24 10° up to 0.74-10-4 emu/g [183]. It was found that an increase in the content of the dopant Ni2+ in YFeO3 and LaFeO3 lattices allows varying the value of the coercive force (Hc) and saturation magnetization (Ms), which expands new possibilities of using doped yttrium and lanthanum ferrites in a strong magnetic field.

In the study [185], YFe1-xMnxO3 (x = 0.1; 0.2; 0.3; 0.4) perovskite nanopowders were synthesized by chemical coprecipitation using 5% KOH as the precipitating reagent. The introduction of manganese ions into the YFeO3 lattice using the proposed method led to an increase in the parameters of the crystal lattice (b = 7.7373^7.5194 A, c=5.3014 v 5.2592 A); unit cell

I. Ya. Mittova et al. Review

volume (V = 229.425^224.4012 A), average particle size (Dxrd = 23.6081^22.9449 nm). An increase in the coercive force (Hc = 56.94^150.95 Oe) and residual magnetization (M. = 0.23-0.50 emu/g) with an increase in the dopant content was revealed.

Nanocrystalline La1-xCdxFeO3 = 0, 0.05, 0.1, 0.15, 0.2) powders, characterized by a narrow region of homogeneity xmax = 0.09 (EPXMA, XRD) were synthesized by co-deposition followed by thermal annealing at 950 °C for 1 h. Introduction of Cd2+ cations led to a decrease in the average crystallite size from 10-70 nm for x = 0 to 5-60 nm for x = 0.1 (TEM). The synthesized nanocrystals exhibited the properties of ferrimagnets [186].

In this direction, the work related to the section of the scientific school of Ya. A. Ugai, continue abroad. Thus, in the Socialist Republic of Vietnam, Nguyen Anh Tien, who defended his PhD thesis in Russia under the supervision of I. Ya. Mittova, is the Head of the Department of General and Inorganic Chemistry of Ho Chi Minh City University of Education, and with his colleagues and co-authors successfully conducts research into the synthesis and characterization of ferrite nanocrystals. The studies are being carried out in co-authorship with Russian colleagues (a scientific group led by I. Ya. Mittova) in accordance with the Memorandum of Understanding, concerning the program for the development of cooperation in the field of higher education, signed between Voronezh State University and Ho Chi Minh City University of Education. To date, new methods for the synthesis of nanocrystals of doped and undoped ferrites, including REE ferrites (neodymium, praseodymium, holmium, etc.) by solution methods have been developed; the regularities of changes in magnetic properties depending on the synthesis method, particle size, physicochemical nature of the dopant, and the level of doping have been established [187-192]. This research has been repeatedly supported by internal grants from the Socialist Republic of Vietnam.

In our country, studies that continue the foundations and traditions of the scientific school of Ya. A. Ugai, supported by the following grants and Programs (Head Researcher - Prof. I. Ya. Mittova):

1. Soros Fund No. NZN000 + NZN300.

2. STP "Scientific research of higher education in priority areas of science and technology", subprogram (208) - electronics, project code 01.01.004.

3. Grant of the Ministry of Education E00-5.0-363 (registration number 01.2.00104702).

4. STP Research of the Higher School in the priority areas of science and technology.

5. Federal Program "Universities of Russia -Basic Research" (grants No. 06.01.07, No. UR.06.01.020, No. UR.06.01.001).

6. Basic Research Program in Radio Engineering and Electronics (Grant No. 97-5-1.1-32).

7. RFBR No. 02-03-32418: Chemically stimulated oxidation of AIIIBV semiconductors during the formation of heterostructures.

8. RFBR No. 03-03-96500-r2003tschr_a -Nonlinear effects in the processes of chemically stimulated synthesis of dielectric oxide layers on AIIIBV.

9. RFBR No. 06-03-96338_r_center_a -Effect of chemostimulators on the kinetics and mechanism of thermal oxidation of semiconductors AIIIBV in the formation of thin films and heterostructures.

10. RFBR No. 09-03-97552-r_center_a -Catalytic and transit solid-phase interactions in nanosystems based on semiconductor materials.

11. RFBR 10-03-00949-a - Size effects in the processes of synthesis of oxide layers on GaAs and InP.

12. RFBR No. 13-03-00705-a - Role of V2O5 as an oxidation catalyst, interface modifier and the nanostructure of functional nanometer films on InP and GaAs.

13. RFBR No. 16-43-360595 p_a - Modification of the surface of GaAs, GaP and InP as a method of controlling the nanostructure, optical and electrophysical properties of oxide films of nanometer thickness range for microelectronics.

14. RFBR No. 18-03-00354_a - Development of the fundamental principles of chemically controlled synthesis of functional nanoscale films on semiconductors A3B5 for opto- and microelectronics, gas-sensitive sensors.

15. Analytical departmental target program (No. G.R. 01200602176) "Development of the scientific potential of higher education" within the framework of program action 1 "Conducting fundamental research within the framework

of thematic plans" "Development of synthesis methods and establishment of the mechanism for the formation of nanoscale layers, nanopowders and crystals of semiconductor, dielectric and magnetic materials".

16. Project of the Ministry of Education and Science of the Russian Federation: Goverment Order 3.1673.2011.

17. Government Order for higher education institutions in the area of scientific research for 2014-2016 (projects No. 673, 225).

18. RFBR grant No. 20-33-90048 "Formation mechanisms, structural features and properties of carbon-containing nanocomposites based on nanocrystalline ferrites with a perovskite-like structure" ("Postgraduate students").

Postgraduate student Kopeichenko E. I. (scientific advisor - Proffessor I. Ya. Mittova) won the competition for the best scientific

projects carried out by young scientists under the supervision of scientists with PhD and DSc degrees in scientific organisations of the Russian Federation (RFBR grant No. 19-33-50104 mol_nr "Mobility").

The Russian Academy of Natural Sciences issued a certificate to I. Ya. Mittova as the head of the scientific school "Control of synthesis processes, composition and properties of functional (semiconductor, dielectric, para- and ferromagnetic) nanoscale films, magnetic nanocrystals and nanophosphors by chemostimulators and dopants "(Russian Academy of Natural Sciences, certificate No. 01165, "Leading scientific schools. - Moscow: Publishing House of the Academy of Natural Sciences, 2018. - Vol. 11. - 132 p.; Mittova Irina Yakovlevna, p. 81; http://www.famous-scientists. ru/school/1393"), which is the embodiment of the

I. Ya. Mittova et al. Review

ideas of Ya. A. Ugai, his students and followers in the study of semiconductors and nanostructured functional films based on them, their spread to the field of new challenges and scientific trends of today.

Author contributions

All authors made an equivalent contribution to the preparation of the publication.

Conflict of interests

The authors declare that they have no known competing financial interests or personal relationships that could have influenced the work reported in this paper.

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36. Mittova I. Ya. Influence of the physicochemical nature of chemical stimulators and the way they are introduced into a system on the mechanism of the thermal oxidation of GaAs and InP. Inorganic Materials. 2014;50(9): 874-881. https://doi.org/10.1134/ S0020168514090088

37. Tomina E. V., Mittova, I. Y., Zelenina, L. S. Thermal oxidation as a method of formation of nanoscale functional films on AIIIBV semiconductors: influence of deposited metal layers. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2018;20(1): 6-24. https://doi.org/10.17308/ kcmf.2018.20/472 (In Russ., abstract in Eng.)

38. Tomina E. V., Mittova I. Ya., Sladkopevtsev B. V., Kostryukov V. F., Samsonov A. A., Tretyakov N. N. Thermal oxidation as a method of formation of nanoscale functional films on AIIIBV semiconductors: chemostimulated influence of metal oxides: overview. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2018;20(2): 184203. https://doi.org/10.17308/kcmf.2018.20/522 (In Russ., abstract in Eng.)

39. Kostryukov V. F., Mittova I. Y., Tomina E. V., Sladkopevtsev B. V., Parshina A. S., Balasheva D. S. Nonlinear effects of oxides of p- and d-elements' coactions in formation of thin films on the GaAs and InP surfaces overview. Kondensirovannye sredy i mezhfaznye granitsy = CondensedMatter and Interphases. 2018;20(4): 506-536. https://doi.org/10.17308/ kcmf.2018.20/625 (In Russ., abstract in Eng.)

40. Mittova I. Ya., Tomina E. V., Golovenko N. A., Agapov B. L. Formation of thermal oxide layers on InP in the presence of SbCl3 in the gas phase. Inorganic Materials. 1993;29(5): 514-516. Available at: https:// www.elibrary.ru/item.asp?id=27651233

41. Mittova I. Ya., Pukhova V. V., Klement'eva I. F., Semenov V. N., Kashkarov V. M. Poluchenie

I. Ya. Mittova et al. Review

termicheskim okisleniem struktur GaAs/Bi2S3 i svoistva dielektricheskikh plenok na GaAs[Thermal oxidation of GaAs/Bi2S3 structures and properties of dielectric layers on GaAs]. Izvestiya Akademii nauk SSSR. Neorganicheskie Materialy. 1988;24(9): 1431-1434. Available at: https://www.elibrary.ru/item. asp?id=27454116

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42. Kostryukov V. F., Mittova I. Ya., Sladkopevtsev B. V., Parshina A. S., Balasheva D. S. The role of BiPO4 introduced through the gas phase in the process of creating thin films on the surface of InP. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(2): 215224. https://doi.org/10.17308/kcmf.2019.21/759 (In Russ., abstract in Eng.)

43. Sladkopevtsev B. V., Tomina E. V., Mittova I. Ya., Dontsov A. I., Pelipenko D. I. On the thermal oxidation of V O -InP heterostructures formed by the

x y J

centrifugation of vanadium(V) oxide gel. Journal of Surface Investigation. X-ray, Synchrotron and Neutron Techniques. 2016;10(2): 335-340. https://doi. org/10.1134/S102745101602018X

44. Sladkopevtsev B. V., Mittova I. Ya., Tomina E. V., Burtseva N. A. Growth of vanadium oxide films on InP under mild conditions and thermal oxidation of the resultant structures. Inorganic Materials. 2012;48(2): 161-168. https://doi.org/10.1134/ S0020168512020173

45. Mittova I. Ya., Tretyakov N. N., Kostryukov V. F., Sladkopevtsev B. V. Thermal oxidation of GaAs under action of V2O5-MnO2 oxide chemostimulating mixture with particles size of 50-150 pm. Russian Journal of General Chemistry. 2016;86(5): 995-1000. https://doi. org/10.1134/S1070363216050017

46. Tret'yakov N. N., Mittova I. Ya., Sladkopevtsev B. V., Samsonov A. A., Andreenko S. Yu. Vliyanie magnetronno napylennogo sloya MnO2 na kinetiku ter-mooksidirovaniya InP, sostav i morfologiyu sinteziro-vannykh plenok [Influence of a magnetron-deposited MnO2 layer on the kinetics of thermal oxidation of InP, composition and morphology of the synthesized films]. Neorganicheskie materialy. 2017;53(1): 41-48. https:// doi.org/10.7868/S0002337X17010171 (In Russ.)

47. Tarasova O. S., Dontsov A. I., Sladkopevtsev B. V., Mittova I. Ya. The effect of sulphur vapour treatment on the speed of InP thermal oxidation, composition, surface morphology, and properties of films. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(2): 296305. https://doi.org/10.17308/kcmf.2019.21/767 (In Russ., abstract in Eng.)

48. Mittova I. Ya., Sladkopevtsev B. V., Dontsov A. I., Syrov Yu. V., Kovaleva A. S., Tarasova O. S. Thermal oxidation of a single-crystal GaAs surface treated in sulfur vapor. Inorganic Materials. 2021;57(7): 663-668. https://doi.org/10.1134/S002016852107013X

49. Mittova I. Y., Sladkopevtsev B. V., Ilyasova N. A., Tomina E. V., Dontsov A. I., Tarasova O. S. The effect of certain complex chemostimulators and modifiers on InP thermal oxidation. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2020;22(2): 245-256. https://doi.org/10.17308/ kcmf.2020.22/2851

50. Tomina E. V., Sladkopevtsev B. V., Dontsov A. I., Perfileva L. I., Mittova I. Y. Influence of nanoscale layers of the Mn3(P01V09O4)2 chemostimulator-modifier on the process of thermal oxidation of GaAs, its composition, and morphology of the resulting films. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2020;22(1): 116123. https://doi.org/10.17308/kcmf.2020.22/2535

51. Mittova I. Y., Tomina E. V., Sladkopevtsev B. V., Dontsov A. I. Effect of different types of annealing on the thermal oxidation of VO y/InP structures formed by the deposition of vanadium(V) oxide gel on the phase composition and morphology of films. Journal of Surface Investigation. X-ray, Synchrotron and Neutron Techniques. 2014;8: 941-949. https://doi.org/10.1134/ S1027451014050140

52. Mittova I. Ya., Tomina E. V., Lapenko A. A., Khorokhordina A. O. Solid-state reactions during thermal oxidation of vanadium-modified GaAs surfaces. Inorganic Materials. 2004;40(5): 441-444. https://doi. org/10.1023/B:INMA.0000027588.78546.af

53. Mittova I. Ya., Tomina E. V., Lapenko A. A., Sladkopevtsev B. V. Kataliticheskoe deistvie vanadiya i ego oksida (V) v protsessakh oksidirovaniya poluprovodnikov AIIIBV. [Catalytic action of vanadium and its oxide (V) in the processes of oxidation of AIIIBV semiconductors]. Nanosystems: Physics, Chemistry, Mathematics. 2012;3(2): 116-138. Available at: https:// www.elibrary.ru/item.asp?id=17881315 (In Russ.)

54. Ievlev, V. M., Mittova, I. Y., Samsonov, A. A., Tomina E. V., Kashkarov V. M. Catalytic effect of a nanolayer of the (V2O5 + PbO) composite in the thermal oxidation of InP crystals. Doklady Chemistry. 2007;417: 277-281. https://doi.org/10.1134/S0012500807120014

55. Mittova I. Y., Sladkopevtsev B. V., Samsonov A. A., Tomina E. V., Andreenko S. Y., Kostenko P. V. Growth and properties of nanofilms produced by the thermal oxidation of MnO2/InP under the effect of Mn3(PO4)2. Inorganic Materials. 2019;55(9): 915-919 https://doi.org/10.1134/S0020168519090073

56. Mittova I. Ya., Pshestanchik V. R., Kostryukov V. F. Nonlinear effect of the joint action of activators on thermal oxidation of gallium arsenide. Doklady Physical Chemistry. 1996;349(4-6): 196-198. Available at: https://www.elibrary.ru/item.asp?id=13233187

57. Mittova I. Ya., Pshestanchik V. R., Kostryukov V. F., Kuznetsov N. T. Alternating nonlinearity of the joint activating effect of binary mixtures of p-element oxides on the chemically activated thermal

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GaAs oxidation. Doklady Chemistry. 2001;378(4-6): 165-167. https://doi.org/10.1023/A:1019238812687

58. Mittova I. Ya., Pshestanchik V. R., Pinyaeva O. A., Kostryukov V. F., Skorokhodova S. M. Nonadditive oxides influence in (CrO3-PbO) and (CrO3-V2O5) compositions as activators of thermal oxidation of gallium arsenide. Doklady Chemistry. 2002;385(4-6): 212-214. https://doi.org/10.1023/A:1019998719921

59. Mittova I. Ya., Pshestanchik V. R., Kostryukov V. F., Donkareva I. A., Saratova A. Yu. Chemostimu-lated GaAs thermal oxidation under the joint action of manganese (IV) oxide with lead (II) oxide and vanadium (V) oxide. Russian Journal of Inorganic Chemistry. 2004;49(7) 991-994. Available at: https:// elibrary.ru/item.asp?id=13464912

60. Mittova I. Ya., Kostryukov V. F., Donkareva I. A., Pshestanchik V. R., Lopatin S. I., Saratova A. Yu. Nonlinear effects of MnO + PbO and MnO + V2O5 compositions on GaAs thermal oxidation. Russian Journal of Inorganic Chemistry. 2005;50(6): 869-873. Available at: https://elibrary.ru/item.asp?id=13487639

61. Mittova I. Ya., Pshestanchik V. R., Kuznetso-va I. V., Kostryukov V. F., Skorokhodova S. M., Medvedeva K. M. Vliyanie razmera chastits aktivatorov na protsess termooksidirovaniya GaAs pod vozdeistviem kompozitsii PbO + V2O5 [Influence of the particle size of activators on the process of thermal oxidation of GaAs under the influence of PbO + V2O5 compositions]. Zhurnal neorganicheskoi khimii. 2005;50(10): 1603-1606. Available at: https://elibrary. ru/item.asp?id=9153646 (In Russ.)

62. Mittova I. Ya., Kostryukov V. F. GaAs thermal oxidation activated by the coaction of p-block oxides. Nanosystems: Physics, Chemistry, Mathematics. 2014;5(3): 417-426. Available at: http://www.mathnet. ru/links/8364620026a0f40f5d8a284be0ba04bf/ nano872.pdf

63. Tret'yakov N. N., Mittova I. Ya., Kozik V. V., Sladkopevtsev B. V., Kostryukov V. F., Studenikina Yu. I. Opredelenie tolshchiny i fazovogo sostava plenok, sintezirovannykh khemostimulirovannym termooksidirovaniem InP pod vozdeistviem kompozitsii oksidov V2O5+MnO2 raznogo sostava [Determination of the thickness and phase composition of films synthesized by chemically stimulated thermal oxidation of InP under the influence of a composition of V2O5 + MnO2 oxides of different compositions]. Izvestiya vysshikh uchebnykh zavedenii. Fizika. 2014;57(7-2): 186-191. Available at: https://elibrary. ru/item.asp?id=23184836 (In Russ.)

64. Mittova I. Y., Tretyakov N. N., Kostryukov V. F., Sladkopevtsev B. V. Combined influence of chemostimulator oxides V2O5 and MnO2 introduced via the gas phase on InP thermal oxidation. Russian Journal of General Chemistry. 2015;85(4): 796-801. https://doi.org/10.1134/S1070363215040040

65. Mittova I. Ya., Kostryukov V. F., Donkareva I. A., Penskoi P. K., Pinyaeva O. A., Pshestanchik V. R. MnO + MnO2 mixture as a nonadditive activator of GaAs thermal oxidation. Russian Journal of General Chemistry. 2005;50(1): 15-19. Available at: https://elibrary.ru/ item.asp?id=13497054

66. Losev V. N., Kudrina Yu. V., Trofimchuk A. K., Komozin P. N. Sorption of ruthenium (III) and ruthenium (IV) on silica gels chemically modified with mercapto and disulfide groups. Russian Journal of Inorganic Chemistry. 2005;50(4): 577-581. Available at: https://elibrary.ru/item.asp?id=13481209

67. Mittova I. Ya., Pshestanchik V. R., Kostryukov V. F., Donkareva I. A. Prostranstvennaya lokalizat-siya vzaimodeistvii mezhdu soedineniyami-aktiva-torami pri khemostimulirovannom termooksidirovanii GaAs [Space localisation of linking interactions between activating compounds at the course of chemically stimulated GaAs thermal oxidation]. Doklady akademii nauk. 2002;386(4): 499-501. Available at: https://elibrary.ru/item.asp?id=44462420 (In Russ.)

68. Mittova I. Ya., Pshestanchik V. R., Kostryukov V. F., Donkareva I. A. Mutual effect of activators on chemostimulated GaAs thermal oxidation with spatially separated coupling stages. Russian Journal of Inorganic Chemistry. 2003;48(4): 480-482. Available at: https://elibrary.ru/item.asp?id=13436411

69. Kostryukov V. F., Pshestanchik V. R., Donkareva I. A., Agapov B. L., Mittova I. Ya., Lopatin S. I. Role of solid- and gas-phase interactions in the coaction of the oxides in MnO2 + PbO and MnO2 + V2O5 compositions activating the thermal oxidation of GaAs. Russian Journal of Inorganic Chemistry. 2007;52(10): 14981502. https://doi.org/10.1134/S0036023607100038

70. Mittova I. Ya., Kostryukov V. F., Pshestanchik V. R., Donkareva I. A., Agapov B. L. Contribution from the solid-phase interactions of activating oxides to their nonlinear joint effect on the thermal oxidation of GaAs. Russian Journal of Inorganic Chemistry. 2008;53(7): 1018-1023. https://doi.org/10.1134/ S0036023608070085

71. Kostryukov V. F., Donkareva I. A., Pshestanchik V. R., Agapov B. L., Mittova I. Ya., Lopatin S. I. GaAs thermal oxidation with participation of spatially separated activator oxides (MnO + PbO and MnO + V2O5). Russian Journal of Inorganic Chemistry. 2008;53(8): 1182-1186. https://doi.org/10.1134/ S0036023608080056

72. Mittova I. Ya., Lopatin S. I., Pshestanchik V. R., Kostryukov V. F., Sergeeva A. V., Penskoi P. K. Rol' inertnogo komponenta Ga2O3 v kompozitsii s oksidom-aktivatorom Sb2O3 v protsesse khemostimulirovannogo okisleniya GaAs [role of an inert component Ga2O3 in the composition with the activator oxide Sb2O3 in chemostimulated GaAs oxidation]. Zhurnal neorganicheskoi khimii. 2005;50(10): 1599-1602.

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Available at: https://elibrary.ru/item.asp?id=9153645 (In Russ.)

73. Penskoi P. K., Kostryukov V. F., Pshestanchik V. R., Mittova I. Ya. Effekt sovmestnogo vozdeistviya kompozitsii khemostimulyatorov (Sb2O3, Bi2O3, MnO2) s inertnym komponentom (Al2O3) v protsesse termooksidirovaniya arsenida galliya [Effect of the combined effect of chemostimulant compositions (Sb2O3, Bi2O3, MnO2) with an inert component (Al2O3) during thermal oxidation of gallium arsenide]. Doklady akademii nauk. 2007;414(6): 765-767. Available at: https://elibrary.ru/item.asp?id=9533571 (In Russ.)

74. Penskoi P. K., Pshestanchik V. R., Kostryukov V. F., Agapov B. V., Mittova I. Ya., Kuznetsova I. V. Nonadditive linearity in the chemostimulating effect of activator oxides + dlient compositions on GaAs thermal oxidation. Russian Journal of Inorganic Chemistry. 2008;53(2): 186-191. https://doi. org/10.1007/s11502-008-2006-0

75. Penskoi P. K., Mittova I. Ya., Kostryukov V. F., Kononova E. Yu., Reutova E. A. Vliyanie inertnogo komponenta A12O3 v kompozitsiyakh s oksidami-aktivatorami (Sb2O3, Bi2O3, MnO2) na protsess termooksidirovaniya GaAs [The influence of inert component Al2O3 in mixtures with oxide activators (Sb2O3, Bi2O3, MnO2) on the process of thermal oxidation of GaAs surface]. Kondensirovannye sredy i mezhfaznye granitsy. 2008;10(3): 236-243. Available at: https://elibrary.ru/item.asp?id=11688570 (In Russ.)

76. Penskoi P. K., Kostryukov V. F., Pshestanchik V. R., Mittova I. Ya., Kutsev S. V., Kuznetsova I. V. Effect of inert components (Y2O3, Al2O3, and Ga2O3) on the chemistimulating effect of the Sb2O3 activator of GaAs thermal oxidation. Russian Journal of Inorganic Chemistry. 2009;54(10): 1564-1570. https://doi. org/10.1134/S0036023609100118

77. Kozhevnikova T. V., Penskoi P. K., Kostryukov V. F., Mittova I. Y., Kuznetsova I. V., Kutsev S. V. Role of an inert component in compositions with manganese (II) and manganese (IV) oxides in studying nonlinear effects in gaas thermal oxidation. Russian Journal of Inorganic Chemistry. 2010;55(12): 18571862. https://doi.org/10.1134/S0036023610120077

78. Kozhevnikova T. V., Penskoi P. K., Kostryu-kov V. F., Mittova I. Ya., Agapov B. L., Kuznetsova I. V., Kutsev S. V. Termicheskoe okislenie GaAs pod vozdeistviem kompozitsii Sb2O3, Bi2O3, MnO, MnO2 i V2O5 s oksidami alyuminiya i ittriya [Thermal oxidation of gaas under influence of compositions of Sb2O3, Bi2O3, MnO, MnO2 and V2O5 with oxides of aluminium and yttrium]. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2010;12(3): 212-225. Available at: https://elibrary.ru/ item.asp?id=15574165 (In Russ.)

79. Penskoi P. K., Salieva E. K., Kostryukov V. F., Rembeza S. I., Mittova I. Ya. Gazochuvstvitel'nost'

slabolegirovannykh sloev, poluchennykh okisleniem GaAs v prisutstvii PbO i Bi2O3 [Gas-sensitivity of the light-alloyed layers. Obtained by the oxidation of GaAs in the presence of PbO and Bi2O3]. Vestnik VGUSeriya Khimiya. Biologiya. Farmatsiya. 2008;1: 26-31.Available at: https://elibrary.ru/item.asp?id=11615172 (In Russ.)

80. Kostryukov V. F., Mittova I. Ya. Ammonia response of thin films grown on GaAs using PbO + Bi2O3 mixtures. Inorganic Materials. 2015;51(5): 425429. https://doi.org/10.1134/S0020168515040056

81. Kostryukov V. F., Mittova I. Ya., Dimitrenko A. A. Chemically stimulated synthesis of gas-sensing films on the surface of GaAs. Inorganic Materials. 2017;53(5): 451-456. https://doi.org/10.1134/S0020168517050132

82. Kostryukov V. F., Mittova I. Ya., Ali Saud Gas-sensing properties of thin films grown on the surface of InP single crystals by thermal oxidation. Inorganic Materials. 2020;56(1): 66-71. https://doi.org/10.1134/ S0020168520010070

83. Kostryukov V. F., Mittova I. Ya. Method for precision doping of thin films on gallium arsenide surface: Patent No 2538415RF. Claim. 17.07.2013. Publ. 10.01.2015. Byul. №2013133382/28 1.

84. Kostryukov V.F., Mittova I. Ya., Sladkopevtsev B. V. Method of precision doping thin films on InP surface: Patent No 2632261 RF. Claim. 17.12.2015. Publ. 03.10.2017. Byul. №28.

85. Sladkopevtsev B. V., Tomina E. V., Mittova I. Ya., Tretyakov N. N. Method of creating nano-sized nanostructured oxide films on InP with application of vanadium pentaxide gel: Patent No 2550316RF. Claim. 30.12.2013. Publ. 10.05.2015. Byul. № 13

86. Tomina E. V., Sladkopevtsev B. V., Mittova I. Ya., Zelenina L. S., Dontsov A. I., Tretyakov N. N., Gudko-va Yu. N., Belashkova Yu. A. Effect of surface V2O5 nanolayers on the thermal oxidation kinetics of GaAs and the composition and morphology of resulting films. Inorganic Materials. 2015;51(11): 1138-1142. https://doi.org/10.1134/S0020168515110126

87. Mittova I. Y., Tomina E. V., Lapenko A. A., Sladkopevtsev B. V. Synthesis and catalytic performance of V2O5 nanoislands produced on the surface of InP crystals by electroexplosion. Inorganic Materials. 2010;46(4): 383-388. https://doi.org/10.1134/ S0020168510040114

88. Mittova I. Ya., Tomina E. V., Tret'yakov N. N., Sladkopevtsev B. V. Zavisimost' mekhanizma khemostimuliruyushchego deistviya V2O5 ot sposoba vvedeniya ego v sistemu pri termooksidirovanii InP [Dependence of the mechanism of the chemostimulating action of V2O5 on the method of its introduction into the system during thermal oxidation of InP.]. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2013;15(3): 305-311.Available at: https://www.elibrary.ru/item. asp?id=20296106 (In Russ.)

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89. Tretyakov N. N., Mittova I. Ya., Sladkopevtsev B. V., Agapov B. L., Pelipenko D. I., Mironenko S. V. Surface morphology, composition, and structure of nanofilms grown on InP in the presence of V2O5. Inorganic Materials. 2015;51(7): 655-660. https://do5. org/10.1134/S002016851507016X

90. Mittova I. Ya., Sladkopevtsev B. V., Tomina E. V., Samsonov A. A., Tretyakov N. N., Ponomarenko S. V. Preparation of dielectric films via thermal oxidation of MnO/GaAs. Inorganic Materials. 2018;54(11): 1085- 1092. https://doi.org/10.1 134/ S0020168518110109

91. Shvets V. A., Rykhlitskii, S. V., Mittova, I. Ya., Tomina E. V. Analysis of the optical and structural properties of oxide films on InP using spectroscopic ellipsometry. Technical Physics. 2013;58: 1638-1645. https://doi.org/10.1134/S1063784213110248

92. Mittova I. Ya., Tomina E. V., Sladkopevtsev B. V., Tret'Yakov N. N., Lapenko A. A., Shvets V. A. Highspeed determination of the thickness and spectral ellipsometry investigation of films produced by the thermal oxidation of InP and VxO/InP structures. Inorganic Materials. 2013;49(2): 179-184. https://doi. org/10.1134/S0020168513020143

93. Mittova I. Ya., Tomina E. V., Samsonov A. A., Sladkopevtsev B. V., Tret'yakov N. N., Shvets V. A. Determination of the thickness and optical constants of nanofilms produced by the thermal oxidation of InP with V2O5, V2O5 + PbO, and NiO + PbO chemical stimulator layers grown by magnetron sputtering. Inorganic Materials. 2013;49(10): 963-970. https://doi. org/10.1134/S0020168513100075

94. Kostryukov V. F., Mittova I. Ya., Shvets V. A., Tomina E. V., Sladkopevtsev B. V., Tret'yakov N. N. Spectral ellipsometry study of thin films grown on GaAs by chemically stimulated thermal oxidation. Inorganic Materials. 2014;50(9): 882-887. https://doi. org/10.1134/S0020168514090052

95. Sladkopevtsev B. V., Mittova I. Ya., Tomina E. V., Zabolotskaya A. V., Samsonov A. A., Dontsov A. I. Osobennosti kinetiki i mekhanizma formirovaniya plenok pri oksidirovanii geterostruktur V2O5/InP, sformirovannykh metodami reaktivnogo magnetronnogo raspyleniya i elektricheskogo vzryva provodnika [Features of kinetics and mechanism of films formation in oxidation of V2O5/InP heterostructures, formed by reactive magnetron sputtering and electric explosion of conductor]. Izvestiya vysshikh uchebnykh zavedenii. Fizika. 2014;57(7-2): 148-153. Available at: https://www. elibrary.ru/item.asp?id=23184829 (In Russ.)

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97. Ugai Y. A., Samoylov A. M., Sharov M. K., Tadeev A. V. Crystal microstructure of PbTe/Si and PbTe/SiO/Si thin films. Thin Solid Films. 1998;336(1-2): 196-200. https://doi.org/10.1016/S0040-6090(98)01278-4

98. Ugai Ya. A., Samoilov A. M., Synorov Yu. V., Yatsenko O. B. Electrical properties of thin PbTe films on Si substrates. Inorganic Materials. 2000;36(5): 449-453. https://doi.org/10.1007/BF02758045

99. Ugai Ya. A., Samoilov A. M., Sharov M. K., Arsenov A. V., Buchnev S. A. Vyrashchivanie plenok PbTe, legirovannykh galliem v protsesse ikh rosta, na Si-podlozhkakh pri pomoshchi modifitsirovannogo metoda "goryachei stenki" [Growing of PbTe films doped with gallium during their growth on Si substrates using a modified "hot wall" method.]. Poverkhnost'. Rentgenovskie, sinkhrotronnye i neitronnye issledovaniya. 2002;3: 28-34. (In Russ.)

100. Ugai Ya. A., Samoylov A. M., Buchnev S. A., Synorov Yu. V., Sharov M. K. Ga doping of thin PbTe films on Si substrates during growth. Inorganic Materials. 2002;38(5): 450-456. https://doi. org/10.1023/A:1015410703238

101. Ugai Ya. A., Samoylov A. M., Sharov M. K., Yatsenko O. B., Akimov B. A. Transport properties of Ga-doped PbTe thin films on Si substrates. Inorganic Materials. 2002;38(1): 12-16. https://doi. org/10.1023/A:1013687024227

102. Samoylov A. M., Buchnev S. A., Khoviv A. M., Dolgopolova E. A., Zlomanov V. P. Comparative study of point defects induced in PbTe thin films doped with Ga by different techniques. Materials Science in Semiconductor Processing. 2003;6(5-6): 481-485. https://doi.org/10.1016Zj.mssp.2003.07.014

103. Samoylov A. M., Khoviv A. M., Buchnev S. A., Synorov Yu. V., Dolgopolova E. A. Crystal structure and electrical parameters of In-doped PbTe/Si films prepared by modified HWE technique. Journal of Crystal Growth. 2003;254(1-2): 55-64. https://doi. org/10.1016/S0022-0248(03)01022-4

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110. Samoylov A. M., Belenko S.V., Dolgopolova E. A., Khoviv A. M., Synorov Y. V. The solubility region of Ga in PbTe films prepared on Si-substrates by modified "Hot Wall" technique. Functional Materials. 2011;18(2): 181-188. Available at: https://www.elibrary.ru/item. asp?id=18002278

111. Samoylov A. M., Belenko S. V., Sharov M. K., Dolgopolova E. A., Zlomanov V. P. The deviation from a stoichiometry and the amphoteric behaviour of Ga in PbTe/Si films. Journal of Crystal Growth. 2012;351(1): 149-154. https://doi.org/10.1016/j.jcrysgro.2012.01.042

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116. Marikutsa A. V., Rumyantseva M. N., Gas-kov A. M., Samoylov A. M. Nanocrystalline tin dioxide: Basics in relation with gas sensing phenomena. Part I. Physical and chemical properties and sensor signal formation. Inorganic Materials. 2015;51(13): 1329-1347. https://doi.org/10.1134/S002016851513004X

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Information about the authors

Irina Ya. Mittova, DSc in Chemistry, Professor at the Department of Materials Science and the Industry of Nanosystems, Voronezh State University, Voronezh, Russian Federation; e-mail: imittova@mail.ru. ORCID iD: https://orcid.org/0000-0001-6919-1683.

Boris V. Sladkopevtsev, PhD in Chemistry, Associate Professor, Department of Materials Science and the Industry of Nanosystems, Voronezh State University, Voronezh, Russian Federation; e-mail: dp-kmins@ yandex.ru. ORCID iD: https://orcid.org/0000-0002-0372-1941.

Valentina O. Mittova, PhD in Biology, Associate Professor, Department of Biochemistry, Voronezh State Medical University named after N. N. Burdenko, Voronezh, Russian Federation; e-mail: vmittova@ mail.ru. ORCID iD: https://orcid.org/0000-0002-9844-8684.

Received 22 June 2021; Approved after reviewing 15 July 2021; Accepted for publication 15 August 2021; Published online 25 September 2021.

Translated by Valentina Mittova

Edited and proofread by Simon Cox

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