Развитие методов исследования и синтеза твердых фаз в научной школе Я. А. Угая. Обзор
Аннотация
Более пятидесяти лет в Воронежском государственном университете существует научная школа, созданная Яковом Александровичем Угаем. Одним из направлений работ этой школы являлось создание физико-химические основ получения твердых фаз в системах с летучими компонентами, что предопределило необходимость развития методов исследования давления пара (тензиметрических методов). В статье делается акцент лишь на части работ сотрудников ВГУ, которые были посвящены исследованию и построению Р-Т-х диаграмм. В настоящем обзоре проводится анализ фазовых равновесий и природы промежуточных фаз в системах AIV – BV, AIV
– BV – СV и AIII – BVI. Вследствие особого характера катион-катионных и анион-анионных связей в этих соединениях существует заметная специфика свойств, что делает их перспективными, в частности, 2D материалами. Приводится обзор работ, посвященных построению Р-Т-х диаграмм и исследованию процессов дефектообразования в двойных и тройных системах на основе соединений AIVBV. Необходимо подчеркнуть, что высокие значения давления пара требовали модернизации известных методик, что позволило проводить эксперименты при давлениях порядка 35-40 атмосфер. Изучение систем AIII - BVI осложняют, напротив, низкие величины давления паров над халькогенидами индия и галлия, а также сложный состав пара. Для такого рода систем был разработан метод вспомогательного компонента, возможности применения которого достаточно широки и не ограничиваются соединениями AIIIBVI. Создан и применен новый метод регулирования нестехиометрии с помощью селективных неразрушающих транспортных химических реакций (т. е. с участием вспомогательного компонента). Основа способа состоит во введении или удалении одного из компонентов образца при помощи селективной транспортной химической реакции. В заключении проведен анализ развития методов исследования и синтеза промежуточных фаз с варьируемым составом (свойствами) на примере рассмотренных систем
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http://www.science.vsu.ru/resources/schools/ugai.pdf
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Marvan P., Mazánek V., Sofer Z. Shear-force exfoliation of indium and gallium chalcogenides for selective gas sensing applications. Nanoscale. 2019;11(10): 4310–4317 https://doi.org/10.1039/C8NR09294J
Woods-Robinson R., Han Y., Zhang H., Ablekim T., Khan I., Persson K. A., Zakutayev A. Wide band gap halcogenide semiconductors. Chemical Reviews. 2020;120(9): 4007–4055. https://doi.org/10.1021/acs.chemrev.9b00600
Zavrazhnov A. Yu, Turchen D. N, Goncharov Eu. G., Zlomanov V. P. Manometric method for the study of P-T-X diagrams. Journal of Phase Equilibria. 2001; 22(4): 482–490. https://doi.org/10.1361/105497101770333063
Zavrazhnov A. Yu. Design of P-T-x diagrams for gallium chalcogenides with the use of an ancillary component. Russian Journal of Inorganic Chemistry. 2003;48(10): 1577–1590.
Kosyakov A. V., Zavrazhnov A. Yu., Naumov A. V., Sergeeva A. S. Specification of the phase diagram of system In-S according to spectrophotometric researches of balance between sulfide of indium and hydrogen. Proceedings of Voronezh State University. Series: Chemistry. Biology. Pharmacy. 2009;2: 28–39. Available at: https://www.elibrary.ru/item.asp?id=12992199 (In Russ., abstract in Eng.)
Kosyakov A. V., Zavrazhnov A. Y. Naumov A. V . Refinement of the In-S phase diagram using spectrophotometric characterization of equilibria between hydrogen and indium sulfides. Inorganic Materials. 2010;46(4): 343–345 (2010). https://doi.org/10.1134/S0020168510040035
Zavrazhnov A. Y., Kosyakov A. V., Naumov A. V., Sergeeva A. V., Berezin S. S. Study of the In–S phase diagram using spectrophotometric characterization of equilibria between hydrogen and indium sulfides. Thermochimica Acta Journal. 2013;566: 169–174. https://doi.org/10.1016/j.tca.2013.05.031
Zavrazhnov A. Y., Turchen D. N., Naumov A. V., Zlomanov V. P. Chemical transport reactions as a new variant of the phase composition control. Journal of Phase Equilibria. 2003;24(4): 330–339. https://doi.org/10.1361/105497103770330316
Zavrazhnov A. Y., Turchen D. N., Naumov A. V., Zlomanov V. P. Chemical vapor transport as a means of controlling the composition of condensed phases. Inorganic Materials. 2004;40(2): 101–127. https://doi.org/10.1007/s10789-005-0056-6
Sidei V. I., Naumov A. V, Turchen D. N., Chukichev V. M. Upravlenie sostavom monoselenida galliya v predelakh oblasti gomogennosti i diagnostika nestekhiometrii GaSe [Controlling the composition of gallium monoselenide within the homogeneity region and diagnostics of GaSe nonstoichiometry]. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2004;6(4): 322–325. Available at: https://www.elibrary.ru/item.asp?id=29833369 (In Russ.)
Zavrazhnov A. Yu., Zartsyn I. D., Naumov A. V., Zlomanov V. P., Davydov A. V. Composition control of low-olatile solids through chemical vapor transport reactions. I. Theory of selective chemical vapor transport. Journal of Phase Equilibria and Diffusion. 2007;28(6): 510–516. https://doi.org/10.1007/s11669-007-9200-0
Zavrazhnov A., Naumov A., Sidey V., Pervov V. Composition control of low-volatile solids through chemical apor transport reactions. III. The example of gallium monoselenide: Control of the polytypic structure, non-stoichiometry and properties. Thermochimica Acta Journal. 2012;527: 118124. https://doi.org/10.1016/j.tca.2011.10.012
Zavrazhnov A. Yu., Naumov A., Riazhskikh M., Pervov V. Chemical vapor transport for the control of composition of low-volatile solids: II. The composition control of indium sulfides: Technique of the charge dilution. Thermochimica Acta Journal. 2012;532: 96102. https://doi.org/10.1016/j.tca.2010.10.004
Zavrazhnov A. Y., Naumov A. V., Sergeeva A. V., Sidey V. I. Selective chemical vapor transport as a means of varying the composition of nonstoichiometric indium sulfides. Inorg Mater 2007;43(11): 1167–1178. https://doi.org/10.1134/S0020168507110039
Zavrazhnov A. Yu., Naumov A., Sergeeva A., Semenov V., Pervov V. Novel approach to the design of optoelectronic heterostructures based on copper and indium sulfides. J. Fudan University (Fudan Xuebao, China). 2007;46(5): 730.
Kosyakov A. V., Nekrylov I. N., Brezhnev N. Yu., Berezin S. S., Malygina E. N., Zavrazhnov A. Yu. Tx diagram of the Ga - Se system in the composition range from 48.0 to 61.5 % Se according to thermal analysis data. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(4): 519–527.
https://doi.org/10.17308/kcmf.2019.21/2363 (In Russ., abstract in Eng.)
Berezin S. S., Berezina M. V., Zavrazhnov A. Y., Kosyakov A. V., Sergeeva A. V., Sidei V. I. Phase ransformations of indium mono- and sesquisulfides studied by a novel static thermal analysis technique. Inorganic Materials. 2013;49: 555–563. https://doi.org/10.1134/S0020168513060010
Berezin S. S., Spesivtseva A. P., Zavrazhnov A. Yu., Okushko A. I. Iron sulfides crystal growth at controlled sulfur pressure with the use of metal-halogenide melts. 2015;17(4): 412–416. Available at: https://www.elibrary.ru/item.asp?id=25946576 (In Russ., abstract in Eng.)
Zavrazhnov A. Y., Naumov A., Kosyakov A., Berezin S., Volkov V., Sergeeva A. The iron sulfides crystal growth from the halide melts. Materials Research. 2018;21(4): e20170648 . https://doi.org/10.1590/1980-5373-mr-2017-0648
Zavrazhnov A., Naumov A., Kosykov A., Kovygin Y. New way of the skeletal metal synthesis. J. Fudan University (Fudan Xuebao, China). 2007;46(5): 786.
Kosyakov A. V., Zavrazhnov A. Y., Naumov A. V., Nazarova A. A., Zlomanov V. P. Chemical vapor transport: A viable approach to controlling the composition of intermetallic phases promising for catalyst engineering. Inorganic Materials. 2007;43(11): 1199–1205. https://doi.org/10.1134/S0020168507110088
Kosyakov A. V., Zavrazhnov A. Yu. Equilibrium in the reaction between nickel or gallium in nickel solid solutions and of with carbon monoxide Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2017;19(1): 68–79. Available at: https://www.elibrary.ru/item.asp?id=29033318 (In Russ., abstract in Eng.)
Zavrazhnov A. Yu., Kosyakov A. V., Sergeeva A. V., Berezin S. S., Chernenko K. K. High-temperature in situ vapor spectrophotometry as a static variant of tensimetric method equilibria in the Ga-I system. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2015;17(4): 417–436. Available at: https://www.elibrary.ru/item.asp?id=25946578 (In Russ., abstract in Eng.)
Zavrazhnov A. Yu., Naumov A. V., Malygina E. N., Kosyakov A. V. Indium monochloride vapor pressure: the vapor-gauge and spectrophotometric experimaental data. Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(1): 60–71. https://doi.org/10.17308/kcmf.2019.21/717
Berezin S. S. Fazovye ravnovesiya v sistemakh Fe-S, Ga-S i sintez sul’fidov galliya i zheleza s ispol’zovaniem galogenidov FeХ2 (X ≠ F) и GaI3. Diss. Cand. Chem. Sciences / Voronezh: Voronezh State University; 2018. 239 p. Available at: https://www.dissercat.com/content/fazovye-ravnovesiya-v-sistemakh-fe-s-ga-s-i-sintezsulfidov-
galliya-i-zheleza-s-ispolzovanie (In Russ.).
Zavrazhnov A. Y., Berezin S. S., Kosykov A., Naumov A., Berezina M., Brezhnev N. The phase diagram of the Ga–S system in the concentration range of 48.0–60.7 mol%. Journal of Thermal Analysis and Calorimetry. 2018;134(1): 483–492 https://doi.org/10.1007/s10973-018-7124-z
Volkov V. V., Sidey V. I., Naumov A. V., Nekrylov I. N., Brezhnev N. Yu.; Malygina E. N., Zavrazhnov A. Yu. The cubic high-temperture modification of gallium sulphide (xS = 59 mol%) and the T, x-diagram of the Ga – S system Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases. 2019;21(1): 37–50. https://doi.org/10.17308/kcmf.2019.21/715
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