Abstract
Chemistry is a science concerned with conversion of substances. From the chemical point of view, a substance is an assemblage of interacting particles, which is characterized by four properties: composition, structure, type of chemical bonding, and particle size. A conversion of a substance is a change in one or several of its properties. Targeted synthesis is a way of controlling a conversion of a substance. This paper considers thermodynamic and kinetic issues in targeted synthesis that are associated with control over the composition, structure, characteristic features of chemical bonding, and particle size and, hence, with the identification of conditions for the preparation of a substance with tailored properties. The concept of pure substance is discussed, which is an important issue for materials research and inorganic chemistry. It is pointed out that the composition of compounds should be characterized not only by their stoichiometry and impurity concentration but also by the related concentrations of native defects and impurities. In connection with this, a defect classification is presented and defect formation processes and techniques for controlling the defect composition are analyzed. Statistical criteria for assessing the compositional homogeneity of a pure substance are considered.
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Devyatykh, G.G. and Elliev, Yu.E., Vvedenie v teoriyu glubokoi ochistki veshchestv (Introduction to the Theory of Ultrapurification of Substances), Moscow: Nauka, 1981.
Novoselova, A.V., Fazovye diagrammy, ikh postroenie i metody issledovaniya (Phase Diagrams: Construction and Investigation), Moscow: Mosk. Gos. Univ., 1987.
Ormont, B.F., Vvedenie v fizicheskuyu khimiyu i kristallokhimiyu poluprovodnikov (Introduction to the Physical Chemistry and Crystal Chemistry of Semiconductors), Moscow: Vysshaya Shkola, 1968.
Medvedev, S.A., Vvedenie v tekhnologiyu poluprovodnikovykh materialov (Introduction to the Technology of Semiconductor Materials), Moscow: Vysshaya Shkola, 1970.
Fistul’, V.I., Fizika i khimiya tverdogo tela (Solid-State Physics and Chemistry), Moscow: Metallurgiya, 1995.
Gibbs, J.W., Elementary principles in statistical mechanics, developed with especial reference to the rational foundation of thermodynamics, in The Collected Works of J. Willard Gibbs, New York: Dover, 1961.
Voronin, G.F., Osnovy termodinamiki (Fundamentals of Thermodynamics), Moscow: Mosk. Gos. Univ., 1987.
Fuks, G.I., The smallest piece and the shortest life, Khim. Zhizn’, 1984, no. 2, p. 74.
Roldugin, V.I., Fizikokhimiya poverkhnosti (Physical Chemistry of Surfaces), Dolgoprudnyi: Intellekt, 2008.
Tret’yakov, Yu.D., Lukashin, A.V., and Eliseev, A.A., Synthesis of functional nanocomposites based on solidstate nanoreactors, Usp. Khim., 2004, vol. 73, no. 9, pp. 874–998.
Vasiliev, Ya., Akhmetshin, R., and Borodlev, Yu., Nucl. Instrum. Methods Phys. Res., Sect A, 1996, vol. 379, p. 533.
Golyshev, V., Gonic, M., et al., Heat transfer in growing Bi4Ge3O12 crystals under weak convection: I—Thermophysical properties of bismuth germanate in solid and liquid state, J. Cryst. Growth, 2004, vol. 262, p. 202.
Chernov, A.A., Givargizov, E.I., Bagdasarov, Kh.S., et al., Obrazovanie kristallov (Crystal Formation), vol. 3 of Sovremennaya kristallografiya (Modern Crystallography), Vainshtein, B.K., Chernov, A.A., and Shuvalov, L.A., Eds., Moscow: Nauka, 1980.
Lawson, W.D. and Nielsen, S., Preparation of Single Crystals, London: Butterworths, 1958. Translated under the title Vyrashchivanie monokristallov, in Protsessy rosta i vyrashchivanie monokristallov (Growth Processes and Preparation of Single Crystals), Moscow: Inostrannaya Literatura, 1963, pp. 13–302.
Kröger, F.A., The Chemistry of Imperfect Crystals, Amsterdam: North-Holland, 1964. Translated under the title Khimiya nesovershennykh kristallov, Moscow: Mir, 1969, p. 654.
Rosenberger, F., Fundamentals of Crystal Growth I: Macroscopic Equilibrium and Transport Concepts, Berlin: Springer, 1979.
Gottshtain, G., The Physicochemical Grounds of Material Science, Moscow: Binom, 2009, p. 400.
Zlomanov, V.P. and Novoselova, A.V., P-T-x diagrammy sostoyaniya sistem metall-khal’kogen (P-T-x Phase Diagrams of Metal-Chalcogen Systems), Moscow: Nauka, 1987.
Storonkin, A.V., Termodinamika geterogennykh sistem (Thermodynamics of Heterogeneous Systems), Leningrad: Leningrad. Gos. Univ., 1967, part 1.
Van Bueren, H.G., Imperfections in Crystals, New York: Interscience, 1961. Translated under the title Defekty v kristallakh, Moscow: Inostrannaya Literatura, 1962, p. 302.
Stalova, M., Semicond. Semimetals, 1998, vol. 51A, p. 47.
Handbook of Semiconductor Technology, Jackson, K.A. and Schröger, W., Eds., Weinheim: Wiley-VCH, 2000, vol. 1. Translated under the title Entsiklopediya tekhnologii poluprovodnikovykh materialov, Moscow: ANO Izdatel’stvo Vodolei, 2003, vol. 1, p. 967.
West, A.R., Solid State Chemistry and Its Applications, Chichester: Wiley, 1985. Translated under the title Khimiya tverdogo tela, teoriya i prilozheniya, Moscow: Mir, 1988, part 1, p. 434.
Gusev, A.V., Gavva, V.A., Kozyrev, E.A., Potapov, A.M., and Plotnichenko, V.G., Preparation of single-crystal 29Si, Inorg. Mater., 2011, vol. 47, no. 7, pp. 691–693.
Devyatykh, G.G. and Churbanov, V.F., Metody polucheniya veshchestv osoboi chistoty (Methods of Producing Extrapure-Grade Substances), Moscow: Znanie, 1976.
Triboulet, R. and Siffer, P., CdTe and Related Compounds: Physics, Defects, Hetero- and Nano-structures, Crystal Growth, Surface and Applications, Amsterdam: Elsevier, 2010.
Zlomanov, V.P., Crystal growth of nonstoichiometric compounds, Inorg. Mater., 2006, vol. 42, suppl. 1, pp. 19–48.
Zlomanov, V.P., Nonstoichiometry and reactivity of inorganic compounds, Russ. J. Inorg. Chem., 2000, vol. 45,suppl. 3, pp. 292–311.
Fochuk, P., Korovyanenko, O., and Panchuk, O., High-temperature point defect equilibrium in CdTe modelling, J. Cryst. Growth, 1999, vol. 97, no. 3, p. 603.
Kukk, P.L. and Altosaar, M., Defect structure of Cl and Cu doped CdS heat-treated in Cd and S2 vapor, J. Solid State Chem., 1983, vol. 98, no. 1, p. 1.
Nishizava, J. and Oyama, Y., Stoichiometry of III-V compounds, Mater. Sci. Eng., 1994, vol. 12, nos. 6–8, pp. 273–426.
Nishizava, J., Abstracts of papers, 1st Int. Symp. on Point Defect and Nonstoichiometry, Sendai, 2003, p. 1.
Neubert, M. and Rudolph, P., Growth of semi-insulating GaAs crystals in low temperature gradients by using the vapour pressure controlled Czochralski method (VCz), Prog. Cryst. Growth Character. Mater., 2001, vol. 43, p. 119.
Zlomanov, V.P. and Yashina, L.V., Lead Chalcogenides: Physics and Applications, 2002, p. 37.
Brebrick, R.F. and Gubner, E., PbSe composition stability limits, J. Chem. Phys., 1962, no. 36, p. 170.
Van Lierder, W. and de Jonghe, L., The controlled oxidation of single crystals of UO2 to U4O9, Solid State Commun., 1964, vol. 2, p. 129.
Van Gool, W., Principles of Defects Chemistry of Crystalline Solids, New York: Academic, 1966, p. 327.
Van Gool, W., Preparation of ZnS and CdS phosphors influenced by oxygen, Philips Res. Rep., Suppl., 1961, no. 3, p. 361.
Prior, A.C., Growth from the vapor of large single crystals of lead selenide of controlled composition, J. Electrochem. Soc., 1961, vol. 108, p. 82.
Goldgirsh, A., Shusterman, S., Zilber, R., and Azouloy, M., Programme and Abstracts of Symp.: Solid Solutions of the II-VI Compounds, Zakopane, 2002, p. 20.
Osvenskii, V.B., in Fundamental’nye problemy rossiiskoi metallurgii na poroge XXI veka (Fundamental Problems of Russian Metallurgy on the Eve of the 21st Century), Moscow: RAEN, 1998, vol. 4, p. 85.
Zlomanov, V.P., Demin, V.N., and Gas’kov, A.M., Predominant defects in semiconductor isovalent solid solutions: Pb1 − y (SexTe1 − x )y, Pb1 − y (SxTe1 − x )y, and Pb1 − y (SxSe1 − x )y, J. Mater. Chem., 1992, vol. 2, no. 1, p. 31.
Zavrazhnov, A.Yu., Turchen, D.N., Naumov, A.V., and Zlomanov, V.P., Transport reactions as a new variant of the phase composition control, J. Phase Equilib., 2003, vol. 24, no. 4, p. 330.
Zavrazhnov, A.Yu., Zarzyn, I.D., Turchen, D.N., Naumov, A.V., and Zlomanov, V.P., Chemical vapor transport as a means of controlling the composition of condensed phases, Inorg. Mater., 2004, vol. 40,suppl. 2, pp. 101–127.
Wagner, J.B. and Wagner, C., Investigations on cuprous sulfide, J. Chem. Phys., 1957, vol. 26, p. 1602.
Miyatani, S., Galvano- and thermomagnetic effects in α-Ag2Te, J. Phys. Soc. Jpn., 1959, vol. 14, p. 750.
Mathieu, H.J. and Rickert, H., Elektrochemisch-thermodynamische Untersuchungen am System Kupfer-Schwefel bei Temperaturen T = 15–90 Deg., Z. Phys. Chem. (Frankfurt), 1972, vol. 79, p. 315.
Leushina, A.P. and Simonova, M.V., Homogeneity range and defect structure of lead sulfide at 310° as determined using emf measurements, Zh Fiz. Khim., 1975, vol. 49, p. 1218.
Leushina, A.P., Kolesnikov, L.A., Makhanova, E.V., and Zlomanov, V.P., Trudy 7-ogo Soveshchaniya “Fundamental’nye problemy ioniki tverdogo tela” (Proc. 7th Conf. Fundamental Issues in Solid-State Ionics), Chernogolovka, 2004, p. 30.
Alcock, C.B., Zador, S., and Steele, B.C.H., A thermodynamic study of dilute solutions of defects in the rutile structure TiO2 − x , NbO2 − x , and Ti0.5Nb0.5O2 ± x , Proc. Br. Ceram. Soc., 1967, vol. 8, p. 231.
Schmalzried, H. and Tretyakov, Yu.D., Irregularity in ferrite, Ber. Bunsen-Ges. Phys. Chem., 1966, vol. 72, p. 180.
Wijn, H.P., A new method of melting ferromagnetic semiconductors. BaFe18O27, a new kind of ferromagnetic crystal with high crystal anisotropy, Nature (London), 1957, vol. 170, p. 707.
Osipov, A.V. and Kukushkin, S.A., A new method for the synthesis of epitaxial layers of silicon carbide on silicon owing to formation of dilatation dipoles, J. Appl. Phys., 2013, vol. 113, paper 024 909.
Belov, N.V., Struktura ionnykh i kovalentnykh kristallov (Structure of Ionic and Covalent Crystals), 1947.
Urusov, V.S., Teoreticheskaya kristallokhimiya (Theoretical Crystal Chemistry), Moscow: Mosk. Gos. Univ., 1987.
Wells, A., Structural Inorganic Chemistry, Oxford: Clarendon, 1984.
Antipov, E.V. and Abakumov, A.M., Structural design of copper-oxide-based superconductors, Usp. Fiz. Nauk, 2008, vol. 178, no. 2, pp. 190–202.
Charkin, D.O., Modul approach as applied to the description, prediction and target synthesis of bismuth oxohalides with layered structures, Russ. J. Inorg. Chem., 2008, vol. 53, no. 13, pp. 1977–1996.
Ginzburg, V.L., Concerning surface conduction, Zh. Eksp. Teor. Fiz., 1964, vol. 47, p. 2318.
Suzdalev, I.P., Nanotekhnologiya: fizikokhimiya klasterov, nanostruktur i nanomaternalov (Nanotechnology: Physical Chemistry of Clusters, Nanostructures, and Nanomaterials), Moscow: KomKniga, 2006.
Murray, C.B., Norris, D.J., and Bawendi, M.G., Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites, J. Am. Chem. Soc., 1993, vol. 115, pp. 8706–8709.
Manna, L., Milliron, D.J., Meisel, A., Scher, E.C., and Alivisatos, A.P., Controlled growth of tetrapodbranched inorganic nanocrystals, Nat. Mater., 2003, vol. 2, pp. 382–385.
Vasiliev, R.B., Dirin, D., and Gas’kov, A.M., Temperature effect on the growth of colloidal CdTe nanotetrapods, Mendeleev Commun., 2009, vol. 19, pp. 126–127.
Nanotekhnologii. Azbuka dlya vsekh (Nanotechnologies: The ABC for Everyone), Tret’yakov, Yu.D., Ed., Moscow: Fizmatlit, 2008.
Nikitina, V.G., Orlov, A.G., and Romanenko, V.N., Problema neodnorodnosti raspredeleniya atomov i defektov pri issledovanii sovershenstva poluprovodnikovykh kristallov (Problem of inhomogeneous atom and defect distributions in studies of the perfection of semiconductor crystals), in Protsessy rosta poluprovodnikovykh kristallov i plenok (Growth of Semiconductor Crystals and Films), Novosibirsk: Nauka, 1981, vol. 6, p. 204.
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Zlomanov, V.P. Key issues in the targeted synthesis of inorganic substances. Inorg Mater 49, 1233–1248 (2013). https://doi.org/10.1134/S0020168513130013
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DOI: https://doi.org/10.1134/S0020168513130013