347 ISSN 1070-4272, Russian Journal of Applied Chemistry, 2018, Vol. 91, No. 3, pp. 347−359. © Pleiades Publishing, Ltd., 2018. Original Russian Text © A.I. Abdulagatov, Kr.N. Ashurbekova, Ka.N. Ashurbekova, R.R. Amashaev, M.Kh. Rabadanov, I.M. Abdulagatov, 2018, published in Zhurnal Prikladnoi Khimii, 2018, Vol. 91, No. 3, pp. 305−318. INORGANIC SYNTHESIS AND INDUSTRIAL INORGANIC CHEMISTRY Molecular Layer Deposition and Thermal Transformations of Titanium(Aluminum)-Vanadium Hybrid Organic-Inorganic Films A. I. Abdulagatov, Kr. N. Ashurbekova, Ka. N. Ashurbekova, R. R. Amashaev, M. Kh. Rabadanov, and I. M. Abdulagatov* Dagestan State University, Makhachkala, ul. Batyraya 4, Dagestan, 367008 Russia *e-mail: ilmutdina@gmail.com Received January 12, 2018 Abstract—In this work Molecular layer deposition (MLD) technique used to synthesize titanium-vanadium (TiV x C y O z ) and aluminum-vanadium (AlV x C y O z ) hybrid organic-inorganic films via alternating surface reac- tions of titanium tetrachloride (or trimethylaluminum), vanadium oxochloride, and ethylene glycol. Using in situ monitoring it was found that the surface reactions were self-limiting at temperatures of 90 and 115°C. The coating thickness per molecular layer deposition cycle (growth rate) at 115°C on a silicon substrate varied from 5.8 to 11.4 Å/cycle, and the film densities, from 1.7 to 2.0 g cm –3 . An analysis of the samples obtained at 115°C revealed their amorphous structure. A thermal treatment of titanium-vanadium films at 450°C in air resulted in formation of highly structured coatings. These coatings were composed of nanowires of single-crystal vanadium oxide (V 2 O 5 ) and mixed nanostructures of titanium and vanadium oxides. Increase in thermal treatment tempera- ture to 500°C resulted in elongation of the V 2 O 5 nanowires up to tens of micrometers and in their separation from the substrate. A thermal treatment of aluminum-vanadium films in air resulted in formation of a low-density film. Pyrolysis of the films in an inert gas yielded composite coatings containing domains of graphitized carbon. These films can be potentially useful in modern devices for energy storage, electronics, medicine and other promising fields of technology. DOI: 10.1134/S1070427218030011 The atomic layer deposition (ALD) method can be used to obtain oxides, sulfides, nitrides, carbonaceous, organic, hybrid organic-inorganic and many other nanostructured thin films [1, 2]. Under the name “molecular layering”, the ALD method was first developed in the 1960’s by the scientific school of Professor V.B. Aleskovskii, a corresponding member of the Academy of Sciences of the USSR [1]. The ALD of organic and organic-inorganic coatings has been reported since some time ago under the name molecular layer deposition (MLD) [3, 4]. At this point, a large number of various kinds of MLD coatings has been developed [5, 6]. Thermal treatment of these films makes possible to obtain a wide variety of new materials that cannot be directly synthesized by the ALD method. For example, a thermal treatment has been used to obtain conducting carbon containing metal oxides [7], porous metal oxides [8], and nanostructured [9] thin films. Both as-synthesized and thermally treated MLD coatings are promising for application in lithium-ion batteries [10–12], flexible electronics [13], catalysis [14], gas separation [15], spintronics [16, 17], reverse-osmosis water desalination technology [18], etc. It is known that doping of titanium oxide with vanadium particles results in a red shift of the spectral lines of TiO 2 , which makes it more effective in photo oxidation under solar light [19, 20]. Films of vanadium and mixed vanadium-titanium (or aluminum) oxides are promising electrode materials for Li + intercalation in lithium-ion batteries [21]. The crystal structure of titanium oxide and vanadium has a higher cycling stability and intercalation capacity than the V 2 O 5 structure [22, 23]. Catalytic systems based on mixtures of titanium