Abstract
The mechanism of hydrolytic decomposition of thiocarbamide upon the interaction with metal salts with deposition of thin films of sulfide was proposed. The kinetic studies of the transformation of metal salt into sulfide and IR spectroscopy confirmed that one of the hydrolysis products of thiocarbamide was cyanamide. The concept about the activation of thiocarbamide decomposition was extended due to the nucleophilic addition of anions to form an intermediate reaction complex thiocarbamide—metal ion—nucleophile. The activation weakens in the order OH− > CH3COO− > Cl− > Br− > I−. The presence and active role of colloidal components of reaction mixtures in the nucleation and formation of films of metal sulfides by chemical bath synthesis were established by spectrophotometric and kinetic measurements. It was concluded that from the viewpoint of fractal formalism metal sulfide films are formed in chemical bath deposition via the mechanism of cluster—cluster aggregation in the form of consecutive evolution of structural levels. A complex scheme of the mechanism of chemical bath deposition of metal sulfides by thiocarbamide was proposed. The results of studies of their phase composition, microstructure, and properties are presented.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
L. N. Kurbatov, Voprosy oboronnoi tekhniki [Problems of Defense Technology], 1995, 1–2, 3 (in Russian).
V. F. Markov, G. A. Kitaev, S. N. Uimin, L. N. Maskaeva, Innovatsiya [Innovation], 1998, 1, 55 (in Russian).
L. Bakueva, S. Musihin, M. A. Hines, T.-W. F. Chang, M. Tzolov, G. D. Scholes, E. H. Sargent, Appl. Phys. Lett., 2003, 82, 2895.
E. I. Rogachena, Y. O. Vekhov, M. S. Dresselhaus, S. B. Cronin, Thin Solid Films, 2003, 423, 115.
P. K. Nair, M. T. S. Nair, A. Fernandez, M. Ocampo, J. Phys. D: Appl. Phys., 1989, 22, 829.
P. K. Nair, M. T. S. Nair, J. Phys. D: Appl. Phys., 1990, 23, 150.
P. K. Nair, M. T. S. Nair, V. M. Garcia, O. L. Arenas, Y. Peña, A. Castillo, I. T. Ayala, O. Gomezdaza, A. Sánchez, J. Campos, H. Hu, R. Suárez, M. E. Rincón, Sol. Energy Mater. Sol. Cells, 1998, 52, 313.
K. Chopra, S. R. Das, Thin Film Solar Cells, Plenum Press, New York, 1983, 607 pp.
S. N. Shtykov, T. Yu. Rusanova, Ros. Khim. Zh., 2008, 52, No. 2, 92 [Mendeleev Chem. J. (Engl. Transl.), 2008, 52, No. 2].
A. Galdikas, A. Mironas, V. Strazdiene, A. Setkus, I. Ancutiene, V. Janickis, J. Sens. Actuators B, 2000, 67, 76.
V. F. Markov, L. N. Maskaeva, J. Anal. Chem., 2001, 56, 754 [Zh. Anal. Khim., 2001, 56, 846].
S. K. Kulkarni, U. Winkler, N. Deshmukh, P. H. Boese, R. Fink, E. Unbuch, Appl. Surf. Sci., 2001, 169–170, 438.
V. A. Oleinikov, A. V. Sukhanova, I. R. Nabiev, Ros. nanotekhnologii [Russian Nanotechnologies], 2007, 2, 160 (in Russian).
P. O’Brien, J. McAleese, J. Mater. Chem., 1998, 8, 2309.
V. F. Markov, L. N. Maskaeva, P. N. Ivanov, Gidrokhimicheskoe osazhdenie plenok sul’fidov metallov: modelirovanie i eksperiment [Chemical Bath Deposition of Metal Sulfide Films: Modeling and Experiment], UrO RAN, Ekaterinburg, 2006, 218 pp. (in Russian).
O. P. Moreno, M. Ch. Portillo, M. M. Flores, J. M. Juarez, G. A. Avila, R. L. Morales, O. Z. Angel, J. Mater. Sci. Eng. A, 2011, 1, 759.
S. Rajpal, V. Bandyopadhyay, J. Nano-Electron. Phys., 2013, 5, 03021.
Yu. N. Makurin, R. N. Pletnev, D. G. Kleshchev, N. A. Zhelonkin, Promezhutochnyi kompleks v khimicheskikh reaktsiyakh [Intermediate Complex in Chemical Reactions], AN SSSR UrO, Sverdlovsk, 1990, p. 78 (in Russian).
N. V. Vorob’ev-Desyatovskii, Yu. N. Kukushkin, V. V. Sibirskaya, Koordinats. Khim., 1985, 11, 1299 [Sov. J. Coord. Chem. (Engl. Transl.), 1985, 11, No. 10].
A. V. Naumov, V. N. Semenov, E. M. Averbakh, Khim. prom-st’ [Chemical Indusry], 2003, 80, 17 (in Russian).
G. Charlot, Les Methodes de la Chimie Analytique: Analyse Quantitative Minerale, Masson, Paris, 1961, 1024 pp.
I. T. Romanov, G. A. Kitaev, Fiziko-khimiya protsessov na mezhfaznykh granitsakh [Physicochemistry of Processes on Interfaces], Izd-vo UPI, Sverdlovsk, 1976, p. 6 (in Russian).
G. A. Kitaev, L. N. Maskaeva, V. F. Markov, A. Yu. Kurkin, Izv. Akad. Nauk SSSR. Neorg. Mater., 1989, 25, 1262 [Inorg. Mater. (Engl. Transl.), 1989, 25, No. 8].
S. Kotrly, L. Sucha, Handbook of Chemical Equilibria in Analytical Chemistry, Ellis Horwood, New York-Brisbane-Chichester-Toronto, 1985, p. 143.
Yu. Yu. Lur’e, Spravochnik po analiticheskoi khimii [Manual on Analytical Chemistry], Khimiya, Moscow, 1989, 448 pp. (in Russian).
Yu. N. Makurin, V. I. Dvoinin, R. N. Pletnev, 15-i Mendeleevskii s"ezd po obshchei i prikladnoi khimii [15th Mendeleev Congress on General and Applied Chemistry] (Minsk, May 24–29, 1993), Minsk, 1993, 2, 273 (in Russian).
A. A. Rempel, Russ. Chem. Rev., 2007, 76, 435.
J. Herrero, M. T. Gutierrez, C. Guillen, J. M. Doña, M. A. Martinez, A. M. Chaparro, R. Bayón, Thin Solid Films, 2000, 361–362, 28.
A. A. Vlasov, Staticheskie funktsii raspredeleniya [Statistical Distribution Functions], Nauka, Moscow, 1966, p. 324–356 (in Russian).
N. N. Sheftal’, Rost kristallov [Crystal Growth], Nauka, Moscow, 1974, 10, 195 (in Russian).
I. T. Romanov, G. A. Kitaev, Kolloid. Zh., 1979, 41, 590 [Colloid. J. USSR (Engl. Transl.), 1979, 41, No. 3].
B. B. Nayak, H. N. Acharya, J. Mater. Sci. Lett., 1985, 4, 651.
M. Dutt, D. Kameshwari, D. Subbarao, Colloids Surf., A., 1998, 133, 89.
B. M. Smirnov, Fizika fraktal’nykh klasterov [Physics of Fractal Clusters], Nauka, Moscow, 1991, 134 pp. (in Russian).
L. N. Maskaeva, G. A. Kitaev, V. F. Markov, Tez. dokl. Vtoroi mezhregion. konf. s mezhdunar. uchastiem “Ul’tradispersnye materialy” [Proc. Second Interdistrict Conference with International Participation "Ultradispersed Materials"] (Krasnoyarsk, October 5–7, 1999), Krasnoyarsk, 1999, 42 (in Russian).
V. F. Markov, L. N. Maskaeva, P. N. Ivanov, Kondensirovannye sredy i mezhfaznye granitsy [Condensed Media and Interfaces], 2004, 6, 374 (in Russian).
J. Feder, Fractals, Plenum Press, New York, 1988, 283 pp.
G. A. Kitaev, L. N. Maskaeva, V. F. Markov, L. E. Vasyunina, L. A. Burkova, Izv. Akad. Nauk SSSR. Neorg. Mater., 1989, 25, 1438 [Inorg. Mater. (Engl. Transl.), 1989, 25, No. 9].
G. A. Kitaev, V. F. Markov, L. N. Maskaeva, L. E. Vasyunina, I. V. Shilova, Izv. Akad. Nauk SSSR. Neorg. Mater., 1990, 26, 248 [Inorg. Mater. (Engl. Transl.), 1990, 26, No. 2].
L. N. Maskaeva, V. F. Markov, T. V. Vinogradova, A. A. Rempel’, A. I. Gusev, Poverkhnost’. Rentgenovskie, sinkhrotronnye i neitronnye issledovaniya [Surface: X-Ray, Synchronous, and Neutron Studies], 2003, 9, 35 (in Russian).
L. N. Maskaeva, V. F. Markov, V. I. Voronin, A. I. Gusev, Thin Solid Films, 2004, 361, 325.
D. S. Epaneshnikova, V. F. Markov, L. N. Maskaeva, Khim. Tekhnologiya[Chemical Technology], 2008, 9, 417 (in Russian).
L. N. Maskaeva, V. F. Markov, I. M. Morozova, N. M. Barbin, V. Ya. Shur, E. I. Shishkin, E. S. Samoilova, Pis’ma v Zh. Eksp. Teor. Fiz., 2008, 34, No. 11, 39 [JETP Lett. (Engl. Transl.), 2008, 38, No. 11].
A. S. Katysheva, V. F. Markov, L. N. Maskaeva, Zh. Neorg. Khim., 2013, 58, 940 [Russ. J. Inorg. Chem. (Engl. Transl.), 2013, 58, No. 7].
S. S. Tulenin, V. F. Markov, L. N. Maskaeva, M. V. Kuznetsov, Butlerov. Soobshch. [Butlerov’s Reports], 2013, 33, 97 (in Russian).
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to Academician of the Russian Academy of Sciences O. N. Chupakhin on the occasion of his 80th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1523–1532, July, 2014.
Rights and permissions
About this article
Cite this article
Markov, V.F., Maskaeva, L.N. Nucleation and mechanism of metal sulfide film growth using deposition by thiocarbamide. Russ Chem Bull 63, 1523–1532 (2014). https://doi.org/10.1007/s11172-014-0630-7
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11172-014-0630-7