ISSN 1070-4272, Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 1, pp. 91−96. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © S.S. Tulenin, A.A. Timina, L.N. Maskaeva, V.F. Markov,
2017, published in Zhurnal Prikladnoi Khimii, 2017, Vol. 90, No. 1, pp. 98−103.
Chemical Bath Deposition of Thin Nanocrystalline Tin(II)
Sulﬁ de Films with Thioacetamide
S. S. Tulenin
, A. A. Timina
, L. N. Maskaeva
*, and V. F. Markov
Ural Federal University after name the First President of Russia B.N. Yeltsin, ul. Mira 19, Yekaterinburg, 620002 Russia
Ural Institute of State Fireﬁ ghting Service, Ministry of Emergency Situations of the Russian Federation,
ul. Mira 22, Yekaterinburg, 620137 Russia
Received November 30, 2016
Abstract—Nanocrystalline tin(II) sulﬁ de layers 100–650 nm thick were prepared by hydrochemical deposition on
glass–ceramic supports from a citrate system at 323−343 K using thioacetamide as chalcogenizing agent. These
ﬁ lms are of interest for the development of thin-ﬁ lm solar radiation converters based on the multicomponent
of kesterite structure, prepared using a cost-saving process. Examination by scanning
electron microscopy shows that tin(II) sulﬁ de layers are formed from spherical nanocrystallites of 20–40 nm size.
X-ray diffraction analysis shows that they crystallize in the orthorhombic system with the unit cell parameters
a = 4.276, b = 11.243, and c = 3.986 Å. Analysis by X-ray photoelectron spectroscopy revealed the presence of
up to 44.86 at. % oxygen in the surface layer of the ﬁ lm. This oxygen is mainly present in surface contaminants
and is also incorporated in SnO present on the surface.
Compounds based on tin(II) sulﬁ de substitude today
a particular place among materials sensitive in the vis-
ible and near-IR range . They are widely used as a
base of the multicomponent compound Cu
kesterite structure, from which thin-ﬁ lm solar energy
converters are prepared [2−5], and also as photocon-
ductors, semiconductor sensors, and microcells used in
robotic engineering, medicine, and space and military
engineering [6, 7].
The majority of the existing methods for preparing
tin(II) sulﬁ de in the form of thin ﬁ lms are based, as
a rule, on physical procedures and have a number of
disadvantages such as the use of high temperatures,
high vacuum, and sophisticated equipment [1, 2, 8].
On the other hand, the procedure for hydrochemical
deposition of SnS from aqueous solution is of much
interest [9–11]. The method is simple and power-
saving and allows wide variation of the composition
and functional properties of the materials by using
different complexing and sulfudizing agents. However,
the main problem in hydrochemical synthesis of SnS
ﬁ lms is the choice of the formulation and determination
of the optimum deposition conditions.
A number of published papers deal with thin tin
sulﬁ de ﬁ lms prepared from alkaline solutions using
as chalcogenizing agent [11−13].
The thermodynamic calculations of the conditions for
the formation of the SnS phase are performed, and
the composition of the deposition baths is suggested.
Sodium thiosulfate [14, 15] and ammonium sulﬁ de 
are also used as chalcogenizing agents for the synthesis
of tin sulﬁ de ﬁ lms. The layers synthesized in these
studies are relatively thick (up to 400–500 nm), but
have heterogeneous composition and imperfect crystal
structure. Such papers are scarce and, as a rule, consist
in search for the deposition conditions. In the majority
of studies, tin sulﬁ de ﬁ lms were deposited from weakly
acidic solutions using thioacetamide CSCH
[17−20]. It should be noted that many researches focus
their attention on formulations without studying in detail
the nucleation and growth of the solid phase, which also
exert a decisive effect on the structure and properties of