ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 6, pp. 1074−1077. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © M.B. Dergacheva, K.A. Urazov, K.A. Leont’eva, G.M. Khusurova, N.N. Gudeleva, V.I. Yaskevich, 2015, published in Zhurnal Prikladnoi
Khimii, 2015, Vol. 88, No. 6, pp. 980−983.
Electrochemical Behavior of Cu(II), Zn(II), and Sn(II) Ions
in Simultaneous Reduction with Thiosulfate Ions
on a Molybdenum Electrode
M. B. Dergacheva, K. A. Urazov, K. A. Leont’eva, G. M. Khusurova,
N. N. Gudeleva, and V. I. Yaskevich
Sokol’skii Institute of Organic Catalysis and Electrochemistry, Kunaeva st. 142, Almaty, 050010 Kazakhstan
Received June 2, 2015
Abstract—Electrochemical behavior of copper(II), zinc(II), tin(II) in joint reduction with thiosulfate ions on
a molybdenum electrode from a citrate solution was studied. It was shown that use of sodium citrate salts as a
complexing substance makes it possible to diminish the difference between the reduction potentials of the metals
in their joint deposition. The results of an analysis of cyclic voltammetric curves were used to develop a method
for electrochemical deposition of a Cu–Zn–Sn–S quaternary compound in a single stage from an aqueous solution
on a molybdenum electrode at a constant potential.
Fabrication of thin photovoltaic cell based on
multicomponent semiconductors including selenium
and sulfur is a new area in the development of a third
generation of devices for sunlight conversion. The
manufacture of cells of this kind should be inexpensive,
highly efﬁ cient, and environment friendly Cu
(CZTS) is a promising material, which is intensively
studied at present and can be used as the absorbing layer
of thin-ﬁ lm solar cells.
CZTS is a p-type semiconductor with a direct energy
gap width of approximately 1.5 eV and high absorption
coefﬁ cient (>1014 cm
) . The crystal structure of
CZTS corresponds to that of kesterite and can be obtained
from the sphalerite structure. The kesterite structure is the
most stable phase of CZTS . The lattice constants of
CZTS: a = 0.54 nm and b = 1.09 nm ; hence the atomic
masses of Cu, Zn, Sn, and S can be calculated [4, 5], as
well as the CZTS density (4.6 g cm
Various methods are known for fabrication of CZTS,
such as thermal evaporation, magnetron sputtering,
reactive magnetron co-sputtering, mild chemical method,
sol-gel precipitation followed by sulfation, spraying co-
deposition, pulse laser deposition, and SILAR technique.
However, especially noteworthy is the electrochemical
deposition method, which makes it possible to perform the
process at low temperatures, with all the four components
(Cu, Zn, Sn, and S) simultaneously deposited.
The goal of our study was to develop a new technique
of simultaneous electrodeposition of four components
of the compound Cu
, which would enable
deposition of elements with strongly different standard
potentials in a single stage on a molybdenum electrode
with the use of a complexing agent.
To find the optimal deposition potential of thin
films of the quaternary compound CZTS, we used
the voltammetric method of analysis. Curves were
recorded in a three-electrode cell a disk molybdenum
electrode (S = 0.07 cm
) as working electrode and a
platinum electrode (S = 1.5 cm
) as auxiliary electrode.
The potentials were measured relative to a silver
chloride reference electrode. Thin CZTS ﬁ lms were
deposited onto 1 × 2 cm molybdenum plates from an
electrolyte containing the following salts: copper(II)