Electrochemical Synthesis and Characterization of Cu2ZnSnS4 Thin Films

Abstract

Cu2ZnSnS4 (CZTS) thin films have been electrochemically deposited from aqueous electrolyte containing CuCl2, ZnCl2, SnCl4 and Na2S2O3 onto fluorine doped tin oxide (FTO) coated glass substrates. A conventional three-electrode geometry consisting working, counter and reference electrodes was used to perform the electrochemical experiments. The films were deposited at - 1.1 V with respect to Ag/AgCl reference, which was optimized by cyclic voltammetry. CZTS layers were annealed in tubular furnace at 400°C for 15 minutes in vacuum. As-deposited and annealed CZTS films were characterized using range of characterization techniques to study the structural, optical, morphological, and compositional and optoelectronic properties. Annealed sample revealed (112), (220) and (312) planes corresponds to tetragonal kesterite CZTS structure and secondary peaks of CuZn alloy. The optical study shows that the band gap of the as-deposited CZTS film was found to be 1.68 eV. Upon annealing the optical band gap ~ 1.49 eV corresponds to CZTS were estimated from UV-Visible Spectroscopy and photoluminescence. Densely packed, void free and relatively uniform thin films were deposited by electrodeposition technique. The grain size has been increased upon the heat treatment. Copper and zinc rich off-stoichiometric films were deposited at -1.1 V. Current density-Voltage (J-V) measurements showed Schottkey behavior. The flat band potential and carrier concentration estimated by C-V measurement for annealed CZTS sample was 0.30 V and ~ 2.4 x 1016 cm-3 respectively.