Cu2ZnSnS4 films properties deposited by spray pyrolysis, subjected to a combined novel thermal treatment: CSS sulfurization and RTA post-treatment

Abstract

CZTS films were obtained by spray pyrolysis, a low-cost technique implemented on an industrial scale. Sulfurization processes generally enhance CZTS properties for its use in solar cells; however, these require high temperatures and long times. In this work, CZTS films properties were studied after being subjected to a combined novel thermal treatment which involved two stages. Sulfur incorporation using close space sublimation technique (CSS) at a temperature (TCSS) in the 350–500 °C range for 60 s, and after a rapid thermal annealing post-treatment (RTA) at TRTA = 500 °C for 10 s, with a heating ramp of 5 °C/s under argon atmosphere. Morphological, structural, chemical composition, optical and electrical properties were studied for CZTS films subjected to CSS as CSS+RTA treatments for all TCSS values. From the results, efficient sulfur incorporation by CSS was obtained without substantial sulfur concentration loss after RTA treatment, associated with the short treatment time. In addition, significant enhancement of crystalline quality and electrical resistivity diminished of the films is obtained after the CSS+RTA process for all TCSS. CZTS films with the best properties are those obtained at TCSS of 400 °C, having Cu/(Zn+Sn) = 0.79 and Zn/Sn = 1.3 ratios, a direct bandgap value of 1.5 eV, and resistivity of 4 Ω-cm. These films can be candidates for their characteristics as an absorbent layer in solar cells.