Effect of solid-H₂S gas reactions on CZTSSe thin film growth and photovoltaic properties of a 12.62% efficiency device

We fabricated CZTSSe thin films using optimized SLG-Mo/Zn/Cu/Sn (MZCT) as a stacked structure and described the phenomenon of Zn elemental volatilization using the MZCT stacked structure. We introduced H₂S gas to effectively control the S/(S + Se) ratio of the film in the sulfo-selenization process and to suppress Zn volatilization. Unlike during the selenization process, a stable ZnSSe thin film was formed on the precursor surface during the sulfo-selenization process. The formation of the ZnSSe thin film inhibited Zn volatilization, which facilitated control of the thin film stoichiometry and played an important role in crystal growth. In addition, the sulfo-selenization process using H₂S forms a grading of the S/(S + Se) ratio in the depth direction in the ZnSSe layer. The ZnSSe layer with this property causes the band gap grading in the CZTSSe absorption layer. Finally, through our optimized annealing process, we realized a world record CZTSSe solar cell with a certified power conversion efficiency of 12.62% and a centimetre-scale (1.1761 cm²) efficiency of 11.28%.