Defect chemistry and chalcogen diffusion in thin-film Cu2ZnSnSe4 materials

Selenium diffusion in polycrystalline thin-film Cu2ZnSn(S,Se)4 (CZTSe) on molybdenum-coated soda-lime glass substrates was investigated by in situ monitoring of the molybdenum back-contact resistance during high-temperature selenization treatments. In these measurements, selenium diffusion through the CZTSe layer results in conversion of the molybdenum layer to MoSe2, increasing the sheet resistance of the film stack. By monitoring the rate of MoSe2 formation as a function of annealing temperature, an activation energy of 0.5 ± 0.1 eV has been measured for selenium diffusion in CZTSe. The partial pressure dependence of chalcogen diffusion suggests that chalcogen vacancies are not the defect controlling chalcogen diffusion in thin-film CZTSe.