Crystallization behaviour of co-sputtered Cu₂ZnSnS₄ precursor prepared by sequential sulfurization processes

Cu₂ZnSnS₄ (CZTS) thin films were prepared by the sequential sulfurization of a co-sputtered precursor with a multitarget (Cu, ZnS, and SnS₂) sputtering system. In order to investigate the crystallization behaviour of the thin films, the precursors were sulfurized in a tube furnace at different temperatures for different time durations. The Raman spectra of the sulfurized thin films showed that their crystallinity gradually improved with an increase in the sulfurization temperature and duration. However, transmission electron microscopy revealed an unexpected result - the precursor thin films were not completely transformed to the CZTS phase and showed the presence of uncrystallized material when sulfurized at 250-400 °C for 60 min and at 500 °C for 30 min. Thus, the crystallization of the co-sputtered precursor thin films showed a strong dependence on the sulfurization temperature and duration. The crystallization mechanism of the precursor thin films was understood on the basis of these results and has been described in this paper. The understanding of this mechanism may improve the standard preparation method for high-quality CZTS absorber layers.