Band Tails and Cu–Zn Disorder in Cu₂ZnSnS₄ Solar Cells

Cu2ZnSnS4 (CZTS) has attracted interest for applications in thin-film solar cells. In this study, the annealing process for CZTS fabrication is systematically varied, resulting in a large variation of materials properties. These variations are connected to the sulfur partial pressure during the annealing. A well-known phenomenon in CZTS is the presence of a high density of Cu-Zn antisite defect pairs, also known as Cu-Zn disorder. Faster Cu-Zn ordering occurs in samples with a similar starting composition annealed in an atmosphere with a higher sulfur partial pressure. This is explained by a higher density of vacancies in these samples. The results indicate that reduction of the vacancy concentration in CZTS annealed in insufficient sulfur partial pressure reduces diffusion, which results in more defective material with a higher density of tail states and poorer device performance.