Structural and electronic properties of low-index stoichiometric Cu2ZnSnS4 surfaces

Over the past few years, quaternary Cu2ZnSnS4 (CZTS) has attracted a great deal of attention as the most promising photovoltaic absorber layer, due to its abundance and non-toxic properties. However, the significant surface structures and properties for photo-catalytic absorption layers have not yet been studied in detail for CZTS. Hence, the surface structure and electronic properties of low-index stoichiometric CZTS surfaces are calculated based on density functional theory. The relaxation is much large for the (001), (100), (101) and (112) surfaces. Moreover, more surface states appear at the bottom of conduction band and the top of valence band. The conduction band is mainly composed of S-3p and Sn-5p orbits. The valence band top is mainly composed of S-3p and Cu-3d orbits. The band gap values of five surfaces do not vary greatly. The dangling bond density for the (112) surfaces is minimal, resulting in minimum surface energy. Finally, the equilibrium morphology of CZTS is constructed by the Wulff rule. It is found that the {101} surface is the dominant surface (72.6%). These results will help us to better understand the surface properties of absorption layer that is related to CZTS surface and provide theoretical support for future experimental studies.