A-Site Effect on the Oxidation Process of Sn-Halide Perovskite: First-Principles Calculations

Tin-halide perovskite solar cells (Sn-PSCs) are promising candidates as an alternative to toxic lead-halide PSCs. However, Sn2+ is easily oxidized to Sn4+, so Sn-PSCs are unstable in air. Here, we use first-principles density functional theory calculations to elucidate the oxidation process of Sn2+ at the surface of ASnBr3 [A = Cs or CH3NH3 (MA)]. Regardless of the A-site cation, adsorption of O2 leads to the formation of SnO2, which creates a Sn vacancy at the surface. The A-site cation determines whether the created vacancies are stabilized in the bulk or at the surface. For CsSnBr3, the Sn vacancy is stabilized at the surface, so further oxidation is limited. For MASnBr3, the Sn vacancy moves into bulk region, so additional Sn is supplied to the surface; as a result, a continuous oxidation process can occur. The stabilization of Sn vacancy is closely related to the polarization that the A-site cation causes in the system.