Surface energy and surface stability of cesium tin halide perovskites: a theoretical investigation.

Abstract

Lead halide perovskites have been widely studied in the fields of photovoltaics and optoelectronics for over a decade. The toxicity of lead poses a big challenge to the potential applications of the materials. In recent years, lead-free halide perovskites have received significant attention due to their excellent optoelectronic properties and environment-friendly character. Tin halide perovskites have emerged as one of the most promising candidates for lead-free optoelectronic materials. It is of fundamental importance to understand the surface properties of tin halide perovskites that remain largely unknown. Using the density functional theory (DFT) method, we explore the surface energy and surface stability of low-index surfaces of cubic CsSnX3 (X = Cl, Br, I), i.e., (100), (110), and (111) surfaces. We calculate the stability phase diagrams of these surfaces and find that the (100) surface is more stable than the (110) and (111) surfaces. Interestingly, Br2-terminated (110) and CsBr3-terminated (111) polar surfaces are relatively more stable in CsSnBr3 than those in CsPbBr3 due to a higher level of valence band maximum and thus lesser energy cost in removing electrons to compensate for the polarity of the former. We calculate the surface energies of CsSnX3 surfaces that are difficult to access from experiments. The surface energies are very low in comparison with that of oxide perovskites. The origin of this lies in the relatively low binding strength of halide perovskites because of the soft nature of their structures. Furthermore, the connection between exfoliation energy and the cleavage energy in CsSnX3 is discussed.