First principles study of 2D layered organohalide tin perovskites.

This article describes the structure and the electronic properties of a series of layered perovskites of a general formula (A)(SnX) where X = I, Br and A is an organic cation, either formamidinium, 1-methylimidazolium, or phenylethylammonium. For each system, two conformations are considered, with eclipsed or staggered stacking of the adjacent inorganic layers. Geometry optimizations are performed at the density functional theory level with generalized gradient approximation (GGA) functional and semiempirical correction for dispersion energies; band profiles and bandgaps are computed including both spin orbit coupling (SOC) and correlation (GW) effects through an additive scheme. The theoretical procedures are validated by reproducing the experimental data of a well known 3D tin iodide perovskite. The results, combined with the calculations previously reported on PbI analogues, allow us to discuss the effect of cation, metal, and halide substitution in these systems and in particular to explore the possibility of changing the electronic bandgap as required by different applications. The balance of SOC and GW effects depends on the chemical nature of the studied perovskites and strongly influences the value of the simulated bandgap.