Phase Stability and Electronic Structure of Prospective Sb-Based Mixed Sulfide and Iodide 3D Perovskite (CH3NH3)SbSI2.

Lead-free antimony-based mixed sulfide and iodide perovskite phases have recently been reported to be synthesized experimentally and to exhibit reasonable photovoltaic performance. Through a combination of experimental validation and computational analysis, we show no evidence of the formation of the mixed sulfide and iodide perovskite phase, MASbSI2 (MA = CH3NH3+), and instead that the main products are a mixture of the binary and ternary compounds (Sb2S3 and MA3Sb2I9). Density functional theory calculations also indicate that such a mixed sulfide and iodide perovskite phase should be thermodynamically less stable compared with binary/ternary anion-segregated secondary phases and less likely to be synthesized under equilibrium conditions. Additionally, band structure calculations show that this mixed sulfide and iodide phase, if possible to synthesize (e.g., under nonequilibrium conditions), should have a suitable direct band gap for photovoltaic application.