Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys

Abstract

Goldschmidt tolerance factor (t) is an empirical index for predicting stable crystal structures of perovskite materials. A t value between 0.8 and 1.0 is favorable for cubic perovskite structure, and larger (>1) or smaller (<0.8) values of tolerance factor usually result in nonperovskite structures. CH(NH2)2PbI3 (FAPbI3) can exist in the perovskite α-phase (black phase) with good photovoltaic properties. However, it has a large tolerance factor and is more stable in the hexagonal δH-phase (yellow phase), with δH-to-α phase-transition temperature higher than room temperature. On the other hand, CsPbI3 is stabilized to an orthorhombic structure (δO-phase) at room temperature due to its small tolerance factor. We find that, by alloying FAPbI3 with CsPbI3, the effective tolerance factor can be tuned, and the stability of the photoactive α-phase of the mixed solid-state perovskite alloys FA1–xCsxPbI3 is enhanced, which is in agreement with our first-principles calculations. Thin films of the FA0.85Cs0.15PbI3 p...