Roles of SnX (X = F, Cl, Br) Additives in Tin-Based Halide Perovskites toward Highly Efficient and Stable Lead-Free Perovskite Solar Cells.

Preserving the stability of Sn-based halide perovskites is a primary concern in developing photovoltaic light-absorbing materials for lead-free perovskite solar cells. Whereas the addition of SnX (X = F, Cl, Br) has been demonstrated to improve the photovoltaic performance of Sn halide perovskite solar cells, the mechanistic roles of SnX in the performance enhancement have not yet been studied appropriately. Here we perform a comparative study of CsSnI films and devices and examine how SnX additives affect their stability, and the results are corroborated by first-principles-based theoretical calculations. Unlike the conventional belief that the additives annihilate defects, we find that the additives effectively passivate the surface and stabilize the perovskite phase, promoting the stability of CsSnI. Our mechanism suggests that SnBr, which shows ca. 100 h of prolonged stability along with a high power conversion efficiency of 4.3%, is the best additive for enhancing the stability of CsSnI.