Abstract
Tin halide perovskites make up the only lead-free material class endowed with optoelectronic properties comparable to those of lead iodide perovskites. Despite significant progress, the device efficiency and stability of tin halide perovskites are still limited by two potentially related phenomena, i.e., self-p-doping and tin oxidation. Both CB processes are likely related to defects; thus, understanding tin halide defect chemistry is a key step toward exploitation of this class of materials. We investigate the MASnI(3) perovskite defect chemistry, as a prototype of the entire materials class, using state-of-the-art density functional theory simulations. We show that the inherently low ionization potential of MASnI(3) is solely responsible of the high stability of tin vacancy and interstitial iodine defects, which are in turn at the origin of the material p-doping. Tin vacancies create a locally iodine-rich environment that could promote Sn(II) -> Sn(IV) oxidation. The higher band edge energies of MASnI(3) compared to those of MAPbI(3) lead to the emergence of deep electron traps associated with undercoordinated tin defects (e.g., interstitial tin) and the suppression of deep transitions associated with undercoordinated iodine defects that are typical of MAPbI(3). Thus, while lead iodide perovskites are dominated by iodine chemistry, tin chemistry dominates tin iodide perovskite defect chemistry. Mixed tin/lead perovskites exhibit an intermediate behavior and are predicted to be potentially free of deep traps. Compositional alloying with different metals is finally explored as a strategy for mitigating defect formation and self-p-doping in tin iodide perovskites.