Organic Cations Protect Methylammonium Lead Iodide Perovskites against Small Exciton-Polaron Formation

Working organic-inorganic lead halide perovskite-based devices are notoriously sensitive to surface and interface effects. Using a combination of density functional theory (DFT) and time-dependent DFT methods, we report a comprehensive study of the changes (with respect to the bulk) in geometric and electronic structures going on at the (001) surface of a (tetragonal phase) methylammonium lead iodide perovskite slab, in the dark and upon photoexcitation. The formation of a hydrogen bonding pattern between the -NH3 groups of the organic cations and the iodine atoms of the outer inorganic layout is found to critically contribute to the relative thermodynamic stability of slabs with varying surface compositions and terminations. Most importantly, our results show that the hydrogen bond locking effects induced by the MA groups tend to protect the external two-dimensional lattice against large local structural deformations, i.e., the formation of a small exciton-polaron, at variance with purely inorganic lead halide perovskites.