Electronic Structure and Optical Properties of Mixed Iodine/Bromine Lead Perovskites. To Mix or Not to Mix?

Abstract Halide mixing is a key strategy to tune the emission wavelength in lead halide perovskites but is also effective in improving the performance of halide perovskite solar cells. Yet, a clear and global picture of how halide alloying and related spatial in/homogeneous distribution influence the electronic and optical properties of halide perovskites is currently lacking. Considering the preeminent mixed iodine/bromine perovskite as a case study, state‐of‐the‐art hybrid density functional theory calculations are performed, exploring the full space of chemical composition and accounting for phase segregation effects. It is shown that, at low doping regime, halide impurities do not act as trap states and that a quasi‐linear opening of the bandgap occurs with increasing the bromine content. Phase segregation at the nanoscale, in turn, drastically affects the electronic structure of mixed halide systems, with namely bromine rich domains acting as barrier to hole diffusion. The energetic disorder probed by optical absorption in these mixed systems is surprisingly insensitive to configurational disorder, but mostly dominated by the coexistence of phases with various degrees of halide segregation.