Mixed halide perovskites that are thermodynamically stable in the dark demix under illumination. This is problematic for their application in solar cells. We present a unified thermodynamic theory for this light-induced halide segregation that is based on a free energy lowering of photocarriers funnelling to a nucleated phase with different halide composition and lower band gap than the parent phase. We apply the theory to a sequence of mixed iodine-bromine perovskites. The spinodals separating metastable and unstable regions in the composition-temperature phase diagrams only slightly change under illumination, while light-induced binodals separating stable and metastable regions appear signalling the nucleation of a low-band gap iodine-rich phase. We find that the threshold photocarrier density for halide segregation is governed by the band gap difference of the parent and iodine-rich phase. Partial replacement of organic cations by cesium reduces this difference and therefore has a stabilizing effect.

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Light-induced halide segregation hampers obtaining stable wide-band-gap solar cells based on mixed iodide–bromide perovskites. So far, the effect of prolonged illumination on the performance of mixed-halide perovskite solar cells has not been studied in detail. It is often assumed that halide segregation leads to a loss of open-circuit voltage. By simultaneously recording changes in photoluminescence and solar cell performance under prolonged illumination, we demonstrate that cells instead deteriorate by a loss of short-circuit current density and that the open-circuit voltage is less affected. The concurrent red shift, increased lifetime, and higher quantum yield of photoluminescence point to the formation of relatively emissive iodide-rich domains under illumination. Kinetic Monte Carlo simulations provide an atomistic insight into their formation via exchange of bromide and iodide, mediated by halide vacancies. Localization of photogenerated charge carriers in low-energy iodide-rich domains and subsequent recombination cause reduced photocurrent and red-shifted photoluminescence. The loss in photovoltaic performance is diminished by partially replacing organic cations by cesium ions. Ultrasensitive photocurrent spectroscopy shows that cesium ions result in a lower density of sub-band-gap defects and suppress defect growth under illumination. These defects are expected to play a role in the development and recovery of light-induced compositional changes.

Photoinduced halide segregation hinders widespread application of three-dimensional (3D) mixed-halide perovskites. Much less is known about this phenomenon in lower-dimensional systems.Here, we study photoinduced halide segregation in lower-dimensional mixed iodide-bromide perovskites (PEA 2 MA n−1 Pb n (Br x I 1−x ) 3n+1 , with PEA + : phenethylammonium and MA + : methylammonium) through time-dependent photoluminescence (PL) spectroscopy. We show that layered two-dimensional (2D) structures render additional stability against the demixing of halide phases under illumination. We ascribe this behavior to reduced halide mobility due to the intrinsic heterogeneity of 2D mixed-halide perovskites, which we demonstrate via 207 Pb solid-state NMR. However, the dimensionality of the 2D phase is critical in regulating photostability. By tracking the PL of multidimensional perovskite films under illumination, we find that while halide segregation is largely inhibited in 2D perovskites (n = 1), it is not suppressed in quasi-2D phases (n = 2), which display a behavior intermediate between 2D and 3D and a peculiar absence of halide redistribution in the dark that is only induced at higher temperature for the quasi-2D phase.