Redox Chemistry of the Subphases of -CsPbI₂Br and -CsPbI₂Br: Theory Reveals New Potential for Photostability

The logic in the design of a halide-mixed APb(I1-xBrx)(3) perovskite is quite straightforward: to combine the superior photovoltaic qualities of iodine-based perovskites with the increased stability of bromine-based perovskites. However, even small amounts of Br doped into the iodine-based materials leads to some instability. In the present report, using first-principles computations, we analyzed a wide variety of alpha-CsPbI2Br and beta-CsPbI2Br phases, compared their mixing enthalpies, explored their oxidative properties, and calculated their hole-coupled and hole-free charged Frenkel defect (CFD) formations by considering all possible channels of oxidation. Nanoinclusions of bromine-rich phases in alpha-CsPbI2Br were shown to destabilize the material by inducing lattice strain, making it more susceptible to oxidation. The uniformly mixed phase of alpha-CsPbI2Br was shown to be highly susceptible towards a phase transformation into beta-CsPbI2Br when halide interstitial or halide vacancy defects were introduced into the lattice. The rotation of PbI4Br2 octahedra in alpha-CsPbI2Br allows it either to transform into a highly unstable apical beta-CsPbI2Br, which may phase-segregate and is susceptible to CFD, or to phase-transform into equatorial beta-CsPbI2Br, which is resilient against the deleterious effects of hole oxidation (energies of oxidation >0 eV) and demixing (energy of mixing <0 eV). Thus, the selective preparation of equatorial beta-CsPbI2Br offers an opportunity to obtain a mixed perovskite material with enhanced photostability and an intermediate bandgap between its constituent perovskites.