Effects of size mismatch of halide ions on the phase stability of mixed halide perovskites

The phase stability of mixed halide perovskites plays a vital role in the performance and reliability of perovskite-based devices and systems. In this work, we incorporate the contribution of the strain energy due to the size mismatch of halideions in Gibbs free energy for the analysis of the phase stability of mixed halide perovskites. Analytical expressions of the chemical potentials of halide ions in mixed halide perovskites are derived and used to determine the critical atomic fractions of halide ions for the presence of spinodal decomposition (phase instability). The numerical analysis of CH₃NH₃PbI_x Br_3-x mixed halide perovskite reveals the important role of the mismatch strain from halide ions in controlling the phase instability of mixed halide perovskite, i.e., increasing the mismatch strain widens the range of x for the phase separation of mixed halide perovskites. To mitigate the phase instability associated with the strain energy from intrinsic size mismatch and/or light-induced expansion, strain and/or field engineering, such as high pressure, can be likely applied to introduce strain and/or field gradient to counterbalance the strain gradient by the mismatch strain and/or light-induced expansion.