Entropy-Driven Stabilization of Multielement Halide Double-Perovskite Alloys

Abstract

Currently, a major obstacle restricting the commercial application of halide perovskites is their low thermodynamic stability. Herein, inspired by the high-stability high-entropy alloys, we theoretically investigated a variety of multielement double-perovskite alloys. First-principles calculations show that the entropy contribution to Gibbs free energy, which offsets the positive enthalpy contribution by up to 35 meV/f.u., can significantly enhance the material stability of double-perovskite alloys. We found that the electronic properties of bandgaps (1.04–2.21 eV) and carrier effective masses (0.34 to greater than 2 m0) of the multielement double-perovskite alloys can be tuned over a wide range. Meanwhile, the parity-forbidden condition of optical transitions in the Cs2AgInCl6 perovskite can be broken because of the lower symmetry of the configurational disorder, leading to enhanced transition intensity. This work demonstrates a promising strategy by utilizing the alloy entropic effect to further improve the material stability and optoelectronic performance of halide perovskites.