Anomalous Alloy Properties in Mixed Halide Perovskites.

Engineering halide perovskite through mixing halogen elements, such as CH3NH3PbI3-xClx and CH3NH3PbI3-xBrx, is a viable way to tune its electronic and optical properties. Despite many emerging experiments on mixed halide perovskites, the basic electronic and structural properties of the alloys have not been understood and some crucial questions remain, for example, how much Cl can be incorporated into CH3NH3PbI3 is still unclear. In this Letter, we chose CsPbX3 (X = I, Br, Cl) as an example and use a first-principle calculation together with cluster-expansion methods to systematically study the structural, electronic, and optical properties of mixed halide perovskites and find that unlike conventional semiconductor alloys, they exhibit many anomalous alloy properties such as small or even negative formation energies at some concentrations and negligible or even negative band gap bowing parameters at high temperature. We further show that mixed-(I,Cl) perovskite is hard to form at temperature below 625 K, whereas forming mixed-(Br,Cl) and (I,Br) alloys are easy at room temperature.