Cations substitution tuning phase stability in hybrid perovskite single crystals by strain relaxation

Methylammonium (MA) and formamidinium (FA) are two typical A site cations in lead halide perovskites. Instability of synthesised crystals will degrade the properties of the photoelectrical device constructed by such perovskites. MAPbI₃ and FAPbI₃ in cubic crystal structure have been demonstrated to be the most stable at room temperature. Herein we synthesised MA(EA)PbI₃ and FA(MA)PbI₃ single crystals using an inverse-temperature crystallization strategy by partially substituting the methylammonium (MA) with ethylammonium (EA) and the formamidinium (FA) with methylammonium (MA) respectively. The XRD results show that both crystal structures are cubic, which means organic incorporation can stabilize the crystal structure of lead halide perovskites. The lattice distortion decrease and strain relaxation in single crystals were considered to be the reason leading to higher stability. The single crystals of MA(EA)PbI₃ and FA(MA)PbI₃ with low trap state density exhibit excellent light-absorbing properties, indicating their potential applications in photoelectric devices.