Photoluminescence Study of the Photoinduced Phase Separation in Mixed-Halide Hybrid Perovskite CH 3 NH 3 Pb(Br x I 1?x ) 3 Crystals Synthesized via a Solvothermal Method

摘要

We systematically synthesized mixed-halide hybrid perovskite CH3NH3Pb(BrxI1?x)3 (0?≤?x?≤?1) crystals in the full composition range by a solvothermal method. The as-synthesized crystals retained cuboid shapes, and the crystalline structure transitioned from the tetragonal phase to the cubic phase with an increasing Br-ion content. The photoluminescence (PL) of CH3NH3Pb(BrxI1?x)3 crystals exhibited a continuous variation from red (768?nm) to green (549?nm) with increasing the volume ratio of HBr (VHBr%), corresponding to a variation in the bandgap from 1.61?eV to 2.26?eV. Moreover, the bandgap of the crystals changed nonlinearly as a quadratic function of x with a bowing parameter of 0.53?eV. Notably, the CH3NH3Pb(BrxI1?x)3 (0.4?≤?x?≤?0.6) crystals exhibited obvious phase separation by prolonged illumination. The cause for the phase separation was attributed to the formation of small clusters enriched in lower-band-gap, iodide-rich and higher-band-gap, bromide-rich domains, which induced localized strain to promote halide phase separation. We also clarified the relationship between the PL features and the band structures of the crystals.