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We systematically synthesized mixed-halide hybrid perovskite CH 3 NH 3 Pb(Br x I 1−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 CH 3 NH 3 Pb(Br x I 1−x ) 3  crystals exhibited a continuous variation from red (768 nm) to green (549 nm) with increasing the volume ratio of HBr (V HBr %), 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 CH 3 NH 3 Pb(Br x I 1−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.

scientific reports

Photoluminescence Study of the Photoinduced Phase Separation in Mixed-Halide Hybrid Perovskite CH3NH3Pb(BrxI1−x)3 Crystals Synthesized via a Solvothermal Method