Structural Transformation and Photoluminescent Property of Manganese-Doped Bismuth-Based Perovskites.

Here, we synthesized pure CsBiCl (CBC) and manganese (Mn)-doped crystals with different feeding ratios, leading to changes in structure and luminescence. The crystals CsBiCl-Mn (CBCM) formed by doping a minor amount of Mn (Bi/Mn = 8:1) maintain the orthorhombic phase structure of the host, but when Bi/Mn = 2:1, the crystal structure is more inclined to form CsMnBiCl (CMBC) of a trigonal phase. Combined with density functional theory (DFT) calculation, the results demonstrate that a moderate amount of Mn doping can create impurity energy levels in the forbidden band. However, as the structure transitions, the type of energy band structure changes from indirect to direct, with completely different electronic orbital features. Temperature-dependent time-resolved and steady-state photoluminescence spectroscopies are used to explore the structure-related thermal properties and transitional process. Differences energy transfer routes are revealed, with CBCM relying on intersystem energy transfer and CMBC mainly depending on direct excitation of Mn to produce d-d transitions. Furthermore, since CMBC is temperature-sensitive, we perform the first photoluminescent (PL) lifetime temperature measurement using CBMC and obtain a maximum relative sensitivity of 1.7 %K and an absolute sensitivity of 0.0099 K. Our work provides insight into the mechanism of Mn doping-induced luminescence and offers a potentially effective doping strategy for improving the PL properties of lead-free metal halide perovskites.