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Improved Energy Transfer in Mn-Doped Cs3Cu2I5 Microcrystals Induced by Localized Lattice Distortion.

With nontoxicity and high emission efficiency, luminescent copper(I)-based halides have attracted much attention as alternatives for lead-based perovskites in photoelectric domains. However, extending the emission wavelength by doping with Mn2+ in a facile way is still a challenge. In this work, Mn2+-doped Cs3Cu2I5 microcrystals were synthesized by a mild solution method, and double emission bands from self-trapped excitons (STEs) and Mn2+ peaking at 445 and 560 nm, respectively, were observed. More importantly, further introduction of alkali metal ions (Rb+, K+, Na+) considerably promoted the luminescence performance of the Cs3Cu2I5-Mn microcrystals. The STE → Mn2+ energy transfer efficiency of the typical sample doped with Na+ increased from ∼0 to 21.30%, and the photoluminescence quantum yield (PLQY) increased from 47.32% to 62.06%. The detailed structural and optical characterizations combined with DFT calculations proved that the doping with alkali metal ions causes lattice distortion and enhances the coupling between [MnI4] and [CuI4] tetrahedra, thus promoting the energy transfer efficiency and the PLQY.