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Zero-dimensional metal halides are of unique structures and tunable photoluminescence properties, showing great potential applications such as light-emitting diodes (LEDs) and sensing. Herein, we successfully synthesized Cu+ doped (MA)2ZnCl4 metal halides by a slow evaporation solvent method. The introduction of Cu+ results in sky-blue self-trapped exciton emission in (MA)2ZnCl4 at 486 nm at room temperature, and a photoluminescence quantum yield is as high as 54.9%. Interestingly, at low temperatures, Cu+-doped (MA)2ZnCl4 exhibits two emission peaks located at 482 and 605 nm, respectively. This temperature-dependent dual emission indicates two excited state structures that exist on the triplet excited-state potential energy surface. In addition, the temperature sensor we fitted has good performance (Sr = 1.65 %·K−1), which is the first attempt in Cu+ doped Zn-based metal halides. Our work enriches the family of sky-blue metal halides and provides a promising strategy for building sky-blue LEDs.

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