Tunable double emission of Sb3+/Mn2+ doping stabilized organic-inorganic hybrid zinc-based halides

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Low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have attracted much attention lately in contrast to all-inorganic metal halides because of their excellent photophysical properties and tunable emission wavelengths. Zn-based metal halides have the following advantages: simplicity of synthesis, wide bandgap, and excellent chemical stability. Therefore, they are well-suited as host materials for photoluminescence by cation ion doping. We have successfully synthesized intrinsically non-emissive 0D (PPZ)ZnCl4 [PPZ (1-phenylpiperazine) = C10H14N2], and by mono/co-doping with Mn2+ and Sb3+, interesting luminescence phenomena have been produced. Single-doped Mn2+ / Sb3+ shows distinctive green and single orange emission, respectively. However, the co-doped Mn2+ and Sb3+ appeared as dynamic double emission peaks at 530 nm and 670 nm. Therefore, the co-doped crystals showed luminescence from two different luminescence centers ([MnCl4]2- and [SbCl4]-). We used DFT to calculate the DOS (density of states) of co-doped crystals, which results in energy transfer between Mn2+ and Sb3+. All of the above samples showed high stability after being left for two months. In addition, two different luminescence centers can be produced by the adjustment of the excitation of the co-doped (PPZ)ZnCl4: Sb0.12Mn0.08 samples, which is a distinguishable and obvious photoluminescence phenomenon having great potential preparation of advanced anti-counterfeiting materials in the future.