Huang Yexin, Pan Yuexiao, Guo Shiting, Peng Chengdong, Lian Hongzhou, Lin Jun
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. China.
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China.
Inorg Chem. 2022 May 30;61(21):8356-8365. doi: 10.1021/acs.inorgchem.2c00995. Epub 2022 May 18.
All-inorganic halide perovskite crystals are considered excellent optical host lattices for various dopants to obtain wavelength-tunable emissions with ultra-broad bands even over a wide spectral range. Here, a series of Mn-doped bulk ligand-free CsCdCl (CCC) perovskite crystals with a hexagonal shape and size of about 1 millimeter (mm) have been prepared by a facile hydrothermal method. These CCC:Mn (CCC:Mn) crystals emit the representative orange-red photoluminescence (PL) of Mn (T(G)-A(S)) in the centers of hexagonal octahedrons coordinated with six Cl ions. A fine-tuning of the Mn concentration from 1 to 50 mol % Cd induces a substantial red shift of emission spectra from 570 to 630 nm due to the shrinkage of the crystalline host lattice, and the maximum intensity of emission is achieved at 20 mol % Mn doping. A further increase in the Mn concentration causes a decrease of the PL intensity due to the phase transition from CCC to CsMnCl·2HO (CMCH). The strong excitation bands at 360, 370, 420, and 440 nm can make the excitation of the emissive CCC:Mn crystals possible with ultraviolet (UV) and blue chips for application in white light-emitting diodes (WLEDs). The similarity of the Mn-concentration-dependent emission spectra excited by various wavelengths indicates that there is only one type of site for Mn occupation in CCC.
全无机卤化物钙钛矿晶体被认为是用于各种掺杂剂的优异光学主体晶格，以便在很宽的光谱范围内获得具有超宽带的波长可调谐发射。在此，通过简便的水热法制备了一系列具有六边形形状且尺寸约为1毫米（mm）的无配体Mn掺杂块状CsCdCl（CCC）钙钛矿晶体。这些CCC:Mn（CCC:Mn）晶体在与六个Cl离子配位的六边形八面体中心发射Mn的代表性橙红色光致发光（PL）（T(G)-A(S)）。由于晶体主体晶格的收缩，将Mn浓度从1 mol% Cd微调至50 mol% Cd会导致发射光谱从570 nm大幅红移至630 nm，并且在Mn掺杂量为20 mol%时达到最大发射强度。Mn浓度的进一步增加会由于从CCC到CsMnCl·2HO（CMCH）的相变而导致PL强度降低。360、370、420和440 nm处的强激发带使得可以用紫外（UV）和蓝色芯片激发发光的CCC:Mn晶体，用于白光发光二极管（WLED）。由各种波长激发的Mn浓度依赖性发射光谱的相似性表明，在CCC中Mn占据的位点只有一种类型。
