Zhao Chen-Yi, Yao Wen-Dong, Li Ming-Yang, Zhou Wenfeng, Liu Wenlong, Guo Sheng-Ping
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P. R. China.
Yunnan Key Laboratory of Electromagnetic Materials and Devices, National Center for International Research on Photoelectric and Energy Materials, School of Materials and Energy, Yunnan University, Kunming 650091, P. R. China.
Inorg Chem. 2024 Mar 4;63(9):4017-4021. doi: 10.1021/acs.inorgchem.4c00131. Epub 2024 Feb 17.
As one of the potential candidates of nonlinear-optical (NLO) materials, rare-earth chalcophosphates have demonstrated promising properties. Here, KREPS (RE = Sm, Gd, Tb, Dy) were synthesized using the facile REO-B-S solid-state method. They crystallize with a monoclinic chiral 2 structure, and their layer structures are built by isolated ethane-like PS dimers and RES bicapped trigonal prisms built {[RES]} layers. By comparing the structures with related ones, the change of the alkali metal or RE ions can cause structural transformation. Their band gaps are tunable between 2.58 and 3.79 eV, and their powder samples exhibit good NLO properties. Theoretical calculations suggest that the NLO properties are mainly contributed by PS units and {[RES]} layers synergistically, in which {[RES]} layers and PS units dominate the contribution to the band gap and second-harmonic-generation response, respectively. This work enriches the application of rare-earth chalcophosphates as NLO materials.
作为非线性光学（NLO）材料的潜在候选材料之一，稀土硫代磷酸盐已展现出有前景的性能。在此，采用简便的REO - B - S固态法合成了KREPS（RE = Sm、Gd、Tb、Dy）。它们以单斜手性2结构结晶，其层状结构由孤立的类乙烷PS二聚体和RES双帽三角棱柱构建而成{[RES]}层。通过将这些结构与相关结构进行比较，碱金属或稀土离子的变化会导致结构转变。它们的带隙在2.58至3.79 eV之间可调，并且其粉末样品表现出良好的NLO性能。理论计算表明，NLO性能主要由PS单元和{[RES]}层协同贡献，其中{[RES]}层和PS单元分别主导对带隙和二次谐波产生响应的贡献。这项工作丰富了稀土硫代磷酸盐作为NLO材料的应用。
