Song Bang-Jun, Ma Zuju, Li Bingxuan, Wu Xin-Tao, Lin Hua, Zhu Qi-Long
College of Chemistry, Fuzhou University, Fuzhou 350002, China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
Inorg Chem. 2021 Apr 5;60(7):4357-4361. doi: 10.1021/acs.inorgchem.1c00115. Epub 2021 Mar 12.
Diamond-like (DL) chalcophosphates, which possess the merits of impressive second-harmonic-generation (SHG) responses, strong laser-induced damage thresholds, and low melting points, are highly desirable for IR nonlinear-optical (NLO) applications. Herein, a new quaternary DL chalcophosphate, CuZnPS, is successfully discovered, taking known CuPS as the template via a single-site aliovalent-substitution strategy. It crystallizes in the orthorhombic system with noncentrosymmetric space group 2, and the 3D DL structure is built by corner-shared [(Cu/Zn)S], [CuS], and [PS] tetrahedra. Compared with its parent CuPS, CuZnPS exhibits a good phase-matching capability and a sharply enhanced SHG effect (10CuPS) benefiting from partial Zn substitution. Moreover, the structure-performance relationships have been illustrated by means of theoretical investigations. Such an aliovalent-substitution strategy based on known DL semiconductors might be widely applied for the discovery of high-performance IR NLO crystals.
类金刚石（DL）硫代磷酸酯具有令人印象深刻的二次谐波产生（SHG）响应、高激光损伤阈值和低熔点等优点，是红外非线性光学（NLO）应用中非常理想的材料。在此，通过单位点异价取代策略，以已知的CuPS为模板，成功发现了一种新型的四元DL硫代磷酸酯CuZnPS。它结晶于正交晶系，具有非中心对称空间群2，其三维DL结构由角共享的[(Cu/Zn)S]、[CuS]和[PS]四面体构建而成。与母体CuPS相比，由于部分Zn取代，CuZnPS表现出良好的相位匹配能力和显著增强的SHG效应（是CuPS的10倍）。此外，通过理论研究阐明了结构-性能关系。这种基于已知DL半导体的异价取代策略可能会广泛应用于高性能红外NLO晶体的发现。
