Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework

• Published in: Inorganic chemistry 2018-08, Vol.57 (15), p.8730-8734
• Main Authors: Li, Meng-Yue, Li, Bing-Xuan, Lin, Hua, Shi, Yong-Fang, Ma, Zuju, Wu, Li-Ming, Wu, Xin-Tao, Zhu, Qi-Long
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.8b01682

Noncentrosymmetric (NCS) mixed-metal chalcogenides have attracted significant attention lately because of their structural multiplicities, strong second-harmonic-generation (SHG) efficiencies (d ij ) and large laser-induced damage thresholds (LIDTs), which make them promising nonlinear-optical (NLO) materials in mid- and far-IR (MFIR) applications. In this work, a ternary mixed-metal material, Cd4GeS6, has been synthesized by reacting CdS with GeS2 via a solid-state method at 1273 K. It exhibits a unique tetrahedral-stacking NCS framework structure consisting of two types of [Cd2S7] asymmetric groups and dispersed GeS4 tetrahedra. Remarkably, Cd4GeS6 shows type-I phase-matching ability and achieves a desired balance between strong d ij (about 1.1AgGaS2) and large LIDT (about 3.6AgGaS2), demonstrating that this material satisfies the essential requirements as a promising MFIR NLO candidate. Moreover, theoretical calculations were performed for a better understanding of the structure–property relationships.