等结构
红外线的
非线性光学
钻石
带隙
四面体
结晶学
二次谐波产生
材料科学
价(化学)
晶体结构
化学
非线性系统
光电子学
光学
激光器
物理
有机化学
量子力学
作者
Xiaoyu Lou,Yu Zhou,Wen‐Fa Chen,Xiao‐Ming Jiang,Bin‐Wen Liu,Guo‐Cong Guo
出处
期刊:Dalton Transactions
[The Royal Society of Chemistry]
日期:2023-01-01
卷期号:52 (15): 4873-4879
被引量:4
摘要
A crystal structure with a diamond-like anionic framework belongs to a non-centrosymmetric macrostructure due to the aligned arrangement of tetrahedral units, meeting the premise of second-order nonlinear optical (NLO) materials. Herein, two new Hg-based sulphides, namely RbHg4Ga5S12 (1) and CsHg4Ga5S12 (2), which are isostructural and crystallise in the trigonal space group R3, are successfully isolated in sealed silica tubes by a solid-state reaction. The features of their three-dimensional open honeycomb frameworks are attributed to the parallel alignment of tetrahedral MS4 (M is disordered by 0.444 Hg and 0.555 Ga) building motifs, accompanied by Rb+ (or Cs+) reseating in the cavities. Notably, although the band gap values of 1 and 2 are 2.30 and 2.36 eV, separately, their thermal expansion anisotropies (0.15 and 0.41, respectively) are favourable for achieving laser-induced damage thresholds (5.6 and 5.8 times that of AgGaS2 for 1 and 2, respectively). In addition, the strong polarisability of tetrahedral MS4 building motifs in the diamond-like anionic structures is responsible for the promising second-harmonic generation (SHG) intensities (1.1 and 1.8 times that of AgGaS2 for 1 and 2, respectively) in the particle size range of 50-75 μm with non-phase-matchable behaviour at 1910 nm. Furthermore, theoretical investigation elaborates that electron transitions in compounds 1 and 2 mainly occur from valence band S-3p to conduction band Hg-6s and Ga-4s states, demonstrating that the linear and nonlinear optical properties originate primarily from the synergy of tetrahedral MS4 units.
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