结晶学
四面体
非线性光学
二次谐波产生
材料科学
镧系元素
化学
离子
物理
非线性系统
光学
激光器
有机化学
量子力学
作者
Jingjing Xu,Xiaobing Yan,Kui Wu,Bingbing Zhang,Dazhi Lu,Haohai Yu,Huaijin Zhang
出处
期刊:Small
[Wiley]
日期:2023-10-24
被引量:1
标识
DOI:10.1002/smll.202306577
摘要
Structural dissymmetry and strong second-harmonic generation (SHG) responses are key conditions for nonlinear optical (NLO) crystals, and targeted combinatorial screening of suitable anionic groups has become extremely effective. Herein, optimal combination of flexible SnSn (n = 5, 6) groups and highly electropositive cations (lanthanides (Ln3+ ) and alkaline earth (Ae2+ : Sr, Ca) metals) affords the successful synthesis of 12 NLO thiostannates including Ln2 Sr3 Sn3 S12 (Pmc21 ) and Ln2 Ca3 Sn3 S12 (P-62m); whereas 17 rigid GeS4 or SiS4 tetrahedra-constructed Ln2 Ae3 Ge3 S12 and Ln2 Ae3 Si3 S12 crystallize in the centrosymmetric (CS) Pnma. This unprecedented CS to noncentrosymmetric (NCS) structural transformation (Pnma to P-62m to Pmc21 ) in the Ln2 Ae3 MIV3 S12 family indicates that chemical substitution of the tetrahedral GeS4 /SiS4 units with SnSn breaks the original symmetry to form the requisite NCS structures. Remarkably, strong polarization anisotropy and hyperpolarizability of the Sn(4+) S5 unit afford huge performance improvement from the nonphase-matching (NPM) SHG response (1.4 × AgGaS2 and Δn = 0.008) of La2 Ca3 Sn3 S12 to the strong phase-matching (PM) SHG effect (3.0 × AgGaS2 and Δn = 0.086) of La2 Sr3 Sn3 S12 . Therefore, Sn(4+) S5 is proven to be a promising "NLO-active unit." This study verifies that the coupling of flexible SnSn building blocks into structures opens a feasible path for designing targeted NCS crystals with strong nonlinearity and optical anisotropy.
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