The centrosymmetric to non-centrosymmetric transformation induced by alkaline-earth cations producing infrared nonlinear optical AeMn_(6)Ga_(6)S_(16)(Ae=Ca,Sr)  

作　　者：Yang-Ping Zhang Shao-Min Pei Wen-Fa Chen Bin-Wen Liu Xiao-Ming Jiang Guo-Cong Guo 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China [3]School of Physical Science and Technology,Shanghai Tech University,Shanghai 201210,China

出　　处：《Science China Chemistry》2024年第9期2941-2948,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21827813,21921001,22175172,22075283,92161125,U21A20508);the Youth Innovation Promotion Association of Chinese Academy of Sciences(2020303,2021300);Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ108)。

摘　　要：Non-centrosymmetric(NCS)structure is an indispensable prerequisite for second-order nonlinear optical(NLO)material.Currently,the mainstream approach for designing new NCS structures still relies on chemical substitution,necessitating an urgent infusion of fresh ideas.In this work,two isomorphic sulfides AeMn_(6)Ga_(6)S_(16)(Ae=Ca,1;Sr,2)are afforded by modifying the skeleton of centrosymmetric(CS)Mn_(2)Ga_(2)S_(5) via introducing strong electropositive alkaline-earth cations.Concretely,the incorporation of Ca^(2+)/Sr^(2+)cations allows the elementary[MnGaS_(9)]_(∞)chains to reconfigure into bumpy[MnS_(6)]-[GaS_(4)]layers in a new engagement manner,thus enabling the conversion from CS to NCS structure.Such modifications cause not only strong second-harmonic generation(SHG)responses(~1.5×benchmark AgGaS_(2)@1,700 nm),but also significantly feasible bandgaps(2.60-2.64 e V)compared to the sulfide Mn_(2)Ga_(2)S_(5)(1.36 e V),which ultimately facilitate ultrahigh laser-induced damage thresholds(4.4-6.6×AgGaS_(2)@1,064 nm for compounds 1 and 2).The present study offers an ingenious approach for the transformation of CS to NCS structure.

关 键 词：second-harmonic generation non-centrosymmetrical structure NLO functional motif solid-state method 

分 类 号：TB34[一般工业技术—材料科学与工程]