通过聚阳离子取代策略实现压缩黄铜矿型硒化物[Rb3BaCl][In_(8)Se_(14)]以获得优异的非线性光学性能  

[Rb_(3)BaCl][In_(8)Se_(14)]:Compressed chalcopyrite-type selenide achieved by polycationic substitution strategy toward excellent nonlinear optical property

作　　者：吴帆 陈文发 吴子璇 姜小明 刘彬文 郭国聪 Fan Wu;Wen-Fa Chen;Zi-Xuan Wu;Xiao-Ming Jiang;Bin-Wen Liu;Guo-Cong Guo(State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China;Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China;University of Chinese Academy of Sciences,Beijing 100049,China;Fujian College,University of Chinese Academy of Sciences,Fuzhou 350002,China)

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]College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China [3]Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China [4]University of Chinese Academy of Sciences,Beijing 100049,China [5]Fujian College,University of Chinese Academy of Sciences,Fuzhou 350002,China

出　　处：《Science China Materials》2024年第6期2000-2007,共8页中国科学（材料科学）（英文版）

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

摘　　要：单价Ag+或Li+引入到类金刚石结构的MQ22-(M=Ga,In;Q=S,Se)阴离子基团中能合成出良好的二阶非线性光学(NLO)晶体材料.然而,这些晶体分别面临着较低的抗激光损伤阈值(LIDT)或二氧化硅易被腐蚀等缺点,严重限制了其在高功率激光应用中的实用性.在本研究中,基于类金刚石结构的ZnSe,我们采用[Se_(4)Zn_(13)]Se_(2)4→[ClRb_(3)Ba]Se_(24)非常规的聚阳离子取代策略,设计并合成了一种新型的盐包硫属化合物[Rb_(3)BaCl][In_(8)Se_(14)](1).化合物1属于压缩黄铜矿型硒化物并保持了与AgInSe_(2)相同的晶体对称性(I-42d空间群).值得注意的是,由于InSe_(4)四面体结构单元的平行排列,化合物1具有相位匹配的强二次谐波(SHG)响应(2.0倍于AgGaS_(2)@2.90μm).此外,聚阳离子[Rb_(3)BaCl]^(4+)的引入促进了光学带隙(2.02 eV)的增强,有效地避免了对2.09μm激光的双光子吸收;同时结合较低的热膨胀系数,使得化合物1表现出高的LIDT(3.2倍于AgGaS2@2.09μm).本研究验证了在类金刚石结构中进行聚阳离子取代的可行性,并成功获得了性能优异的中远红外NLO材料.Incorporation of monovalent Ag+or Li+ions into the anionic groups MQ22-(M=Ga,In;Q=S,Se)within diamond-like structures holds great promise for the second-order nonlinear optical(NLO)crystals.However,these crys-tals are significantly challenged by a low laser-induced damage threshold(LIDT)or the drawbacks associated with silica tube corrosiveness,which severely limit their suitability for high-power applications.In this study,we employed the unusual polycationic substitution strategy based on ZnSe,specifically[Se_(4)Zn_(13)]Se_(24)→[ClRb_(3)Ba]Se_(24),to design and synthesize a novel salt-inclusion chalcogenide,denoted as[Rb_(3)BaCl][In_(8)Se_(14)](1).Compound 1 shares similarity with AgInSe_(2),as it maintains crystallographic symmetry in the space group I-42d and pos-sesses a compressed chalcopyrite-type selenide structure.Re-markably,compound 1 displays remarkable phase-matching second-harmonic generation(SHG)intensity(2.0×Ag-GaS_(2)@2.90μm)owing to the parallel arrangement of tetra-hedral InSe4 units.Moreover,the incorporation of the polycation[Rb_(3)BaCl]^(4+)that promotes the enhancement of the band gap(2.02 eV),avoiding two-photon absorption of 2.09-μm laser,combined with a low thermal expansion coefficient,enables compound 1 to exhibit a substantial LIDT(3.2×Ag-GaS_(2)@2.09μm).This study establishes the potential of poly-cationic substitution within diamond-like structures for the rational design of exceptional mid-and far-infrared NLO materials.

关 键 词：CHALCOGENIDE nonlinear optical material substitution strategy diamond-like structure structure-property relationship 

分 类 号：TB34[一般工业技术—材料科学与工程]