通过聚阳离子取代策略实现压缩黄铜矿型硒化物[Rb3BaCl][In8Se14]以获得优异的非线性光学性能

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中文摘要：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[Se4Zn13]Se24→[ClRb3Ba]Se24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[Rb3BaCl][In8Se14](1).化合物1属于压缩黄铜矿型硒化物并保持了与AgInSe2相同的晶体对称性(I-42d空间群).值得注意的是,由于InSe4四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AgGaS2@2.90 µm).此外,聚阳离子[Rb3BaCl]4+的引入促进了光学带隙(2.02 eV)的增强,有效地避免了对2.09 μm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@2.09 μm).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.

外文标题：[Rb3BaCl][In8Se14]:Compressed chalcopyrite-type selenide achieved by polycationic substitution strategy toward excellent nonlinear optical property

外文摘要：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[Se4Zn13]Se24 →[ClRb3Ba]Se24,to design and synthesize a novel salt-inclusion chalcogenide,denoted as[Rb3BaCl][In8Se14](1).Compound 1 shares similarity with AgInSe2,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-GaS2@2.90 μm)owing to the parallel arrangement of tetra-hedral InSe4 units.Moreover,the incorporation of the polycation[Rb3BaCl]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-GaS2@2.09 μm).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.

外文关键词：

chalcogenidenonlinear optical materialsubstitution strategydiamond-like structurestructure-property relationship

作者：

吴帆、陈文发、吴子璇、姜小明、刘彬文、郭国聪

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作者单位：

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 College,University of Chinese Academy of Sciences,Fuzhou 350002,China

University of Chinese Academy of Sciences,Beijing 100049,China

Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China,Fuzhou 350108,China

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关键词：

chalcogenide nonlinear optical material substitution strategy diamond-like structure structure-property relationship

基金：

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaYouth Innovation Promotion Association of Chinese Academy of SciencesYouth Innovation Promotion Association of Chinese Academy of SciencesFujian Science & Technology Innovation Laboratory for Optoelectronic Information

项目编号：

21921001U21A20508921611252207528321827813202130020203032020ZZ108

出版年：

2024

DOI：

10.1007/s40843-024-2908-6

中国科学:材料科学(英文)

CSTPCD

ISSN：

年,卷(期)：2024.67(6)