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

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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Abstract

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 crystals 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 possesses a compressed chalcopyrite-type selenide structure. Remarkably, compound 1 displays remarkable phase-matching second-harmonic generation (SHG) intensity (2.0 × AgGaS2@2.90 µm) owing to the parallel arrangement of tetrahedral 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 × AgGaS2@2.09 µm). This study establishes the potential of polycationic substitution within diamond-like structures for the rational design of exceptional mid- and far-infrared NLO materials.

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.

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Acknowledgements

This work was 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), and Fujian Science & Technology Innovation Laboratory for Optoelectronic Information (2020ZZ108).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Fan Wu  (吴帆), Wen-Fa Chen  (陈文发), Zi-Xuan Wu  (吴子璇), Xiao-Ming Jiang  (姜小明), Bin-Wen Liu  (刘彬文) & Guo-Cong Guo  (郭国聪)

  2. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China

    Fan Wu  (吴帆)

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

    Xiao-Ming Jiang  (姜小明) & Guo-Cong Guo  (郭国聪)

  4. University of Chinese Academy of Sciences, Beijing, 100049, China

    Wen-Fa Chen  (陈文发) & Zi-Xuan Wu  (吴子璇)

  5. Fujian College, University of Chinese Academy of Sciences, Fuzhou, 350002, China

    Fan Wu  (吴帆)

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  1. Fan Wu  (吴帆)
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Contributions

Author contributions Wu F performed the experiments, data analyses and manuscript writing. Chen WF and Jiang XM performed the theoretical analyses. Wu ZX offered some advice on the manuscript writing. Liu BW and Guo GC guided and supervised the experiments, and revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Bin-Wen Liu  (刘彬文) or Guo-Cong Guo  (郭国聪).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Experimental details and supporting data are available in the online version of the paper.

Fan Wu received his BE degree in applied chemistry from Gannan Normal University in 2021. Currently, he is pursuing his Master’s degree at Fujian Normal University, specializing in the field of NLO materials.

Bin-Wen Liu earned his BE degree from Hunan University in 2010 and PhD degree in inorganic chemistry from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 2016. Since 2019, he has been serving as a professor at Fujian Institute of Research on the Structure of Matter. His current research focuses on solid-state inorganic chemistry and NLO materials.

Guo-Cong Guo obtained his BS degree from Xiamen University in 1986 and PhD degree from The Chinese University of Hong Kong in 1999. Since 2000, he has been serving as a full professor at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. His current research focuses on inorganic-organic hybrid photo functional materials, infrared NLO materials, electronic structure crystallography, and catalytic materials.

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Supporting Information: [Rb3BaCl][In8Se14]: Compressed Chalcopyrite-type Selenide Achieved by Polycationic Substitution Strategy toward Excellent Nonlinear Optical Property

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Wu, F., Chen, WF., Wu, ZX. et al. [Rb3BaCl][In8Se14]: Compressed chalcopyrite-type selenide achieved by polycationic substitution strategy toward excellent nonlinear optical property. Sci. China Mater. (2024). https://doi.org/10.1007/s40843-024-2908-6

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