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Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy

三元AGa5S8 (A = K, Rb, Cs): 通过“一替多取代”策略制备的红外非线性光学材料

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Abstract

Commercially available infrared (IR) nonlinear optical (NLO) materials, such as diamond-like AgGaQ2 (Q = S, Se), display large NLO coefficients but relatively low laser-induced damage thresholds (LIDTs), which seriously hinder their widespread laser applications. Herein, the “one-for-multiple substitution” strategy, namely, [SZn46+ + 5Zn2+ ⇒ A+ + 5Ga3+] (A = K, Rb and Cs), is applied on the diamond-like zinc-blende ZnS, and affords three new polar ternary crystals AGa5S8 (A = K, Rb and Cs) through the solid-state method. These compounds inherit the diamond-like anionic backbone framework in ZnS where the NLO functional motifs GaS4 are arranged in a parallel manner. This characteristic accounts for the remarkable phase-matchable second-harmonic generation intensities (1.1–1.2 × AgGaS2). In addition, the inclusion of the highly electropositive A+ cations affords a band gap ranging from 3.10 to 3.37 eV, which facilitates the improvement of LIDT (9.3–12.4 × AgGaS2). To the best our knowledge, crystals AGa5S8 (A = K, Rb and Cs) are the first series of ternary A-inclusion chalcogenides with large second-harmonic generation responses (≥1.0 × AgGaS2) and wide band gaps (≥3.0 eV), fulfilling the rigorous requirements of outstanding IR NLO materials. In addition, the “one-for-multiple substitution” strategy presents the great significance of diamondlike structure evolution and provides a remarkable opportunity to achieve NLO materials.

摘要

目前, 商用的红外非线性光学晶体材料, 如具有类金刚石结构的硫属化合物AgGaQ2 (Q = S, Se), 具有强的非线性光学系数. 然而, 相对较低的抗激光损伤阈值制约了其在高能激光领域的应用. 以类金刚石结构的闪锌矿ZnS为模板, 我们通过“一替多取代”策略, 即[SZn46+ + 5Zn2+ ⇒ A+ + 5Ga3+] (A = K、 Rb和Cs), 采用固相合成方法, 获得了三元晶体AGa5S8 (A = K、 Rb和Cs). 极性结构的AGa5S8保持了类金刚石阴离子骨架框架, 非线性光学功能基元GaS4四面体以平行排列的方式堆积, 使其具有高的相位匹配倍频强度(1.1–1.2 × AgGaS2); 另外, 含有高正电性A+阳离子使其表现出3.10–3.37 eV的宽带隙, 进而提高抗激光损伤阈值(9.3–12.4 × AgGaS2). 晶体AGa5S8 (A = K、 Rb和Cs)是第一个具有大倍频响应(≥1.0 × AgGaS2)和宽带隙(≥3.0 eV)的三元含碱金属的硫属化合物, 满足了优秀红外非线性光学材料的严格要求. 此外, “一替多取代”策略在类金刚石结构演变中具有重要意义, 并为获得新非线性光学材料提供了良好的机遇.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21827813, 21921001, 22175172, 22075283, and 92161125), the Youth Innovation Promotion Association of Chinese Academy of Sciences (2020303 and 2021300), and the Natural Science Foundation of Fujian Provinces, China (2020J01115).

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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

    Wen-Fa Chen  (陈文发), Xiao-Ming Jiang  (姜小明), Shao-Min Pei  (裴绍敏), Ming-Shu Zhang  (张铭枢), Bin-Wen Liu  (刘彬文) & Guo-Cong Guo  (郭国聪)

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

    Wen-Fa Chen  (陈文发), Shao-Min Pei  (裴绍敏) & Ming-Shu Zhang  (张铭枢)

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  1. Wen-Fa Chen  (陈文发)
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Contributions

Author contributions Chen WF performed the experiments, data analyses, and paper writing; Jiang XM performed the theoretical analyses; Liu BW and Guo GC guided and supervised the experiments, and revised the paper. All authors contributed to the general discussion.

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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.

Supplementary information Supporting data are available in the online version of the paper.

Wen-Fa Chen received his BE degree from Beijing University of Chemical Technology in 2017 and ME degree in materials engineering from the University of Chinese Academy of Sciences in 2021. He is currently a PhD student and focuses on nonlinear optical materials at the University of Chinese Academy of Sciences.

Bin-Wen Liu received 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 working as an associate professor at Fujian Institute of Research on the Structure of Matter. His current research interests include solid-state inorganic chemistry, and nonlinear optical materials.

Guo-Cong Guo received 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 working as a full professor at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. His current research interests include inorganic-organic hybrid photofunctional materials, infrared nonlinear optical materials, and catalytic materials.

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Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy

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Chen, WF., Jiang, XM., Pei, SM. et al. Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy. Sci. China Mater. 66, 740–747 (2023). https://doi.org/10.1007/s40843-022-2181-4

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