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A BBO-like trithiocyanate with significantly enhanced birefringence and second-harmonic generation

一种同时具备显著增强的双折射和二次谐波效应的类BBO三聚硫氰酸盐

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Abstract

There is presently a great demand for nonlinear optical (NLO) crystals that can demonstrate both strong second-harmonic generation (SHG) and high birefringence in emerging spin-orbit angular momentum photonic technologies. Here we report a new chiral trithiocyanate compound, K4(HC3N3S3)2·H2O, which is composed of highly π-conjugated [HC3N3S3]2− rings and is structurally analogous to commercial NLO crystal β-BaB2O4 (BBO). Compared with BBO, which has optimally arranged π-conjugated [B3O6]3− rings, K4(HC3N3S3)2·H2O does not have an optimal arrangement of [HC3N3S3]2− rings. However, this trithiocyanate exhibits a significantly enhanced SHG response of up to 1.8 times that of BBO and an enhanced birefringence of up to 0.402 at the wavelength of 550 nm (about 3.3 times that of BBO). The first-principles calculations show that the π-conjugated [HC3N3S3]2− is the cause of the superior optical properties of K4(HC3N3S3)2·H2O. These findings demonstrate that the π-conjugated [HC3N3S3]2− is an excellent bi-functional “material gene” and merits more attention in the study of optical integrated devices for emerging photonic technologies.

摘要

在新兴的自旋轨道角动量光子技术领域, 对兼具强二次谐波和大双折射的非线性光学晶体有很大的需求. 基于此, 本文采用具有大π共轭效应的[HC3N3S3]2−和碱金属阳离子K+相结合, 成功合成了一例新型类β-BaB2O4 (BBO)手性三聚硫氰酸盐K4(HC3N3S3)2·H2O(1). 与具有最优排列的π共轭[B3O6]3−环的BBO相比, 1中[HC3N3S3]2−环的排列并不理想, 但倍频响应和双折射显著增强(1.8 × BBO; ∆n = 0.402@550 nm,~3.3 × BBO). 第一性原理计算分析表明, π共轭[HC3N3S3]2−环是产生优异光学性能的根本原因. 这项工作证明了π共轭[HC3N3S3]2−是优秀的双功能“材料基因”, 在新兴光子技术的光学集成器件研究中值得更多的关注.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22122507, 21833010, 61975207, 22193042, and 21921001), the Natural Science Foundation of Fujian Province (2022J02012), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y202069), and the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (ZDBS-LY-SLH024), as well as Fujian Institute of Innovation (FJCXY18010201) in the Chinese Academy of Sciences. We are grateful for the help from Pei Shao-Min and Liu Bin-Win at FJIRSM in the measurement of power-dependent SHG spectra.

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Authors and Affiliations

  1. Qingyuan Innovation Laboratory, Quanzhou, 362801, China

    Qianting Xu  (许倩婷) & Linxi Hou  (侯琳熙)

  2. Department of Materials-Oriented Chemical Engineering, School of Chemical Engineering, Fuzhou University, Fuzhou, 350116, China

    Qianting Xu  (许倩婷) & Linxi Hou  (侯琳熙)

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

    Youchao Liu  (刘有超), Yanqiang Li  (李雁强), Lina Li  (李丽娜), Sangen Zhao  (赵三根) & Junhua Luo  (罗军华)

  4. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Qingchen Wu  (吴清宸) & Zheshuai Lin  (林哲帅)

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

    Qingchen Wu  (吴清宸), Yanqiang Li  (李雁强), Zheshuai Lin  (林哲帅), Sangen Zhao  (赵三根) & Junhua Luo  (罗军华)

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

    Lina Li  (李丽娜), Sangen Zhao  (赵三根) & Junhua Luo  (罗军华)

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  1. Qianting Xu  (许倩婷)
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Contributions

Xu Q and Liu Y carried out the experiments, performed the data processing, and wrote the manuscript. Wu Q and Lin Z performed the theoretical calculation of the crystal properties. Li Y and Li L helped with the analysis of the experimental data. Zhao S revised the manuscript. Hou L and Luo J designed the organization of the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Linxi Hou  (侯琳熙) or Junhua Luo  (罗军华).

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Supplementary information

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

Conflict of interest

The authors declare that they have no conflict of interest.

Qianting Xu is engaged in postdoctoral research at Qingyuan Innovation Laboratory and Fuzhou University. She received her PhD degree from Yangzhou University in 2022. Her current research focuses on exploring new hybrid photoelectric crystal materials.

Linxi Hou received his PhD degree from Zhejiang University in 2005. From 2005 to 2013, he worked at Ningbo University. In September 2013, he joined Fuzhou University as a professor. His research area includes the green synthesis and application of new interfacial materials, and the design and synthesis of electronic chemicals.

Junhua Luo received his PhD degree from Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences in 2003, followed by postdoctoral research at the North Carolina State University and University of Florida from 2003 to 2005. From 2006 to 2009, he was funded by the Los Alamos National Laboratory at the Neutron Diffraction Center. He became a professor of chemistry at FJIRSM in 2009. His current research interests focus on the development of photoelectric functional materials based on organic-inorganic hybrids.

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Xu, Q., Liu, Y., Wu, Q. et al. A BBO-like trithiocyanate with significantly enhanced birefringence and second-harmonic generation. Sci. China Mater. 66, 3271–3277 (2023). https://doi.org/10.1007/s40843-023-2439-8

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  • DOI: https://doi.org/10.1007/s40843-023-2439-8

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