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Syntheses, characterization and calculations of LimAnM6O15 (A=Rb, Cs; M=Si, Ge; m+n=6)

LimAnM6O15 (A=Rb, Cs; M=Si, Ge; m+n=6)的合成、 表征以及计算

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Abstract

Alike phosphates, silicates and germanates exclusively containing tetrahedral basic building units (BBUs) can also exhibit ultraviolet (UV) even deep-UV transitions. They are important for the design of new UV or deep-UV nonlinear optical (NLO) materials. In this paper, four new alkali metal silicates and germanates, Li2Rb4Si6O15, Li2Cs4Si6O15, Li3Rb3Ge6O15 and Li3Cs3Ge6O15 were successfully synthesized by a high temperature solid state reaction. They obey the general formula of LimAnM6O15 (A=Rb, Cs; M=Si, Ge; m+n=6) and all exhibit the Sr2Be2B2O7 (SBBO)-like structures. More importantly, Li3Rb3Ge6O15 and Li3Cs3Ge6O15 crystallize in the noncentrosymmetric (NCS) structures and exhibit remarkable phase-matched second harmonic generation (SHG) effect, 0.8×KH2PO4 (KDP) and 1×KDP, respectively. These indicate that they are potential as UV or deep-UV NLO materials. Furthermore, their optical and NLO properties as well as thermal properties were measured. The structure-property relationships were studied by the dipole moment calculations and the first-principles calculations.

摘要

与磷酸盐类似, 含四面体基本结构基元的硅酸盐和锗酸盐也能表现出紫外甚至深紫外的透过, 因此, 它们对新型紫外或深紫外非线性光学材料的研究具有十分重要的意义. 本文采用高温固相法成功合成了4种新型碱金属硅酸盐和锗酸盐, 即Li2Rb4Si6O15, Li2Cs4Si6O15, Li3Rb3Ge6O15和Li3Cs3Ge6O15. 它们具有相同的结构通式LimAnM6O15 (A=Rb, Cs; M=Si, Ge; m+n=6), 且都表现出 Sr2Be2B2O7 (SBBO)类型的结构. 更重要的是, Li3Rb3Ge6O15和 Li3Cs3Ge6O15结晶于非中心对称(NCS)空间群, 表现出相对较大的二次谐波(SHG)效应(分别为0.8×KDP和1×KDP), 并且可以实现相位匹配. 这表明它们是潜在的紫外/深紫外非线性光学晶体材料. 此外, 我们也研究了它们的光学性能、 非线性光学性质以及热学性质. 通过偶极矩和第一性原理计算, 我们还详细分析了它们的结构-性能关系.

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Acknowledgements

This work was supported by the Natural Science Foundation of Tianjin (19JCZDJC38200), the National Natural Science Foundation of China (51802217, 51972230, 61835014, 51890864 and 51890865), and the National Key R&D Program of China (2016YFB0402103).

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Authors and Affiliations

  1. Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, Tianjin University of Technology, Tianjin, 300384, China

    Jingjing Xu  (徐晶晶), Hongping Wu  (吴红萍), Hongwei Yu  (俞洪伟), Zhanggui Hu  (胡章贵), Jiyang Wang  (王继扬) & Yicheng Wu  (吴以成)

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  1. Jingjing Xu  (徐晶晶)
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  2. Hongping Wu  (吴红萍)
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  3. Hongwei Yu  (俞洪伟)
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  4. Zhanggui Hu  (胡章贵)
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  5. Jiyang Wang  (王继扬)
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  6. Yicheng Wu  (吴以成)
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Contributions

Author contributions Xu J performed the experiments, data analysis, and paper writing; Wu H, Yu H, Hu Z, Wang J and Wu Y designed the concept and supervised the experiments. All authors contributed to the general discussion.

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Correspondence to Hongwei Yu  (俞洪伟).

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Jingjing Xu received her BSc degree in applied physics from Tianjin University of Commerce in 2018. She is currently a master student in Professor Hongwei Yu’s research group at Tianjin University of Technology. Her research focuses on the syntheses, crystal growth, and evaluation of new optical electronic functional materials.

Hongwei Yu received his PhD degree in material physics and chemistry from the University of Chinese Academy of Sciences. He did post-doctoral research at Houston University and Northwestern University in USA from 2014 to 2017. From 2018, he has been working as a full professor at Tianjin University of Technology. His current research interests include the design, syntheses, crystal growth, and evaluation of new optical electronic functional materials.

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Xu, J., Wu, H., Yu, H. et al. Syntheses, characterization and calculations of LimAnM6O15 (A=Rb, Cs; M=Si, Ge; m+n=6). Sci. China Mater. 63, 1769–1778 (2020). https://doi.org/10.1007/s40843-020-1310-1

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