一种锗酸盐中红外非线性光学晶体的合成及性能研究
Synthesis and Properties Study of a Germanate Mid-Infrared Nonlinear Optical Crystal
DOI: 10.12677/ms.2024.147125, PDF,    科研立项经费支持
作者: 师海彦, 杨超凡:天津理工大学材料科学与工程学院,天津
关键词: 非线性光学晶体锗酸盐体系中红外波段光学性能Nonlinear Optical Crystals Germanates System Mid-Infrared Range Optical Properties
摘要: 本研究在锗酸盐体系引入含孤对电子和重元素的[PbOX]多面体,通过高温固相法合成了一种中红外非线性光学晶体——PbSrGeO4。该化合物结晶于非中心对称空间群P212121 (No. 19),具有优良的热稳定性(1066℃)。光谱分析显示PbSrGeO4的紫外截止边位于293 nm左右,红外截止边约为6.0 μm,在0.293~6.0 μm范围内具有良好的透过特性,可覆盖3~5 μm波段的关键大气透过窗口。粉末倍频测试结果表明,PbSrGeO4表现出适中的二次谐波响应(0.3 × KDP)。此外,本研究进一步探讨了PbSrGeO4微观结构与光学性能之间的内在关系。该研究提供了一种潜在的锗酸盐中红外非线性光学晶体,为设计探索新型锗酸盐中红外非线性光学材料提供了有益参考。
Abstract: In this study, a [PbOX] polyhedra containing lone pair electrons and heavy elements was introduced to the germanate system, and a mid-infrared nonlinear optical crystal, PbSrGeO4, was synthesized through high-temperature solid-state method. The compound crystallizes in the acentric space group P212121 (No. 19) and exhibits excellent thermal stability (1066˚C). Spectral analysis reveals that the ultraviolet cutoff edge of PbSrGeO4 is around 293 nm, while the infrared cutoff edge is around 6.0 μm. It demonstrates good transmittance characteristics in the range of 0.293~6.0 μm, effectively covering the key atmospheric windows of the 3~5 μm region. Second harmonic generation tests indicate that PbSrGeO4 exhibits moderate second harmonic response (0.3 × KDP) and can achieve phase matching. Furthermore, this study explores the intrinsic relationship between the microstructure of PbSrGeO4 and its optical properties. The research provides a potential mid-infrared nonlinear optical crystal in the germanate system, offering valuable insights for the design and exploration of novel germanate mid-infrared nonlinear optical materials.
文章引用:师海彦, 杨超凡. 一种锗酸盐中红外非线性光学晶体的合成及性能研究[J]. 材料科学, 2024, 14(7): 1110-1117. https://doi.org/10.12677/ms.2024.147125

参考文献

[1] Halasyamani, P.S. and Poeppelmeier, K.R. (1998) Noncentrosymmetric Oxides. Chemistry of Materials, 10, 2753-2769. [Google Scholar] [CrossRef
[2] 王继扬, 于浩海, 吴以成, 等. 中国功能晶体研究进展[J]. 工程, 2015, 1(2): 67-102.
[3] 张兵兵, 武奎, 王颖, 等. 第一性原理计算在非线性光学材料领域的应用及进展[J]. 中国科学(化学), 2021, 51(9): 1137-1149.
[4] Xia, M., Jiang, X., Lin, Z. and Li, R. (2016) “All-Three-In-One”: A New Bismuth-Tellurium-Borate Bi3TeBO9 Exhibiting Strong Second Harmonic Generation Response. Journal of the American Chemical Society, 138, 14190-14193. [Google Scholar] [CrossRef] [PubMed]
[5] Hu, Y., Wu, C., Jiang, X., Wang, Z., Huang, Z., Lin, Z., et al. (2021) Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo2O8F. Journal of the American Chemical Society, 143, 12455-12459. [Google Scholar] [CrossRef] [PubMed]
[6] Yu, J., Zhang, B., Zhang, X., Wang, Y., Wu, K. and Lee, M. (2020) Finding Optimal Mid-Infrared Nonlinear Optical Materials in Germanates by First-Principles High-Throughput Screening and Experimental Verification. ACS Applied Materials & Interfaces, 12, 45023-45035. [Google Scholar] [CrossRef] [PubMed]
[7] Kim, S.W., Deng, Z., Yu, S., Padmanabhan, H., Zhang, W., Gopalan, V., et al. (2017) A(II)GeTeO6 (A = Mn, Cd, Pb): Non-Centrosymmetric Layered Tellurates with PbSb2O6-Related Structure. Inorganic Chemistry, 56, 9019-9024. [Google Scholar] [CrossRef] [PubMed]
[8] Jia, Z., Jiang, X., Lin, Z. and Xia, M. (2018) PbTeGeO6: Polar Rosiaite-Type Germanate Featuring a Two Dimensional Layered Structure. Dalton Transactions, 47, 16388-16392. [Google Scholar] [CrossRef] [PubMed]
[9] Xia, M., Tang, C. and Li, R. (2019) Rb4Li2TiOGe4O12: A Titanyl Nonlinear Optical Material with the Widest Transparency Range. Angewandte Chemie, 131, 18425-18428. [Google Scholar] [CrossRef
[10] Han, T., Li, C., Zhao, W., She, Y., Jiao, J., Liang, F., et al. (2021) Investigations on the Synthesis, Crystal Structure, Linear-and Nonlinear-Optical Properties of the Zinc Germanate Rb2ZnGe2O6. Inorganic Chemistry, 61, 706-712. [Google Scholar] [CrossRef] [PubMed]
[11] Halasyamani, P.S. (2004) Asymmetric Cation Coordination in Oxide Materials: Influence of Lone-Pair Cations on the Intra-Octahedral Distortion in D0 Transition Metals. Chemistry of Materials, 16, 3586-3592. [Google Scholar] [CrossRef
[12] Ok, K.M., Halasyamani, P.S., Casanova, D., Llunell, M., Alemany, P. and Alvarez, S. (2006) Distortions in Octahedrally Coordinated D0 Transition Metal Oxides: A Continuous Symmetry Measures Approach. Chemistry of Materials, 18, 3176-3183. [Google Scholar] [CrossRef
[13] Petschnig, L.L., Wurst, K., Perfler, L., Johrendt, D. and Huppertz, H. (2014) Synthesis and Characterization of the New Lead Strontium Germanate PbSrGeO4. Zeitschrift für Naturforschung B, 69, 845-850. [Google Scholar] [CrossRef
[14] Kubelka, P. and Munk, F. (1931) An Article on Optics of Paint Layers. Zeitschrift für Physik, 12, 259-274.
[15] Jiang, X., Kang, L., Luo, S., Gong, P., Lee, M. and Lin, Z. (2014) Development of Nonlinear Optical Materials Promoted by Density Functional Theory Simulations. International Journal of Modern Physics B, 28, Article ID: 1430018. [Google Scholar] [CrossRef
[16] Kurtz, S.K. and Perry, T.T. (1968) A Powder Technique for the Evaluation of Nonlinear Optical Materials. Journal of Applied Physics, 39, 3798-3813. [Google Scholar] [CrossRef
[17] Shirai, H., Morioka, Y., Nakagawa, I. and Takei, H. (1984) Raman Scattering and Phase Transitions in BaZnGeO4 Crystal. Journal of the Physical Society of Japan, 53, 456-465. [Google Scholar] [CrossRef