Abstract
Explorations of new second harmonic generation materials in Ag+-Hg2+/Bi3+-selenites systems afforded three new silver selenium oxides, namely, Ag4Hg(SeO3)2(SeO4) (1), Ag2Bi2(SeO3)3(SeO4) (2) and Ag5Bi(SeO3)4 (3). They exhibit flexible crystal chemistry. Compounds 1 and 2 are mixed valence selenium oxides containing Se(IV) and Se(VI) cations simultaneously. Compounds 1 and 3 exhibit a 3D open framework with 4-, 6- and 8-member polyhedral ring tunnels along a, b and c axes. Compound 1 crystallized in a polar space group and could display a subtle frequency doubling efficiency about 35% of the commercial KH2PO4 (KDP). UV-vis-NIR spectra reveal that compounds 1–3 are wide-band semiconductors with the optical bandgaps of 3.11, 3.65, 3.58 eV respectively. Theoretical calculations disclose that compounds 2 and 3 are indirect band gap structures and their bandgaps are determined by Ag, Bi, Se and O atoms together.
摘要
我们在Ag+-Hg2+/Bi3+-SeO32−体系探索合成新型非线性光学材料时获得了三例结构新颖的银硒氧化物: Ag4Hg(SeO3)2(SeO4)(1), Ag2Bi2(SeO3)3(SeO4) (2) 和 Ag5Bi(SeO3)4 (3). 它们展现了丰富的晶体化学: 1和2 为同时含六价和四价硒的混价氧化物; 1和3为在a, b或c轴含四, 六或八元环孔道的三维开放式骨架结构; 1结晶于非心和极性空间群, 并且可以显示出明显的倍频信号, 约为商用KDP的35%. 紫外漫反射光谱表明这三例化合物均为宽带隙半导体, 其光学带隙分别为3.11, 3.65和3.58 eV. 理论计算发现材料. 2和3为间接带隙半导体, 其带隙是由Ag, Bi, Se和O原子共同决定的.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (21773244 and 21875248), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), and the Natural Science Foundation of Fujian Province (2018J01025).
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Author contributions Wang XX performed the experiments and data analysis, and wrote the first draft of the paper; Li XB gave assistance on the data analysis, Hu CL performed the theoretical data analysis; Kong F and Mao JG supervised the experiments and revised the manuscript. All authors contributed to the general discussion.
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Xiaoxue Wang received her Bachelor degree in chemistry at the Department of Chemistry and Chemical Engineering of Liaocheng Universtiy. She is currently a Master candidate of the Department of Chemistry at Fuzhou University and Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS) under the supervision of Prof. Fang Kong. Her research focuses on the synthesis, structure and characterization of new non-centrosymmetric materials based on metal selenites or tellurites.
Fang Kong received her PhD degree on inorganic chemistry from FJIRSM, CAS under the direction of Prof. Jianggao Mao. Then she joined the faculty of FJIRSM as an Assistant Professor and is currently a Full Professor. She is a member of Youth Innovation Promotion Association of CAS. Her research interest is focused on new SHG materials based on oxyanions of lone pair cations.
Jiang-Gao Mao received his PhD from Changchun Institute of Applied Chemistry, CAS under the supervision of Professor Jiazuan Ni (Academician). He did post-doctoral research at FJIRSM, Chinese University of Hong Kong, University of Houston and Texas A&M University from 1994 to 2002. Since 2002, he has been working as a full professor at FJIRSM, CAS. His current research interest includes the design, syntheses, and crystal structures of new functional inorganic solids, especially NLO materials.
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Wang, XX., Li, XB., Hu, CL. et al. Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis. Sci. China Mater. 62, 1821–1830 (2019). https://doi.org/10.1007/s40843-019-1193-x
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DOI: https://doi.org/10.1007/s40843-019-1193-x