摘要
Explorations of new second harmonic generation materials in Ag^+-Hg^2+/Bi^3+-selenites systems afforded three new silver selenium oxides, namely, Ag4 Hg(SeO3)2(SeO4)(1), Ag2Bi2(SeO3)3(SeO4)(2) and Ag5 Bi(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 3 D 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 e V respectively. Theoretical calculations disclose that compounds2 and 3 are indirect band gap structures and their bandgaps are determined by Ag, Bi, Se and O atoms together.
我们在Ag^+-Hg^2+/Bi^3+-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3.58e V.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.
作者
Xiao-Xue Wang
Xiao-Bao Li
Chun-Li Hu
Fang Kong
Jiang-Gao Mao
王晓雪;李小宝;胡春丽;孔芳;毛江高(College of Chemistry,Fuzhou University,Fuzhou 350108,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China)
基金
supported by the National Natural Science Foundation of China (21773244 and 21875248)
the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)
the Natural Science Foundation of Fujian Province (2018J01025)
