|卤素硼硅酸盐Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br)紫外非线性光学晶体的设计、合成及性能研究|
|关键词||硼硅酸盐 非线性光学晶体 极性模板效应 次级构筑单元|
本论文将BO3和SiO4基团结合，引入畸变的离子盐单元XBa6次级构筑单元(SBU)，利用其极性模板效应，首次成功设计合成了两种离子盐型卤素硼硅酸盐，Ba4(BO3)3(SiO4)·Ba3X(X = Cl, Br)，解析了其晶体结构，并对其性能进行了系统研究。研究表明：Ba4(BO3)3(SiO4)·Ba3X是首例非线性碱土金属卤素硼硅酸盐，具有良好的非线性光学性质，在深紫外非线性光学材料方面有潜在的应用前景。另外，本论文通过等离子替换法对已知化合物进行结构改性，探索了化合物Sr4Ba3(BO3)Cl5及Ba7(BO3)3(SiO4)F的纯相合成、小晶体的生长。具体工作如下：
Based on the combination of two different anionic groups (SiO4 and BO3) and the utility of XBa6 (X = Cl, Br) secondary building unit (SBU) polar template, two new salt-inclusion solids, Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br) have been successfully designed and synthesized for the first time. The crystal structures and properties have been studied in this paper. They are the first alkaline-earth metal borosilicate halides as nonlinear optical (NLO) materials and their good optical properties make Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br) potential deep UV NLO materials. In addition, by using the method of ion substitution to modify known crystal structures, it has attempted to explore and obtain the polycrystalline sample and single crystal of new compounds, Sr4Ba3(BO3)Cl5 and Ba7(BO3)3(SiO4)F. Main contents and results are as follows: (1) The single crystals of Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br) have been obtained by high-temperature solution method and the structures determined by the single crystal X-ray diffraction measuments. As far as we know, Ba4(BO3)3(SiO4)?Ba3X are the first examples of the alkaline-earth metal borosilicate halides. Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br) crystallize in polar space group P63mc of the hexagonal system with lattice parameters a = 11.195 (4) ?, c = 7.263 (6) ? and Z = 2 for Ba4(BO3)3(SiO4)?Ba3Cl and a = 11.279(3) ?, c = 7.324(4) ? and Z = 2 for Ba4(BO3)3(SiO4)?Ba3Br. They are isostructural and their structures feature a noncentrosymmetric 3D network composed of the ∞3[Ba4(BO3)3(SiO4)] covalent framework as well as the polar ∞1[Ba3Cl] chain as ionic salt units. (2) The optical and thermal properties of Ba4(BO3)3(SiO4)?Ba3X are comprehensively characterized. The UV?Vis?NIR diffuse reflectance spectra show that they exhibit a wide transparent region with the UV cut-off edge below 190 nm. Meanwhile, powder second-harmonic generation (SHG) measurements on sieved crystals reveal that Ba4(BO3)3(SiO4)?Ba3X are type-I phase-matchable with moderate SHG responses similar to that of KDP (KH2PO4). Furthermore, both of them melt congruently, which proved by the TG-DSC techques and powder XRD analyses. These properties show that Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br) are promising deep UV NLO materials. And the current studies shed some light on the design and synthesis of novel deep UV NLO crystals in the borosilicate halide systems. (3) By comparison of the crystal structures of Ba7(BO3)4–yF2+3y and Ba4(BO3)3(SiO4)?Ba3X, the probability of (SiO4)4??(BO3X)4?, (X4)4? isomorphism substitution have been analyzed. Meanwhile, via (Cl4)4??(SiO4)4?, Sr2+?Ba2+ and F??X? ionic substitutions, the synthesis of the polycrystalline samples of Sr4Ba3(BO3)Cl5 and Ba7(BO3)3(SiO4)F as well as the growth of their single crystals have been investigated.
|林晓霞. 卤素硼硅酸盐Ba4(BO3)3(SiO4)?Ba3X (X = Cl, Br)紫外非线性光学晶体的设计、合成及性能研究[D]. 北京. 中国科学院大学,2014.|
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