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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
Thesis Advisor潘世烈
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline材料物理与化学
Keyword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:
(1)利用高温熔液法得到了离子盐型卤素硼硅酸盐Ba4(BO3)3(SiO4)·Ba3X单晶,是目前已知的首例碱土金属卤素硼硅酸盐。利用X射线单晶衍射仪解析了晶体结构,发现Ba4(BO3)3(SiO4)·Ba3X(X = Cl, Br)是同构晶体,都属于六方晶系的P63mc极性空间群,其晶胞参数分别为:a= 11.195(4) Å,c= 7.263(6) Å,Z = 2和a = 11.279(3)Å,c= 7.324(4) Å,Z = 2。它们的整体结构都是由∞3[Ba4(BO3)3(SiO4)]共价晶格与极性链∞1[Ba3X]的离子晶格共同组成的极性非中心对称的三维网状结构。
(2)对Ba4(BO3)3(SiO4)·Ba3X的光学、热学等性质进行了详细研究。紫外漫反射实验分析表明,Ba4(BO3)3(SiO4)·Ba3X具有宽的透光波段和低于190 nm紫外截止边;粉末倍频测试表明Ba4(BO3)3(SiO4)·Ba3X为I类相位匹配,倍频效应约为1倍的KDP。另外,热重/差热分析(TG-DSC)以及熔融前后粉末XRD图谱表明,Ba4(BO3)3(SiO4)·Ba3X是一致熔融的化合物,有利于通过熔体法生长大尺寸单晶。这些性质表明Ba4(BO3)3(SiO4)·Ba3X在深紫外非线性光学材料方面有潜在应用前景,同时也表明卤素硼硅酸盐是探索紫外深紫外非线性光学材料的新体系。
(3)通过对比Ba4(BO3)3(SiO4)·Ba3X与Ba7(BO3)4-yF2+3y等化合物,分析了(SiO4)4与(BO3F)4以及拓展到(SiO4)4与(X4)4,(BO3X)4阴离子替换的可能性。并利用(Cl4)4↔(SiO4)4, Sr2+↔Ba2+和F↔X的阴离子替换尝试探索了Sr4Ba3(BO3)Cl5、Ba7(BO3)3(SiO4)F的纯相粉末合成及其单晶的生长。

Other Abstract

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.

Document Type学位论文
Recommended Citation
GB/T 7714
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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