XJIPC OpenIR  > 材料物理与化学研究室
Thesis Advisor潘世烈
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline微电子学与固体电子学
Keyword非线性光学晶体 四面体基团 硼酸盐 晶体结构 光学性质

非线性光学晶体材料,在激光和和光谱学等方面具有非常重要的应用,是光电功能材料领域的一个研究热点。本论文以探索新型的非线性光学晶体材料为目标,选择了含四面体基团的硼酸盐体系,合成了几种新型镓硼酸盐和锗硼酸盐化合物,并就这些化合物的结构、性能及理论计算等方面进行了研究,主要取得的成果如下:1. 两种镓硼酸盐卤化物:NaBa4(GaB4O9)2X3 (X=Cl, Br)高温熔液法合成NaBa4(GaB4O9)2X3 (X=Cl, Br)化合物,并对其晶体结构,热学性能,线性和非线性光学性质进行了表征。其结晶于四方晶系,空间群为P42nm (No. 102),结构框架为由GaO4四面体与B4O9基团相互连接形成的三维网络。热重-差热以及熔融前后xrd实验证明NaBa4(GaB4O9)2X3 (X=Cl, Br)为非同成分熔融化合物。其带隙分别为3.76 eV和3.71 eV。NaBa4(GaB4O9)2X3 (X=Cl, Br)的粉末倍频效应分别为1.5倍和1.1倍的KH2PO4 (KDP),是所有碱金属、碱土金属镓硼酸盐中最大的,并且能实现相位匹配。理论计算表明其倍频效应的主要来源是GaO4四面体与B-O基团。2. 两种锗硼酸盐卤化物:Ba7(BO3)3GeO4X (X=Cl, Br) 高温溶液法合成了Ba7(BO3)3GeO4X (X=Cl, Br)化合物,其结晶于正交晶系的Pbam (no. 55)空间群,由BaOn (n=8, 9)和BaO7Br2多面体组成了其三维结构框架,而孤立的GeO4四面体和BO3基团填充在此框架中。通过调研我们发现Ba7(BO3)3SiO4X (X=Cl, Br)与Ba7(BO3)3GeO4X (X=Cl, Br)具有非常相似的化学式,但是它们却并不同构,而其它具有相似化学式的硅硼酸盐和锗硼酸盐却大多同构。我们通过对结构的深入分析,解释了这种不寻常的现象,这对以后我们更加深入地理解结构转变提供了新的思路。通过漫反射光谱的测量,发现Ba7(BO3)3GeO4X (X=Cl, Br)具有大的带隙,分别为5.28和5.31 eV。

Other Abstract

Nonlinear optical (NLO) material is a hot spot of photo-electronic functional material study for its important application in laser and spectroscopy. This thesis chooses borates including tetrahedral units to search new NLO materials and we obtain several new gallium borates and borogermanates. 1. Two gallium borate halides:NaBa4(GaB4O9)2X3 (X=Cl, Br)Two gallium borates, NaBa4(GaB4O9)2X3 (X=Cl, Br), were synthesized by high temperature solution method. Their crystal structures, thermal property, linear and nonlinear optical properties are measured. They crystallize in the noncentrosymmetrical space group P42nm. Their structures feature a 3D [GaB4O9]∞ framework composed of the GaO4 tetrahedra and the B4O9 groups. Thermal analysis indicates that they are not congruent melting compounds and UV–Vis–IR diffuse reflectance spectra show that their band gaps are 3.76 and 3.71 eV, respectively. NaBa4(GaB4O9)2Cl3 and NaBa4(GaB4O9)2Br3 show the largest SHG responses (1.5 and 1.1 times of KDP respectively) among alkali metal and alkaline-earth metal gallium borates. The B-O groups and GaO4 tetrahedron have major contribution to SHG response. 2. Two borogermanate halides:Ba7(BO3)3GeO4X (X=Cl, Br)The first borogermanate halides, Ba7(BO3)3GeO4X (X=Cl, Br) have been synthesized by high temperature solution method. Ba7(BO3)3GeO4X (X=Cl, Br) are isostructural and crystallize in the orthorhombic space group Pbam (no. 55). They feature a Ba?based 3D framework, while isolated GeO4 tetrahedra and BO3 triangles are filled in the space created by the framework. Significantly, Ba7(BO3)3GeO4X (X=Cl, Br) possess similar formula with the borosilicate halides, Ba7(BO3)3SiO4X (X=Cl, Br), while they are not isostructural. A interpretation for the structural transformation between them is demonstrated considering rigid GeO4 tetrahedra and flexible XBa6 (X=Cl, Br) octahedra. This interpretation can give new insights into structural transformation. The UV?vis?NIR diffuse reflectance spectra of Ba7(BO3)3GeO4X (X=Cl, Br) indicate that their experimental optical band gaps are 5.28 and 5.31 eV, respectively.

Document Type学位论文
Recommended Citation
GB/T 7714
文明. 含四面体基团的镓硼酸盐和锗硼酸盐的合成、结构及性能的研究[D]. 北京. 中国科学院大学,2016.
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