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钡、铅硼酸盐和钡钒酸盐的合成、结构及光学性能研究
鹿娟娟
学位类型博士
导师潘世烈
2017-05-31
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料物理化学
关键词非线性光学晶体 离子替换 水热合成 碱土金属硼酸盐和钒酸盐 倍频效应 第一性原理计算
摘要

非线性光学材料在激光领域有着十分重要的应用,近年来受到各国科学家的广泛关注和深入研究。本论文以探索离子替代对晶体结构与性能影响为目标,采用水热法合成出一系列新的含钡、铅的硼酸盐以及高温固相法合成含钡的钒酸盐。主要取得如下成果:1. 采用水热法通过Ba离子和Pb离子替代合成了三种具有非线性光学性质的碱土金属硼酸盐,A3(OH)(B9O16)[B(OH)3] (A=Ba、Ba0.72Pb0.28、Pb)。它们结晶于非心的P31c空间群,阴离子基本结构基元均为B9O16,通过分享氧原子进一步连接形成带有孔道的 ∞(B9O16)5? 三维网络结构,金属阳离子(A=Ba、Ba0.72Pb0.28、Pb)和硼酸分子位于孔道中。Ba3(OH)(B9O16)[B(OH)3]具有1.1倍KDP的倍频效应并能实现第一类相位匹配,还具有较大的带隙(5.11 eV)和较高的热稳定性(加热到400°C无明显失重),是具有潜在应用价值的紫外非线性光学材料。随着铅离子逐渐替换钡离子,化合物的热学性能以及带隙、倍频效应等光学性质发生规律性变化。通过第一性原理计算,从电子结构角度对铅离子替换钡离子引起的光学性质变化给与合理的解释。在本体系的探索中也得到了NaBa3(OH)(B9O16) [B(OH)4])化合物,对其进行了漫反射、热重等物化性能表征。 2. 阴离子间的替换也是合成新化合物的策略之一。采用水热法对本课题组前期合成的化合物Pb2BO3F进行OH与F替换,合成出了Pb2(BO3)(OH)。Pb2(BO3)(OH)结晶于中心的C2/m空间群,由PbO3多面体与孤立的BO3基团相互连接组成二维的层状结构。而替换前的Pb2BO3F结晶于P63/m空间群,这是由于OH替换F离子后,Pb的配位环境发生了变化导致其晶体结构的变化。同时我们比较了OH和F替换后生成等分子式的其它化合物,从而进一步阐明了OH与F相互替换对化合物结构的影响。 3. 采用高温固相法,合成了一种新的钒酸盐化合物Na2BaZn(VO4)2,解析了该化合物的晶体结构,测试了相关物化性质。该化合物结晶于三方晶系 空间群,具有三维立体结构。孤立的ZnO6多面体和VO4四面体通过共享氧原子相连形成Zn-V-O层,钠原子填充在层面的空隙中。由BaO12多面体连接二维的Zn-V-O层,形成了化合物的三维立体结构。

其他摘要

Nonlinear optical (NLO) materials have very important applications and have been attracted more and more attention in the field of laser in recent years. In order to explore the effect of ion substitution on crystal structure and properties, we synthesize a series of new borates containing barium and lead through the hydrothermal method and vanadate containing barium through high temperature solution method. Main results are as follows:1. Based on the substitution of Ba ions and Pb ions, three kinds of alkaline earth metal borates with nonlinear optical properties, A3(OH)(B9O16)[B(OH)3] (A=Ba, Ba0.72Pb0.28, Pb), have been synthesized hydrothermally. They crystallize in an acentric space group P31c and their structures feature a three-dimensional (3D) B9O16 framework with 21-membered-ring tunnels along c axis, in which the Ba or Pb/Ba cations and [B(OH)3] groups reside. Ba3(OH)(B9O16)[B(OH)3] exhibits a SHG response of 1.1 times of KDP and is type-I phase-matchable. In addition, it has a large band gap (5.11 eV) and is thermally stable to 400°C. These make Ba3(OH)(B9O16)[B(OH)3] become a promising UV NLO material. With the substitution of Pb ions for Ba ions, the thermal properties, as well as the optical properties of band gap and second-harmonic generation of three compounds change regularly. Moreover, by the first principles calculation, the change of optical properties of Pb ion instead of Ba ion is explained reasonably from the point of view of electronic structure. In this system, we also obtained NaBa3(OH)(B9O16)[B(OH)4]) and its IR and UV-Vis-NIR spectra and TG-DSC curves have been reported.2. Anion substitution is also one of the useful strategies for the synthesis of new compounds. We synthesized Pb2(BO3)(OH) compound hydrothermally through the substitution of OH- with F- in Pb2BO3F, that is previously synthesized by our group. Pb2(BO3)(OH) crystalizes in the space group C2/m and features a 2D framework composed of PbO3 polyhedra and isolated BO3 triangles. While Pb2BO3F crystalizes in the space group P63/m, the structure transformation is caused by the change of the coordination environment of Pb in the two compounds. To further study the effect of OH-F substitution on the crystal structure, we have also compared other structures with OH-F substitution in borates.3. A new vanadate compound Na2BaZn(VO4)2 was synthesized by high temperature solid state method. The crystal structure, the physical and chemical properties were analyzed and measured. Na2BaZn(VO4)2 crystallizes in trigonal system with space group of p-3. In the crystal structure, isolated ZnO6 polyhedra and VO4 tetrahedra are connected each other to form Zn-V-O layers, which are further connected by BaO12 polyhedra to construct the three-dimensional framework. The sodium atoms are filled in the framework.

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4983
专题材料物理与化学研究室
作者单位中国科学院新疆理化技术研究所
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鹿娟娟. 钡、铅硼酸盐和钡钒酸盐的合成、结构及光学性能研究[D]. 北京. 中国科学院大学,2017.
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