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短波长碱金属及碱土金属硼酸盐、磷酸盐非线性光学晶体的研究
李琳
学位类型硕士
导师潘世烈
2016-05-26
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料工程
关键词非线性光学晶体 硼酸盐 磷酸盐 晶体结构 光学性质
摘要

本文在Li2O-Cs2O-B2O3、Li2O-Cs2O-BaO-P2O5和Cs2O-PbO-P2O5体系中探索并合成了Li5Cs2B7O14, Li4CsB5O10, Cs2Ba3(P2O7)2, Cs2BaP2O7, LiCsBaP2O7, I, II和CsPbPO等十余种化合物,解析了化合物的晶体结构,并对其性能进行了初步表征。研究表明,在合成的化合物中,有6种具有非中心对称结构,2种(化合物I和II)在深紫外非线性光学领域具有潜在的应用前景。1. 化合物Li5Cs2B7O14Li5Cs2B7O14单晶是由高温熔液法自发结晶得到的。Li5Cs2B7O14属于正交晶系,Ama2空间群,a = 21.277(5) ?,b = 13.629(6) ?,c = 4.428(3) ?,Z = 4。该化合物具有三条不同类型的一维(1D)链:链I由Li(3)O5和Li(2)O5基团构成,链II由B(3)O3基团构成,链III由一个B3O6环和两个B(1)O3基团通过共享O(7)和O(8)原子构成;三条链通过共享O原子构筑三维(3D)框架结构。该化合物与Li4Cs3B7O14都符合通式LimCs7-mB7O14 (m = 4, 5)。2. 化合物Li4CsB5O10Li4CsB5O10单晶是由高温熔液法自发结晶得到的,其粉末纯相是由高温固相法合成。Li4CsB5O10属于单斜晶系,P21/c空间群,a = 6.894(5) ?,b = 9.369(6) ?,c = 16.004(11) ?,β = 98.271(9)°,Z = 4。该化合物是由两条1D链与孤立的B5O10基团构成3D框架结构;两条链分别由LiOn (n = 4, 5)和CsO10基团构成。该化合物与Li3Cs2B5O10都符合通式LimCs5-mB5O10 (m = 3, 4)。3. 化合物Cs2Ba3(P2O7)2Cs2Ba3(P2O7)2单晶是由高温熔液法自发结晶得到的,Cs2Ba3(P2O7)2属于正交晶系,P212121空间群,a = 9.017(6) ?,b = 9.606(6) ?,c = 18.689(1) ?,Z = 4。Cs2Ba3(P2O7)2的结构中有两种类型的孤立P2O7基团构成的四个伪层,按着ABA’B’……的方式排列。Cs2Ba3(P2O7)2紫外截止边低于176 nm。4. 化合物Cs2BaP2O7Cs2BaP2O7单晶是由高温熔液法自发结晶得到的。Cs2BaP2O7属于单斜晶系的P21/n空间群,Cs2BaP2O7晶胞参数为a = 10.758(3) ?,b = 6.182(2) ?,c = 13.867(4) ?,β = 105.215(3)°,Z = 4;该化合物中孤立的P2O7基团和BaO6基团构成3D框架,Cs原子嵌在框架的间隙内。Cs2BaP2O7是同成分熔融化合物。5. 化合物LiCsBaP2O7LiCsBaP2O7单晶是由高温熔液法自发结晶得到的。LiCsBaP2O7与Cs2BaP2O7空间群相似,属于单斜晶系的P21/c空间群。 LiCsBaP2O7晶胞参数为a = 7.0782(7) ?,b = 10.8240(1) ?,c = 10.7132(1) ?,β = 105.616(6)°,Z = 4;该化合物的结构中,孤立的P2O7基团,LiO4, BaO8和CsO9基团构成3D框架结构。

其他摘要

In this paper, lots of researches in Li2O-Cs2O-B2O3, Li2O-Cs2O-BaO-P2O5, and Cs2O-PbO-P2O5 systems have been studied, and Li5Cs2B7O14, Li4CsB5O10, Cs2Ba3(P2O7)2, CsBaP2O7, LiCsBaP2O7, I, II and CsPbPO have been synthesized. The crystal structures and properties of these compounds have been described. Among these compounds, five of which possess the noncentrosymmetric structures, and two (compound I and II) of which are promising deep-UV NLO materials.1. Li5Cs2B7O14The single-crystal of Li5Cs2B7O14 has been synthesized by high tempurature solution method. Li5Cs2B7O14 crystallizes in orthorhombic space group Ama2 with unit cell parameters of a = 21.277(5) ?, b = 13.629(6) ?, c = 4.428(3) ?, Z = 4. In Li5Cs2B7O14, there is an interesting feature that the structure contains three kinds of 1D chain. Among these chains, the chain I is composed of Li(3)O5 and Li(2)O5 groups; the chain II is formed by the B(3)O3 groups; and the chain III is composed of the B5O12 units, which consists of one B3O6 ring and two B(1)O3 groups by sharing O(7) and O(8) atoms. Li5Cs2B7O14 and Li4Cs3B7O14 have a certain relationship in their chemical formulas which can be simplified to LimCs7-mB7O14 (m = 4, 5).2. Li4CsB5O10The Li4CsB5O10 crystal has been synthesized by high tempurature solution method. Li4CsB5O10 belongs to the monoclinic crystal system with a centrosymmetric space group P21/c with unit cell parameters of a = 6.894(5) ?, b = 9.369(6) ?, c = 16.004(11) ?, β = 98.271(9) °, Z = 4. In the structure, two types of chains and isolated B5O10 groups construct a 3D network. The two types of chains are built by the LiOn (n = 4, 5) and CsO10 groups, respectively. Li4CsB5O10 and Li3Cs2B5O10 have a certain relationship in their chemical formulas which can be simplified to LimCs5-mB5O10 (m = 3, 4).3. Cs2Ba3(P2O7)2The single-crystal of Cs2Ba3(P2O7)2 has been obtained by high tempurature solution method. Cs2Ba3(P2O7)2 belongs to the monoclinic crystal system with a centrosymmetric space group P212121 with unit cell parameters of a = 9.017(6) ?, b = 9.606(6) ?, c = 18.689(1) ?, Z = 4. It is worth to note that the two types of P2O7 units build four kinds of pseudo-layers, all these pseudo-layers are along the same orientations, with an ABA'B'...arrangement. The cut-off edge is below 176 nm.4. Cs2BaP2O7The single-crystal of Cs2BaP2O7 has been synthesized by high tempurature solution method. Cs2BaP2O7 crystallizes in the monoclinic space group P21/n. The unit cell parameters are a = 10.758(3) ?, b = 6.182(2) ?, c = 13.867(4) ?, β = 105.215(3) °, Z = 4. The structure analysis reveals that isolated units, P2O7 and BaO6 are interconnected through corner-sharing O atoms to construct a 3D framework with six-member channels where the Cs atoms reside in. And Cs2BaP2O7 melts congruently.5. LiCsBaP2O7The single-crystal of LiCsBaP2O7 has been synthesized by high tempurature solution method. LiCsBaP2O7 and Cs2BaP2O7 have similar space groups. LiCsBaP2O7 belongs to the monoclinic crystal system with a centrosymmetric space group P21/c. The unit cell parameters are a = 7.0782(7) ?, b = 10.8240(1) ?, c = 10.7132(1) ?, β = 105.616(6) °, Z = 4. The structure exhibits a 3D framework that is built by isolated P2O7 and LiO4, BaO8 and CsO9 units.

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4582
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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李琳. 短波长碱金属及碱土金属硼酸盐、磷酸盐非线性光学晶体的研究[D]. 北京. 中国科学院大学,2016.
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