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新型Ba7(BO3)3F5和KSr4B3O9等硼酸盐化合物的合成、结构和性能研究
赵文武
学位类型博士
导师潘世烈
2012-05-20
学位授予单位中国科学院研究生院
学位授予地点北京
学位专业微电子学与固体电子学
关键词非线性光学晶体 硼酸盐 二阶姜-泰勒畸变 碘酸盐
摘要本论文研究工作分为两部分:一部分是对两种非中心对称的晶体材料(Ba7(BO3)3F5和KSr4B3O9)的晶体生长、结构及其性能进行了研究,并系统的寻找了适合生长KSr4B3O9晶体生长的助熔剂体系,制备出了比较透明的单晶;另一部分是合成新型的复合晶体材料:Pb2BO3F、Pb8B9O21F、Pb3OBO3F、PbBiBO4和K2Bi(IO3)4Cl,解析其单晶结构并测试了其物化性能: 1. 将具有较大半径的Ba2+离子与硼氧功能基团相结合,合成出了一种新的化合物Ba7(BO3)3F5。用高温溶液法生长出了该化合物的晶体,并解析其晶体结构;Ba7(BO3)3F5晶体属六方晶系,空间群为P63mc,晶胞参数:a = 11.1562(15)Å,c = 7.2415(14)Å,Z = 2,V = 780.5(2)Å3。Ba7(BO3)3F5晶体结构是由Ba(1)O7F3多面体,Ba(2)O4F3多面体,Ba(3)O6F4多面体和独立的BO3基团相互连接形成的三维空间网络结构。粉末倍频测试显示化合物Ba7(BO3)3F5的倍频效应约为1/3倍KDP;紫外-可见-近红外漫反射光谱测试结果显示该晶体紫外吸收边小于190nm。 2. 通过高温溶液法生长KSr4B3O9晶体,探索了其生长的助熔剂体系,即KSr4B3O9与NaF、H3BO3 为1:3:1比例的混和体系,生长出了尺寸达15mm × 15mm × 6mm的较透明晶体,并解析了其晶体结构。该化合物属正交晶系,空间群为Ama2,晶胞参数:a = 10.987(2)Å, b = 11.948(2)Å, c = 6.8865(2)Å, Z = 4, V = 907.4(14)Å3;在空间中呈三维网络结构。非线性光学测试表明其粉末倍频效应与KDP相当;紫外-可见-近红外漫反射光谱测试结果表明KSr4B3O9晶体紫外吸收边在230nm附近。 3. 将具有孤对电子的Pb2+金属阳离子与硼氧基团相结合,在PbO-PbF2-B2O3三元体系中生长出三种氟硼酸铅化合物,Pb2BO3F,Pb8B9O21F和Pb3OBO3F;并用高温溶液法分别生长出三种晶体,分析了其单晶结构。化合物Pb2BO3F属六方晶系,空间群为P63/m,晶胞参数为a = 7.2460(3)Å, c = 14.5521(17)Å, Z = 6, V = 661.69(9)Å3;化合物Pb8B9O21F晶体属三方晶系,空间群为 ,晶胞参数为a = 9.740(3)Å, b = 9.740(3)Å, c = 38.167(15)Å, Z = 6, V = 3135.5(8)Å3;化合物Pb3OBO3F属正交晶系,空间群为Pbcm,晶胞参数为a = 7.6313(14)Å, b = 6.5229(12)Å, c = 11.906(2)Å, Z = 4, V = 592.66(19)Å3。随后分别对这三种化合物的结构进行分析,三种化合物的空间排布皆为空间网络结构;其中在Pb8B9O21F晶体的空间结构中发现了一种新型的独立存在的[B9O21]15-基团。 以具有孤对电子的Bi3+金属阳离子为基础基元,探索出两种新的化合物,PbBiBO4和K2Bi(IO3)4Cl。用高温溶液法生长出透明的PbBiBO4晶体,并进行单晶解析,分析表明:化合物PbBiBO4属正交晶系,空间群为Cmca,晶胞参数为a = 10.782(3)Å, b = 10.502(3)Å, c = 7.477(2)Å, Z = 8, V = 846.7(4)Å3,空间结构是由扭曲的BiO6八面体、PbO4基团和BO3基团组成的三维网状结构;用水热法生长出透明的K2Bi(IO3)4Cl晶体,并解析出该晶体的晶体结构;K2Bi(IO3)4Cl晶体属单斜晶系,空间群为P21/c,晶胞参数为:a = 11.216(3)Å, b = 12.260(3)Å, c = 10.444(2)Å, Z = 4, V = 1352.2(5)Å3。K2Bi(IO3)4Cl化合物的晶体结构是由BiO7 基团,K(1)O10基团,K(2)O7Cl2基团和IO3基团相互连接构成的三维网络结构。
其他摘要This thesis was divided into two parts. In the first part, two kinds of non-centrosymmetry crystals (Ba7(BO3)3F5 and KSr4B3O9) have been studied, the major work consisted of synthesis, crystal growth, crystal structure determination and properties measurement, etc. In the second part, five new crystals have been obtained, Pb2BO3F, Pb8B9O21F, Pb3OBO3F, PbBiBO4 and K2Bi(IO3)4Cl, and the synthesis, structure determination and properties have been studied. 1. Introduction of the F- anion in the BaO-B2O3 system generates a new nonlinear optical materials, Ba7(BO3)3F5, with BO3 triangles and the UV cutoff wavelength below 190nm. Ba7(BO3)3F5 crystallizes in the non-centrosymmetric hexagonal space group P63mc. It produces SHG intensity about 1/3 times as large as that of KH2PO4 (KDP) and is phase matchable. 2. Polycrystalline samples of KSr4B3O9 were synthesized by solid-state reaction techniques. Single crystal of KSr4B3O9 with size up to 15mm × 16mm × 6mm have been successfully grown from the NaF-H3BO3 flux system and the selection of the flux was discussed. It crystallizes in the polar space group Ama2. The material exhibits a three-dimensional structure consisting of interconnecting KO10 groups, SrOx (x = 8, 9) units and isolated BO3 triangles. It produces SHG intensity about as large as that of KDP and is phase matchable. 3. Second-order Jahn-Teller (SOJT) distortion are easily occurred for Pb2+ due to the stereo-effect of the lone pair. Combined Pb2+ with borate, three new compounds, Pb2BO3F, Pb8B9O21F, Pb3OBO3F, have been grown by high temperature solution method from the PbO-PbF2-B2O3 system for the first time. (a) Pb2BO3F crystallizes in the hexagonal system, space group P63/m with unit-cell parameters a = 7.2460(3)Å, c = 14.5521(17)Å, Z = 6, V = 661.69(9)Å3, and Pb2BO3F consists of the distorted PbO3F2 groups and BO3 triangles which are all symmetric with each other in the gestalt structure to the extent that the Pb2BO3F compound crystallizes in the symmetric space group; (b) Pb8B9O21F crystallizes in the trigonal system, space group with unit-cell parameters a = 9.740(3)Å, b = 9.740(3)Å, c = 38.167(15)Å, Z = 6, V = 3135.5(8) Å3. The structure of the compound is solved by the direct methods and to the best of our knowledge, Pb8B9O21F is the first structure reported so far with isolated boron-oxygen anionic [B9O21]15- compound; (c) Pb3OBO3F crystallizes in the orthorhombic system, space group Pbcm with unit-cell parameters a = 7.6313(14) Å, b = 6.5229(12)Å, c = 11.906(2)Å, Z = 4, V = 592.66(19)Å3. Pb3OBO3F consists of Pb(1)O3F tetrahedra, Pb(2)O4 tetrahedra and BO3 triangles which build up the symmetrical chains extended along the c-axis. Bismuth(III) is a heavy metal cation containing a lone electron pair which may induce SOJT distortion in the structure. Two bismuth-containing compounds have been obtained: (a) A new phase of the compound PbBiBO4 has been successfully synthesized via the standard solid-state reaction. It crystallizes in orthorhombic space group Cmca with lattice constants a = 10.782(3)Å, b = 10.502(3)Å, c = 7.477(2)Å, Z = 8, V = 846.7(4)Å3. The crystal structure is characterized by a three-dimensional structure consisting of BiO6 octahedra, PbO4 tetrahedra and BO3 triangles. The UV-Vis-NIR Diffuse-Reflectance spectrum shows that the ultraviolet cutoff edge for the PbBiBO4 crystal is about 310nm; (b) A new chlorine iodate, K2Bi(IO3)4Cl, has been grown using hydrothermal method from the KIO3-BiCl3 system. It crystallizes in the monoclinic system, space group P21/c with unit-cell parameters a = 11.216(3)Å, b = 12.260(3)Å, c = 10.444(2)Å, Z = 4, V = 1352.2(5)Å3. The material exhibits a three-dimensional structure consisting of interconnecting BiO7 units, K(1)O10 groups, K(2)O7Cl2 groups and IO3 groups. The powder X-ray diffraction pattern, Fourier transform infrared spectrum, thermal analysis and elemental analysis of the K2Bi(IO3)4Cl have been measured.
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4399
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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赵文武. 新型Ba7(BO3)3F5和KSr4B3O9等硼酸盐化合物的合成、结构和性能研究[D]. 北京. 中国科学院研究生院,2012.
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