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新型硼酸盐溴硼酸钾及氯氟硼酸钡非线性光学晶体的生长及性质研究
张敏
学位类型博士
导师潘世烈
2012-05
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
关键词溴硼酸钾 氯氟硼酸钡 非线性光学晶体 晶体生长 硼酸盐
摘要本论文在含卤素碱金属和碱土金属硼酸盐体系,以及复合金属硼酸盐体系合成了一系列化合物,包括K3B6O10Br、BaClBF4、Li2Sr4B12O23、NaPbB5O9和BaCd(BO3)2,其中K3B6O10Br和BaClBF4化合物为非中心对称结构。对这五种化合物的合成,晶体生长、性能表征等进行了研究。 首次利用顶部籽晶法生长出25 mm × 25 mm × 12 mm高光学质量的含卤素碱金属硼酸盐K3B6O10Br单晶,针对该晶体生长体系中含有易挥发的溴,采用了KF·2H2O-PbO复合助熔剂,将晶体生长温度降低到595 °C。晶体结构解析表明,K3B6O10Br晶体属于三方晶系,空间群为R3m,晶胞参数为a = 10.1153(8) Å,b = 10.1153(8) Å,c = 8.8592(14) Å,Z = 3,V = 785.02(15) Å3,晶体结构为相互嵌套的K–Br三维框架和3∞[B6O10]网络。其粉末倍频效应为3倍KDP,偶极矩计算显示BO3和KO6Br2多面体的偶极矩方向朝向相同,微观二阶极化率得到叠加,导致其倍频效应较大。K3B6O10Br晶体透过范围为230-3500 nm,能带及态密度计算表明该晶体为直接能隙,带宽为4.873 eV,主要由Br 4p,K 3p和O 2p轨道决定。采用直角棱镜法测试了晶体的主折射率no、ne,结果显示K3B6O10Br晶体为负单轴晶,可见光范围内的双折射率为0.046-0.049之间,拟合其Sellmeier方程,利用该方程计算K3B6O10Br晶体的I类和II类相位匹配区间倍频波范围分别为:290-3000 nm和420-3000 nm。按照计算相位匹配角切割晶片进行倍频输出实验表明,K3B6O10Br晶体能够输出532 nm及355 nm激光,证明计算的相位匹配角较为准确。热膨胀测试表明,晶体在[100],[001]和[110]方向的热膨胀系数分别为α[100] = 8.96 × 10-6/K,α[001] = 13.23 × 10-6/K和α[110] = 8.41 × 10-6/K,三个方向上的热膨胀差异较小,在晶体生长及加工时不易发生开裂,有利于获得优良的晶体器件。K3B6O10Br晶体莫氏硬度为4-5之间,激光损伤阈值大于6 GW/cm2,在空气中不潮解,溶解实验表明其微溶于水。综合晶体性能测试结果,K3B6O10Br是一种潜在的紫外非线性光学晶体材料。 采用水热法生长了尺寸为5 mm × 5 mm × 2 mm的含卤素碱土金属硼酸盐BaClBF4晶体,结构解析表明该晶体为正交晶系,空间群Pmn21,晶胞参数a = 5.228(3) Å,b = 9.351(5) Å,c = 4.734(3) Å,V = 231.4(2) Å3,Z = 2。晶体结构特点为[Ba2Cl2]2+层与孤立的BF4基团,沿b方向交叠形成,该结构是类Aurivillius型结构(pseudo-Aurivillius type),能量弥散X射线能谱仪(EDS)结果验证了结构解析的正确性。BaClBF4的透过范围为0.19-8.5 μm,能带及态密度计算表明其为间接能隙,能隙为5.55 eV,主要是Cl 3p和Ba 6s轨道决定。偶极矩计算表明,BaCl4F7多面体具有较大的偶极矩,但是其在y方向上的相反排列,使得微观极化率抵消,最终宏观倍频效应较小,仅为1/5倍KDP。 报道了三种新的复合金属硼酸盐化合物,Li2Sr4B12O23 、NaPbB5O9和BaCd(BO3)2。其中Li2Sr4B12O23晶体为单斜晶系,空间群P21/c,晶胞参数a = 6.4664(4) Å,b = 8.4878(4) Å,c = 15.3337(8) Å,β = 102.024(3) °,V = 823.13(8) Å3,Z = 2。结构中含有3∞[B10O18]6-三维网络和孤立的[B2O5]4-基团,Li和Sr原子位于3∞[B10O18]6-三维网络结构间的孔洞中。NaPbB5O9为单斜晶系,空间群P21/c,晶胞参数a = 6.5324(10) Å,b = 13.0234(2) Å,c = 8.5838(10) Å,β = 104.971(10) °,V = 705.471(17) Å3,Z = 4。基本结构单元B5O9基团之间沿ac平面相连形成起伏的2∞[B5O9]3-层状结构。Na和Pb原子嵌在层之间平衡电价形成最终结构。Ba2Cd(BO3)2晶体为单斜晶系,空间群C2/m,晶胞参数a = 9.6305(4) Å,b = 5.3626(3) Å,c = 6.5236(2) Å,β= 118.079(3)°,V = 297.25(2),Z = 2。基本结构单元BO3和CdO6通过端氧相连在ab平面上形成2∞[Cd(BO3)2]4-层。
其他摘要Several new compounds, K3B6O10Br, BaClBF4, Li2Sr4B12O23, NaPbB5O9 and BaCd(BO3)2 were synthesized, therein K3B6O10Br and BaClBF4 crystallize in non-centrosymmetric space group. In this dissertation, the synthesis, crystal growth and properties characterization of above compounds were investigated. The K3B6O10Br single crystal with high quality (25 mm × 25 mm × 12 mm) was obtained using top-seeded solution growth (TSSG) method. Since the volatilization of bromine in the crystal growth system, KF·2H2O and PbO binary fluxes were introduced, and the crystal growth temperature were decreased to 595 °C. K3B6O10Br crystallizes in a non-centrosymetric trigonal system, space group R3m with cell parameters a = 10.1153(8) Å, c = 8.8592(14) Å, Z = 3, V = 785.02(15) Å3. It has a three–dimensional network consisting of B6O13 units, which are surrounded by K–Br framework. Nonlinear optical measurements demonstrate that the material has second harmonic generation (SHG) properties, with efficiency approximately three times that of KH2PO4. Dipole moments calculation shows BO3 and KO6Br2 polyhedra has similar direction, micro-second-order polarizability stacks and leads to a relatively strong second harmonic generation. K3B6O10Br crystal is found to be transparent from 230 to 3500 nm, band structures and density of states calculation indicate that K3B6O10Br is direct band gap 4.873 eV. The band gap is determined by Br 4p, K 3p and O 2p orbitals. The refractive indices no and ne were measured by the right angle wedge method, the birefringence value is about 0.046 to 0.049 between 404.7 nm and 694.3 nm, and using the value to fit the Sellmeier equation. The phase matching range has been calculated using Sellmeier equation, and it could be phase matchable for type I and type II in the double frequency wavelength of 290-3000 nm and 420-3000 nm, respectively. Hence, K3B6O10Br theoretically could obtain 290-3000 nm SHG. The SHG experiment, using the crystal cut in the calculated phase matching angle, shows that K3B6O10Br crystal can achieve 532 and 355 nm frequency-doubled wavelength, which proves accuracy of the phase matching calculation. The thermal expansion coefficient of K3B6O10Br crystal in the [100], [001] and [110] direction are 8.96 × 10-6/K, 13.23 × 10-6/K and 8.41 × 10-6/K, respectively. The difference between three direction thermal expansion coefficients is neglectable, which is beneficial to the machining and cutting. The hardness of K3B6O10Br is about 4-5 Mohs, and optical damage threshold is more than 6 GW/cm2. K3B6O10Br is nonhygroscopic and slightly dissolved in the distilled water. Based on the experiment results, K3B6O10Br is a potential UV nonlinear optical crystal. The BaClBF4 crysal is grown via hydrothermal method with size up to 5 mm × 5 mm × 2 mm, it crystallizes in the orthorhombic space group Pmn21 with a = 5.228(3) Å, b = 9.351(5) Å, c = 4.734(3) Å, Z = 2. The crystal structure can be described as an alternate stacking of the cationic [Ba2Cl2]2+ layers with the anionic [BF4]- layers along the b direction, and the [Ba2Cl2]2+ layer in BaClBF4 is a pseudo-Aurivillius type layer similar to the [Bi2O2]2+ layer in Aurivillius phase. The Energy Dispersive X-ray Spectroscopy (EDS) results verified the structure. The transmittance range of BaClBF4 is from 0.19 to 8.5 µm. The band structure and DOS calculation conclude an indirect energy gap 5.55 eV, Cl 3p and Ba 6s orbitals determine the energy band gap of BaClBF4. Dipole moments of BaCl4F7 polyhedra in y direction canceled out lead to a weak SHG response of BaClBF4, which is about 1/5 times of KH2PO4. Three new metal complex borate, Li2Sr4B12O23, NaPbB5O9 and BaCd(BO3)2 were synthesized. Li2Sr4B12O23 crystallizes in the monoclinic space group P21/c with a = 6.4664(4) Å, b = 8.4878(4) Å, c = 15.3337(8) Å, β= 102.02(3)°, Z = 2. The crystal structure is composed of [B10O18]6- network and isolated [B2O5]4- units. NaPbB5O9 crystallizes in the monoclinic space group P21/c with a = 6.5324(10) Å, b = 13.0234(2) Å, c = 8.5838(10) Å, β =104.971(10)°, Z = 4. The crystal structure is composed of double ring [B5O9]3- units, [PbO7] and [NaO7] polyhedra. The [B5O9]3- groups connect with each other forming two-dimensional infinite ∞[B5O9]3- layers, [PbO7] polyhedra linked together via corner–sharing O atom forming novel infinite ∞[PbO6] chains along the c axis. Ba2Cd(BO3)2 crystallizes in the monoclinic space group C2/m with a = 9.6305(4) Å, b = 5.3626(3) Å, c = 6.5236(2) Å, β= 118.079(3)°, Z = 2. The crystal structure is composed of isolated BO3 triangles, CdO6 octahedra and [BaO9] polyhedra. CdO6 are vertex-connected with six BO3 to form infinite ∞[Cd(BO3)2] layers extending in (001) plane, and two rows of Ba atoms closely occupy two side of ∞[Cd(BO3)2] layers to form stoichiometric sheets.
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4400
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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张敏. 新型硼酸盐溴硼酸钾及氯氟硼酸钡非线性光学晶体的生长及性质研究[D]. 北京. 中国科学院研究生院,2012.
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