Crystal Growth,Thermal and Linear Optical Properties of LiGeBO4

The origin of reported twin domains of LiGeBO₄ was investigated by methods of thermal analysis. The twins were found to result from a phase transition which occurs 2‐3 K below the peritectic decomposition of the compound. Large single crystals of LiGeBO₄ were grown by an improved growth method using the top‐seeding technique. Linear optical properties (refractive indices between 404 nm and 2325 nm and unpolarized absorption spectrum) as a basis for nonlinear optical investigations were determined. Unfortunately, LiGeBO₄ is not phase matchable.     

K2Al2B2O7晶体的热学性质研究

K2Al2B2O7(KABO)晶体是近年发现的一种有应用前景的深紫外非线性光学晶体,也是目前唯一一种可以生长出大尺寸单晶的BO3基团非线性光学晶体.KABO有可能用于固态激光器的266nm及193nm高功率输出.本文对该晶体的物理化学性质及热学性质进行了研究,KABO晶体不潮解,不溶于水、酒精等溶剂,可溶于盐酸,硝酸和磷酸等强酸;测得莫氏硬度为5.5～6.5,用浮力法测得其密度为2.47g/cm3;用差热分析(DTA)方法测量其熔点为1109.7℃.用热重分析(TGA)方法结合分解产物的粉末X射线衍射(XRD)分析,确定KABO在900℃以上开始分解,分解产物主要为KAl11O17和K2Al24O37;用热机械分析仪测量了其热膨胀系数,沿物理学轴X、Y、Z方向分别为8.4×10-6/K、7.7×10-6/K、1.65×10-5/K.在室温至300℃温度范围内测量了KABO晶体的比热变化,比热随温度的升高线性增大.在47.6℃和294.6℃时比热分别为1.0084J/g℃与1.39J/g℃.     

Linear Optical Properties of the Nonlinear Optical Calcium and Strontium Tartrato-Antimonates (III), Ca[Sb2 {(+) - C4H2O6}2] x2H2O and Sr[Sb2{(+) - C4H2O6}2 ] x2H2O

The study of nonlinear optical properties of crystals requires a thorough knowledge of the linear optical properties: knowledge of the transparency range is necessary, some information about the optical activity is useful. Above all, high quality refractive indices (with errors less than 10^-4) and their dispersion are the most important basic data, as they enable a detailed analysis of phase-matching conditions of nonlinear optical processes and an estimation of the nonlinear optical potential of a new non-centrosymmetric crystal. Such high quality refractive indices are also necessary in other areas of nonlinear optics, for example for the evaluation of nonlinear optical measurements like measurements of Maker fringes. In this short communication we present the linear optical basis for nonlinear optical investigations of the title compounds. The Sr compound has been known for a long time; its morphological crystallography is already presented in the famous Chemische Krystallographie by Paul Groth (1910). The Ca salt was first synthesized 1983 by one of us (L.B.).     

Preparation and Properties of a Novel Nonlinear Optical Crystal: MnHg(SCN)4(H2O)2.2(C3H6CONCH3)

In this article, diaquatetrakis (thiocyanato) manganese(II) mercury(II)‐N‐methyl‐2‐pyrrolidone, MnHg(SCN)₄(H2O)₂.2(C₃H₆CONCH₃), (abbreviated as MMTWMP), a new organometallic nonlinear optical crystal material is reported. The structure, optical and thermal characterizations were determined by elemental analysis, infrared and Raman spectroscopy, X‐ray powder diffraction, thermogravimetric analysis, differential scanning calorimetry, special heat, SHG measurements and UV/Vis/NIR optical transmission spectra. It belongs to the tetragonal crystallographic system, with cell parameters: a = 12.1294, c = 8.2238Å, V = 1211.27ų. Single crystals with dimensions up to 8 × 7 × 5 mm³ have been obtained. The morphology of the crystals was indexed. The MMTWMP crystal exhibits good physicochemical stability at normal temperature and pressure. Its UV transparency cutoff is 360 nm, which is shifted to the violet by 13 nm, as compared with MnHg(SCN)₄ (MMTC); the optical transmission is 44.82% at 404 nm, which is by 17.46% higher than that of MMTC.     

Growth and Optical Properties of NaY(WO4)2:Eu Crystals

NaY_0.99Eu_0.01(WO₄)₂ crystals were grown along <101> and <001> directions. Single crystals with high quality can be obtained when they were grown along <101> direction from a melt with a small deviation from stoichiometric composition. Eu ions exist in two valences in the as‐grown crystals, in one valence after annealing only. The fluorescence spectrum shows the Stark splitting of energy levels of Eu ions is in accordance with the site symmetry of S₄.     

Nd3+:Na3La9O3(BO3)8晶体生长和光谱性能

采用顶部籽晶法生长Nd3+:Na3La9O3(BO3)8 晶体.在室温下测试了吸收光谱、发射光谱和荧光寿命.应用Judd-Ofelt理论评价了Nd3+:Na3La9O3(BO3)8晶体的光谱性能.812 nm处较宽的吸收峰适合AlGaAs LD泵浦的吸收.分别计算了Nd3+离子的唯象强度、谱线强度、辐射寿命、荧光分支比和荧光量子效率.     

有机模板硼酸盐[C6N2H18]0.5[B5O6(OH)4]的合成、晶体结构及变温荧光性质

以硼酸和有机胺为原料在水溶液体系中合成了一种有机模板硼酸盐[C6N2H18]0.5[B5O6(OH)4](1a),通过X射线单晶衍射仪对其晶体结构进行了检测.此外,对其进行了元素分析、X射线粉末衍射、红外光谱、热重差热分析及固态荧光光谱等表征.结果表明,该化合物属单斜晶系,空间群为P21/n,晶胞参数为a=0.8593(2) nm,b=1.4015(4) nm,c=1.0293(3) nm,β=104.723(3)°,V=1.1989(6) nm3,Z=4.阴离子基团[B506 (OH)4]-通过强的氢键连接形成具有三种不同形状孔道的新颖三维超分子骨架结构.该化合物在波长为248 nm的激发光下,发射出最大发射波长为375 nm的紫外光.对化合物进行不同温度的热处理后,其荧光性质发生了明显的变化.     

羟基硅酸镁纳米棒的制备及光吸收性能研究

以Mg(NO3)2·6H2O和纳米SiO2为原料,采用水热法,合成了Mg3Si2O5(OH)4纳米棒.采用X射线衍射(XRD)及场发射扫描电子显微镜(FE-SEM)对样品的物相组成和微观形貌进行了表征.并采用紫外-可见漫反射测试(UV-vis DRS)测定了样品的光吸收性能,DRS结果显示Mg3Si2O5(OH)4纳米棒的光吸收主要集中在紫外光区,结合Kubelka-Munk方程计算得出Mg3Si2O5(OH)4纳米棒的光学带隙为4.98 eV.     

Na3La2(BO3)3晶体生长及光谱特性

本文以起始摩尔比为1:1的Na2CO3:H3BO3,并添加5;质量分数的NaF为助熔剂,用顶部籽晶法生长出φ35mm×5mm的透明Na3La2(BO3)3单晶.该晶体属正交晶系,空间群:Amm2,晶胞参数为a=0.51580(10)nm,b=1.1350(2)nm,c=0.73230(15)nm,α=β=γ=90°.测量了Na3La2(BO3)3晶体在室温下的透过光谱,紫外截止波长约为200nm.该晶体常温下稳定,不吸潮,但却易溶于稀酸.     

Nonlinear optical properties of strontium tartrato‐antimonate(III) dihydrate,Sr[Sb2{(+)‐C4H2O6}2]·2H2O

The tensor of nonlinear optical susceptibility for second harmonic generation [d^SHG _ijk ] of hexagonal (point group 6) strontium tartrato‐antimonate(III) dihydrate, Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O, was determined using the Maker fringes method and a Nd:YAG laser with a wavelength of 1064 nm. The largest component of the tensor d^SHG ₃₃₃ amounts two times d^SHG ₁₁₁ of α‐quartz. Effective nonlinear optical susceptibility d^SHG _eff is given for phase matching type I for several wavelengths (for type II d^SHG _eff is nearly zero). The thermal stability of crystals of Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O was determined in the temperature range from 153 K to 573 K by means of thermal expansion measurements and thermogravimetry. The temperature dependence of thermal expansion coefficients is given in the range from 153 K to 293 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of Rb2[GeO2(OH)2]·2H2O

Single crystals of Rb₂[GeO₂(OH)₂] · 2H₂O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna2₁, a = 13.523(6) Å, b = 8.143(4) Å, c = 13.407(6) Å, Z = 8, R ₁ = 0.0506. In [GeO₂(OH)₂]^2? anions, the Ge-O distances (1.71–1.73(1) Å) are shorter than the Ge-OH distances (1.76–1.80(1) Å). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.     

Y0.145Gd0.855Ca4O(BO3)3混晶的晶体生长和压电、热膨胀性能

利用提拉法成功生长出了Y0.145Gd0.855Ca4O(BO3)3(Y0.145Gd0.855COB)混晶.对其压电系数和热膨胀系数进行了测量,测得压电系数d26为9 pC/N,计算得到热膨胀系数α11,α22 α33分别为12.97×10-6/℃,5.94×10-6/℃,8.03×10-6/℃.通过与YCa4O(BO3)3和GdCa4O(BO3)3晶体的对比,分析了Re3+半径和Re3+、Ca2+的无序分布对于Y0.145 Gd0.855COB混晶的压电性能和热膨胀性能的影响.     

Electronic Structure of [Cu(C7H4NO3S)2(H2O)4] · 2H2O Crystal

The electronic absorption spectrum and ESR spectrum of the crystal of the title compound [Cu(C₇H₄NO₃S)₂(H₂O)₄] · 2 H₂O, are measured. The experimental results are discussed quantitatively by using the ligand field theory and the radial wave function of non-free Cu(II). The electronic structure of the compound is in agreement with its crystal structure.     

Structure of diaqua(itaconato) cadmium(II), [Cd(C5H4O4)(OH2)2]

[Cd(C₅H₄O₄)(OH₂)₂] (1), crystallizes in the monoclinic system, space groupP2₁/n, with lattice parametersa=7.323(2),b=16.028(6),c=7.202(2) Å, β=113.11(1)°, andZ=4. The Cd atom coordinates to seven oxygens in a monocapped trigonal antiprism fashion. The antiprisms share one vertex to form chains which run approximately parallel to thec axis. The itaconate ligands link the chains to form layers which stack along theb axis.     

Na3Sm2(BO3)3的晶体生长及热学和光谱性质

以Na2CO3-H3BO3为助溶剂,用顶部籽晶法生长了14mm×8mm×2mm的Na3Sm2(BO3)3晶体.差热分析(DTA)表明Na3Sm2(BO3)3非同成分熔融,熔点为1089.1℃.该晶体易溶于酸,在空气条件下能稳定存在,不易潮解.测量了室温下晶体在200～2500nm范围内的吸收光谱,并对跃迁能级进行了初步指认.     

CdWO4闪烁晶体的生长及其光学性能的研究

本工作生长出了φ57mm×45mm的大尺寸CdWO4单晶,并报道了该晶体的最佳生长工艺.对CdWO4原料的一次烧结物、生长炉壁的挥发物进行了XRD谱的测试分析,结果表明一次烧结可以得到基本成相的多晶料;生长原料CdO较WO3更易挥发.同时,测试了CdWO4晶体的一些光学性能,初步探讨了该晶体的发光特性,分析表明氧退火有利于提高晶体的透过率,这可能是由氧退火使氧空位减少所致.此外,该晶体的本征发光主要是由蓝、绿光所组成的.     

水热法生长非线性光学晶体K4Gd2(CO3)3F4

采用水热法,探索了 K4Gd2(CO3)3F4晶体的析晶条件,诸如生长原料及配比、生长温度、生长周期等,并成功生长了毫米级的透明单晶.对生长的晶体进行了XRD、UV-Vis-NIR、SHG等测试,结果表明,K4Gd2( CO3)3F4晶体在380～2000 nm波段的透过率超过80;,紫外吸收截止边低于200nm;其二阶非线性光学效应约为KDP的3.5倍.     

助熔剂法生长非线性光学晶体Cd3Zn3B4O12及其性质研究

本文以PbO-0.25B2O3为助熔剂,利用顶部籽晶法获得了较大块的Cd3Zn3B4O12单晶.透过率测试结果显示该晶体的紫外截止波长位于310 nm处.利用Kurtz-Perry的方法对晶体的倍频效应进行了测试,结果显示该晶体的粉末倍频效应约为KDP的5倍,且能实现相位匹配.晶体的光损伤阈值约为840 MW(1064 nm,10 ns).该晶体的热分析结果显示Cd3Zn3B4O12晶体在熔点温度以上会产生分解,这也是阻碍高质量大块Cd3Zn3B4O12晶体生长最主要的因素.