SrTiO3单晶体生长过程中的溢流问题

本文以氯化锶和氯化钛为原料,采用控制水解法制备SrTiO3原料粉末,使用焰熔法生长了SrTiO3单晶体.晶体生长参数为:原料粉末粒度为-200+250目,炉膛气氛的氢氧比H/O为6.00,生长速度为12mm/h,获得了直径30mm,长60mm的单晶.晶体生长过程中,晶体顶部熔体的溢流是妨碍获得大尺寸完整晶体的一个最主要的问题.本文详细讨论了SrTiO3单晶体生长过程中的溢流的成因和解决办法.     

非真空密闭条件下的Ce3+: LiYF4晶体生长

本文报道了氟化物激光晶体Ce3+: LiYF4的坩埚下降法生长工艺.以高纯氟化物LiF、YF3和CeF3为初始试剂,按照LiF: YF3: CeF3 = 51.5: 47.5: 1.0的物质的量比配料,经高温氟化处理合成严格无水的Ce3+: LiYF4多晶料.将Ce3+: LiYF4多晶料密封于铂坩埚中,添加少量聚四氟乙烯粉末,可避免氟化物熔体的氧化与挥发,从而在非真空条件下实现Ce3+: LiYF4晶体的坩埚下降法生长,成功生长出尺寸达28 mm×70 mm的无色透明完整单晶.采用XRD、差热/热重分析、透射光谱和荧光光谱对Ce3+: LiYF4单晶基本性质的进行表征.结果表明,该晶体在320~3000 nm区域内的光透过率达90;以上,晶体在297 nm处有一强吸收峰;荧光光谱显示晶体在紫外光区310 nm、325 nm处有两个强发射峰.     

Ce3+单掺和Ce3+,Eu3+共掺杂CaF2晶体生长与光学特性研究

采用Bridgman方法在氩气氛保护的单晶炉内生长出了Ce3+掺杂的以及Ce3+和Eu3+共掺的CaF2晶体,利用Ce2O3和E2O3分别与氢氟酸反应合成了CeF3和EuF3掺杂试剂,对掺杂晶体生长的起始原料-特定组成的CaF2、CeF3、EuF3混合物进行了高温氟化处理,确定了掺杂晶体的物相,讨论了掺杂浓度对晶体紫外波段透过率的影响.此外,还初步分析了Ce3+和Eu3+共掺的CaF2晶体作为紫外滤光材料的可行性.     

磁性Fe3O4六方片状晶体和单晶纳米棒的水热合成

本文分别以FeSO4·7H2O、(NH4)2Fe(SO4)2·6H2O和NaOH、NH3·H2O为原料,以KClO4与KNO3为氧化剂,采用水热合成法分别合成出Fe3O4六角片状晶体和单晶纳米棒.产物分别用X射线衍射仪(XRD)谱图、透射电子显微镜(TEM)、选区电子衍射(SAED)谱图以及磁滞回线图谱加以表征.结果表明,反应物原料及氧化剂的选择对Fe3O4单晶的制备及其形态的影响至关重要.反应温度控制在110℃,时间为14h.室温下,Fe3O4六方片状晶体和单晶纳米棒的磁化率(Ms)和矫顽力(Hc)均有所区别.     

乙醇/ 水混合溶剂热法制备BaHfO3:Ce超微粒子

以Ba(NO3)2和HfOCl2·8H2O为原料,KOH为矿化剂,乙醇/ 水作溶剂,Ce(NO3),作为激活剂,在150～220 ℃和16～36 h的条件下,制备了掺杂Ce3+的BaHfO3超微粒子.用XRD,SEM等手段表征了粒子合成过程的物相变化及形貌特征;用荧光光度计分析了样品的激发光谱和发射光谱.结果表明,在n(Ba):n(Hf)=1:1,水热合成温度200℃,保温时间24 h,pH=13.5的条件下制备的BaHfO3:Ce粒子分散性好,形貌近球形,粒径约52nm.当掺杂Ce3+浓度为0.3 mol;时BaHfO3发光效果最佳.     

溶胶-凝胶法制备Y_(3-x)Ce_xAl_5O_(12)纳米粉体的研究

以Y(NO3)3.6H2O、Ce(NO3)3.6H2O、Al(NO3)3.9H2O、柠檬酸为主要原料,以聚乙二醇作为分散剂,采用溶胶-凝胶法合成了纳米级YAG∶Ce3+粉体。研究了煅烧温度、溶液中金属离子浓度、溶液pH值及Ce3+掺杂量等因素对制备纳米YAG∶Ce3+粉体的颗粒尺寸、颗粒形貌、物相的影响。结果表明:当溶液pH为=4.0、金属离子浓度为0.50 mol/L、煅烧温度为1000℃时,可以制备出具有良好的分散性,平均粒径在30 nm的粉体。     

棒状MnPO4·H2O单晶的生长及其形成机理研究

以MnCl2,NaNO3和H3PO4为原料,在温度为150℃的水热条件下反应12 h制备出了棒状MnPO4·H2O单晶.利用X射线粉末衍射(XRD)、场发射扫描电镜(FESEM)和透射电子显微镜等手段对产物进行表征.结果表明,合成的产物为MnPO4·H2O单晶棒,直径为0.78～1.9 μm,长度达几十微米.讨论了水热条件下反应时间对产物形貌的影响,并对棒状MnPO4·H2O单晶的生长机理进行了分析.     

KCl辅助EDTA水热合成t-LaVO4∶Eu3+粉体

以LaCl3·nH2O、Eu2O3和NH4VO3为原料,采用KCl和EDTA为辅助剂,在较高pH值下水热合成了t-LaVO4∶Eu3+粉体.通过添加KCl和EDTA的不同组合,分析了对LaVO4∶Eu3粉体微观结构及荧光性能的影响.结果表明:当初始溶液pH=11和12时,添加KCl+EDTA可制备单一四方相LaVO4∶Eu3+粉体,并推断了LaVO4∶Eu3+晶体的形成机理.加入KCl影响了LaVO4∶Eu3的晶体结构,使LaVO4∶Eu3+粉体颗粒尺寸增大,荧光性能增强.当Eu掺杂摩尔浓度为5;时,LaVO4∶ Eu3+束状棒有最高的红光发射强度.     

闪烁晶体用高纯无水稀土卤化物的制备与表征

LaBr3 ∶Ce、LuI3 ∶Ce、SrI2 ∶Eu等新型卤化物闪烁晶体因其高光输出、高能量分辨率等优异的闪烁特性而引起人们的广泛关注.高纯无水稀土卤化物是生长上述闪烁晶体所必需的原料,但其制备困难和高昂成本,严重制约了这些晶体的发展和应用.本文报道了无水LaBr3、CeBr3、LaCl3、CeCl3、LuI3、GdI3、YI3、CeI3、EuI2等常用稀土卤化物的制备方法,并对其有效表征手段进行了介绍.     

Ce:YAG单晶复合红色荧光粉的制备及其在白光LED上的应用

采用提拉法生长了Ce:YAG单晶,并以Ce:YAG单晶取代传统Ce:YAG荧光粉用于制备白光发光二极管(LED),研究了Ce:YAG单晶厚度的变化对其色坐标、亮度、发光效率和色温的影响.由于460 nm 蓝光芯片激发的Ce:YAG单晶白光LED缺少红光成分,采用流延法将红色荧光粉CaAlSiN3:Eu2+涂覆在Ce:YAG单晶衬底上制备白光LED.制备的白光LED色度随红粉含量的变化由冷白光逐渐向暖白光区域移动,色温逐渐降低、显色指数上升.研究结果表明Ce:YAG单晶复合红色荧光粉的方式可以应用于大功率LED照明.     

Infrared vibrational Modes in Tl3SbS3, Tl3AsS3, and Tl3AsSe3 crystals

Reflectivity spectra of Tl₃SbS₃, Tl₃AsS₃, and Tl₃AsSe₃ crystals have been investigated in the wave number range 50–600 cm⁻¹ for the polarizations E∥c and E⟂c. The fundamental phonon parameters, the limiting dielectric constants ϵ_∞ and ϵ_S and the reflectivity spectra contours have been calculated by using classical dispersion relations for both E∥c and E⟂c configurations. The Szigeti effective charges and the relative ion charges of As, Tl, Sb, Se, S anions and cations have been calculated in dependence on the incident light polarization.     

The structures of three trimethylarsine-boron trihalide adducts: (CH3)3AsBCl3, (CH3)3AsBBr3, and (CH3)3AsBI3

An X-ray structure analysis of three trimethylarsine-boron trihalide adducts has been undertaken. Crystals of (CH₃)₃AsBCl₃ and (CH₃)₃AsBBr₃ are monoclinic with space groupP2₁/m (No. 11) withZ=2 while those of (CH₃)₃AsBI₃ are orthorhombic with space groupPnma (No. 62) withZ=4. For (CH₃)₃AsBCl₃,a=6.497(3) Å,b=10.735(3) Å,c=7.070(2) Å,=111.8(3)°,V=458.4(3) ų,R=0.0343. For (CH₃)₃AsBBr₃,a=6.672(4) Å,b=11.135(7) Å,c=7.199(4) Å,=111.5(1)°,V=497.7(5) ų,R=0.0434. For (CH₃)₃ÅsBI₃,a=13.113(7) Å,b=11.733(5) Å,c=7.387(3) Å,V=1136.5(5) ų,R=0.0329. The As-B bond lengths are 2.065(6), 2.04(1), and 2.03(1) Å, respectively, for the chloride, bromide, and iodide. These and other structural parameters are discussed with reference to previous predictions based on vibrational spectra and previous structural studies on the trimethyl-phosphine and trimethylamine adducts.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

Second harmonic generation properties of Ca3(O3C3N3)2 ‐Sr3(O3C3N3)2 solid solutions

Solid solutions of the second harmonic generation (SHG) materials Ca₃(O₃C₃N₃)₂ (CCY) and Sr₃(O₃C₃N₃)₂ (SCY) were prepared via exothermic solid state metathesis reactions from appropriate amounts of the corresponding metal chlorides and potassium cyanate at 525 °C. The change in SHG intensity caused by the successive cation substitution is reported. Differential thermal analyses are used to explore the SCY–K(OCN) phase diagram as a medium for the growth of SCY crystals.     

Crystal Growth and Spectroscopic Characterisation of BiB3O6:RE3+ (RE3+ = Pr3+, Nd3+, Gd3+, Er3+, Tm3+)

Large single crystals of optical quality of BiB₃O₆:RE³⁺ (RE³⁺ = Pr³⁺, Nd³⁺, Gd³⁺, Er³⁺, Tm³⁺) were grown from nearly stoichiometric melts using the top‐seeding growth technique to dimensions up to 12 x 12 x 18 mm³. Absorption spectra were measured in the wavelength range from 10000 cm^‐1 to 30000 cm^‐1 with an absorption spectrometer to estimate the doping concentration of RE³⁺. For the determination of the phonon energies and the quenching behaviour of the host lattice IR and Raman spectra were recorded.     

Growth and characteristic of Sr3Tb(BO3)3 crystal

A new borate single crystal of Sr₃Tb(BO₃)₃ with dimension Ф20×25 mm² has been grown by the Czochralski method. The grown crystal was characterized by DTA–TGA, FTIR and X-ray powder diffraction analysis. The results showed the crystal with [BO₃]^3? is congruently melting at 1351.35 °C which belongs to hexagonal structure. The hardness of Sr₃Tb(BO₃)₃ crystal is 422.5 VDH, and is equal to 5.0 moh. The thermal expansion coefficients were determined to be 2.08×10^?5/°C along (1 0 0) direction and 7.43×10^?6/°C along (0 0 1) direction and the transmission spectrum was measured in 320–1800 nm at room temperature. The magnetic properties of the single crystal were studied which showed its paramagnetism and magnetic anisotropy. The specific Faraday rotation of single crystal was measured at room temperature in 532, 633, and 1064 nm wavelength. The Verdet constants and magneto-optical figures of merit were investigated. The primary emphasis is laid to explore a new magneto-optical material, all the magneto-optical properties of Sr₃Tb(BO₃)₃ are comparing to the ones of TGG.     

Growth and magnetic‐optical properties of Sr3Gd(BO3)3 and Sr3TbxGd1‐x(BO3)3 single crystals

Single crystals of Sr₃Gd(BO₃)₃ (SGB) and Sr₃Tb_xGd_1‐x(BO₃)₃ (TSGB) with dimension Ø 20 mm×20 mm have been grown by Czochralski method. The grown crystals were characterized by X‐ray powder diffraction analysis which showed the crystals belong to hexagonal structure with lattice parameters of a=b=1.254 nm, c=0.926 nm (SGB) and a=b=1.253 nm, c=0.925 nm (TSGB). In TSGB, x=17.7% was obtained by X‐ray fluorometry which showed the segregation coefficient of Tb is closed to 1. The transmission spectrum was measured, which indicated the crystals have high transmittance in 400‐1100 nm region. The Faraday rotation of single crystals at 532 nm wavelength was measured at room temperature. Finally, the Verdet constants were investigated, (SGB) V=17.9 degcm^‐1T^‐1 and (TSGB) V=21.3 degcm^‐1T^‐1. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

3-Methyl-3a,4-Dihydro-3H-Thiochromeno[4,3-c]isoxazol

Abstract  The crystal structure of the title compound, C₁₁H₁₁NOS, was determined by an X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P2₁/c with cell parameters a = 10.533(2) ?, b = 12.7826(19) ?, c = 7.6491(17) ?, β = 107.997(17)^°, V = 979.5(3) ?³ and Z = 4. The S containing heterocycle adopts a sofa conformation, whereas the 5-membered ring adopts an envelope conformation. The crystal packing is characterized by weak C–H···N contacts and π-stacking interactions. Graphical Abstract  The title compound, 3-methyl-3a,4-dihydro-3H-thiochromeno[4,3-c]isoxazol was synthesized by an 1,3 dipolar cycloaddition reaction and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the aromatic 6-membered ring is planar, whereas the ring containing the S atom adopts a sofa conformation and the 5-membered ring an envelope conformation. The methyl group is in an equatorial position.      

铒镱双掺的钒酸钇和铌酸锂晶体中的铒离子的上转换发光

利用J-O理论,计算了在铒、镱双掺的钒酸钇和铌酸锂晶体中的铒离子在室温下的晶场唯象参数Ωλ(λ=2,4,6)及辐射跃迁几率、无辐射跃迁几率和共振跃迁几率.考虑到铒、镱间的能量转移,写出了在这些晶体中的铒离子的速率方程.速率方程的解表明,在铒、镱双掺的钒酸钇晶体中的铒离子的550 nm的上转换发光,比它在铒、镱双掺的铌酸锂晶体中更为有效.这一理论结果与我们的实验观察结果一致.