水热法制备PEG-400辅助下的Bi3+敏化NaLa(WO4)2:Eu3+荧光粉及其发光性能研究

本文通过PEG-400辅助水热合成了NaLa(WO4)2:Eu3+-Bi3+红色荧光粉,并且运用XRD、SEM、EDS、PL等测试手段对荧光粉体的结构、形貌、荧光性能进行了表征.实验结果表明:在pH=7.0~10.0范围内,可以制备出纯相的NaLa(WO4)2:Eu3+-Bi3+.当Eu3+的掺量达到5mol;,产品呈现为分散性较好的四方状微晶,粒径为5~6 μm.增加Bi3+的掺量,产物形貌向圆球状转变.在λex=396 nm的波长激发下,粉体发出强烈红光,此时的Eu3+位于NaLa(WO4)2晶体中非反演对称中心位置.当Bi3+的掺杂量为0.8mol;时,Eu3+的荧光强度提升了近4.2倍,持续增加Bi3+掺量,会出现浓度猝灭现象.不仅如此,关于铋离子桥:WO2-4 →Bi3+→Eu3+的级联能量传递机理也进行了探究.     

Eu3+对Ba3La(PO4)3∶Dy3+白光荧光粉发光性能的影响及发光机理的研究

采用高温固相法制备了Ba3La1-x-y(PO4)3∶ xDy3+,yEu3+白光荧光粉,并通过XRD和荧光光谱性能分析手段对样品的物相组成、发光性能和发光机理进行了研究.结果表明:由于Eu3+的掺杂影响了Ba3La(PO4)3∶ Dy3+荧光粉的晶体场环境,在Dy3+的6F9/2能级与Eu3+的5D0能级间发生交叉弛豫,并通过能量共振转移,Dy3向Eu3+传递能量,Ba3La1-x-y(PO4)3∶xDy3+,yEu3+荧光粉在350 nm紫外光激发下同时出现了Dy3+和Eu3+的特征发射,发射光谱中增加了红光成分,改善了色温.实验得出Dy3+和Eu3+掺杂浓度分别为0.08和0.06时,荧光粉的发射光最接近于理想白光.     

ZnWO4∶Eu3+,Dy3+白色荧光粉的微波水热合成及其发光性能

采用微波水热法快速合成了Zn0.9975-xWO4∶0.0025Eu3+,xDy3+ (x =0,0.0025,0.005,0.01,0.02)一系列单一基质白色荧光粉.通过X射线粉末衍射仪、扫描电镜、荧光分光光度计、光谱分析仪等对样品进行分析表征.结果 表明:在180℃下仅用2h即可合成单斜晶系黑钨矿结构的ZnWO4∶Eu3+,Dy3纯相,且有较高的结晶度;样品颗粒为类球形,尺寸在50 nm左右.在303 nm的紫外光激发下,该荧光粉可以同时产生WO2-、Dy3和Eu3+的特征发射,主峰分别位于472 nm、583 nm和617 nm.当样品组成为ZnWO4∶0.0025 Eu3,0.005Dy3+时,其色坐标为:x=0.3359,y=0.3064,接近理想白光,色温:5290 K.     

NaY(Mo/WO4)2∶Eu3+红色荧光粉的合成和发光性能

利用固相法合成了Eu3+掺杂的NaY(Mo/WO4)2红色荧光粉,并用对所获得的样品进行了XRD和激发-发射光谱表征.研究发现随着Eu3+掺杂量逐渐增加,发光强度随之变化.当Eu3掺杂浓度为30mo1;,荧光粉具有最强的发光强度.荧光粉能被395 nm波长紫外光有效激发,发射光谱主要体现为Eu3+的5 D0→7F2电偶极跃迁的红光发射,因此适合于解决白光LED缺乏红光成分而导致的显色性差问题.研究发现适量的W6+取代Mo6+,不但可以提高荧光粉的发光强度,而且有利于改善材料的色纯度.W6的最佳掺杂浓度为10at;.在395 nm激发下,NaY(Mo0.9W0.1O4)2∶Eu3+荧光粉的色度坐标为(0.666,0.331),优于传统商业红色荧光粉Y2O2S:Eu3+.     

适用于近紫外LED芯片的白光荧光粉Y2(MoO4)3∶DY3+的发光特性

采用高温固相法制备纯相Y2( MoO4)3∶Dy3+荧光粉,并对其晶场及发光性质进行研究.晶场分析结果表明:Y3+格位晶场结构近似为对称性很低的C2,因此样品在近紫外区有很强f-f激发峰,适合于近紫外LED芯片.在387 nm激发下,主要发射峰为Dy3+的特征发射487 nm(蓝光,4F9/2→6H15/2)和574 nm(黄光,4F9/2→6H13/2).增大Dy3+掺杂浓度,黄光与蓝光的强度比值(Y/B)随之增大.387 nm激发下,不同Dy3+掺杂浓度荧光粉发射光的色坐标均在白光区域中.以上结果表明Y2( MoO4)3∶Dy3+是一种新型的适于近紫外LED芯片激发的白光荧光粉,发光性能良好.     

PEG-400辅助水热合成NaLa(WO4)2及掺杂Eu3+发光性能的研究

通过PEG-400辅助水热法制备了NaLa(WO4)2,利用XRD、SEM、FTIR、TG等方法对粉体的结构、形貌、成分进行了表征.研究结果表明,pH值变化从pH=1.0到pH=9.0时,产物会发生由WO3-NaLa(WO4)2的物相转化.在180℃,pH =9.0,VPEG-400∶VH2O=1∶1时获得单分散“千层酥”状三维微晶NaLa(WO4)2,Eu3+掺入后,在λex=394 nm的激发波长下,Eu3+的5D0→7F2的跃迁强度远大于5D0→7F1的跃迁强度,Eu3+处于NaLa(WO4)2晶格非反演对称中心位置,粉体表现出较强的红光发射,继续增大Eu3+掺杂量至20mol;,会出现浓度猝灭.     

单一基质白光荧光粉Sr3Bi1-x（PO4）3∶Dy3+的制备与发光性能研究

本文采用高温固相法合成了Sr3Bi1-x(PO4)3∶xDy3+荧光粉。XRD图谱表明合成物质为纯相Sr3Bi(PO4)3晶体结构。主激发峰位于323 nm,348 nm,362 nm,385 nm,423 nm,451 nm和471 nm,分别对应Dy3+的6H15/2到4L19/2,6P7/2,6P5/2,4I13/2,4G11/2,4I15/2,4F9/2的跃迁。主发射峰位于482 nm(4F9/2→6H15/2),575 nm(4F9/2→6H13/2),分别对应于黄光和蓝光发射,其中以348 nm激发得到的峰值最强。研究了不同Dy3+掺杂浓度对发光性能的影响。随着Dy3+浓度的增大,样品的发光强度先增大后减小。当掺杂浓度x=0.08时,发光强度最好。并测试了样品的色坐标,为x=0.33,y=0.35,属于白光区域。     

Eu3+,Tb3+共掺杂的NaGd(WO4)2颜色可调荧光粉的水热合成及发光性质研究

在不添加任何模板剂的情况下,采用温和水热法,制备了一系列NaGd0.96-x(WO4)2:0.04Tb3+,xEu3+(x=0,0.005,0.01,0.02,0.04,0.06,0.08,0.10,0.12,0.14,0.16,0.18)荧光粉.采用X射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)以及荧光分光光度计分别对所得样品的物相结构、形貌粒度及发光性能进行分析表征.结果表明:所合成的样品为NaGd(WO4)2的纯相,属四方晶系白钨矿结构.其形貌为规整的四方盘形,尺寸均一、分散性良好.系列样品均能被近紫外光有效激发,通过改变NaGd(WO4)2中Eu3+/Tb3+的掺杂浓度,实现了对荧光粉发光颜色由绿色到红色的全色调控.     

Ca3(PO4)2:Dy3+纳米荧光粉 的制备及发光性能研究

采用水热法制备出Ca3(PO4)2:Dy3+纳米荧光粉,通过XRD、SEM和荧光光谱对样品进行了分析,主要研究了制备工艺以及Dy3+离子掺杂浓度对材料发光性能的影响规律.研究结果表明:初始溶液pH值为7,反应釜填充度为80;,在180℃条件下反应24 h所得的Ca3(PO4)2:0.02 Dy3+纳米荧光粉发光性能最佳.SEM分析表明荧光粉颗粒的平均粒径为100 nm,分散性好.     

微波法制备CaMoO4:Tb3+,Eu3+白色荧光粉及其发光性能研究

通过微波法制备了CaMoO4:Tb3+,Eu3+白色荧光粉.采用X射线粉末衍射仪、扫描电子显微镜和荧光光谱仪对样品材料的结构、形貌和发光性能进行了表征.分别讨论了在不同助剂、不同反应浓度、不同反应温度及稀土离子Eu3+和Tb3+共掺比例变化对荧光粉的发光性能的影响.结果表明:不加活性剂所得CaMoO4:Tb3+,Eu3+样品在反应浓度为0.06 mol/L、反应温度为120℃时发光性能最好;通过调节CaMoO4:Tb3+,Eu3+荧光粉中稀土离子Eu3+和Tb3+共掺比例荧光粉的发光颜色可以很容易地从冷白光变为暖白光.     

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.      

Second harmonic generation in Na3Gd2(BO3)3 crystals

Na₃Gd₂(BO₃)₃ crystals with dimensions up to 22 × 20 × 5 mm³has been grown from NaBO₂ flux by the top‐seeded solution growth (TSSG) method for the first time. Differential scanning calorimetry (DSC) result shows that Na₃Gd₂(BO₃)₃ melts incongruently. The infrared spectrum indicates that Na₃Gd₂(BO₃)₃ contains characteristic triangular [BO₃]^3– groups responsible for the nonlinear optical effect. For the as‐grown crystal, the transmittance exceeds 80% in the wavelength range of 315 nm to 2670 nm, and the UV cutoff wavelength is 207 nm. The damage threshold is 0.47 GW cm^–2 at 1064 nm. Moreover, Na₃Gd₂(BO₃)₃ crystal exhibits an optical second harmonic generation effect which is 1.3 times as large as that of KH₂PO₄ (KDP). (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)