白光LED用绿色荧光粉Ba3(PO4)2∶Tb3+的发光性能研究

本文采用高温固相法制备出一种绿色荧光粉Ba3(PO4)2∶Tb3+,并通过X射线粉末衍射仪(XRD)和荧光分光光度计对所得荧光粉的结构和光谱性能进行了表征.结果 表明:Ba3(PO4)2体系中掺杂稀土离子Tb3+并没有引起结构的变化;荧光粉Ba3(PO4)2∶Tb3+的激发光谱的主峰位于485 nm,发射光谱的主峰位于548 nm、560 nm和647 rnm;荧光粉Ba3(PO4)2∶Tb3+中Tb3的最佳掺杂浓度为20mol;.由此可见,荧光粉Ba3(PO4)2∶Tb3是可被蓝光LED有效激发的绿色荧光粉.     

Tb3+,Yb3+共掺杂LuBO3荧光粉的下转换发光

利用水热法成功合成了近红外量子剪裁荧光粉LuBO3∶15;Tb3+,x; Yb3+(x=0,1,2,4,8,12).通过X射线衍射(XRD)、光致发光谱(PL)、激发谱(PLE)和荧光寿命测试了合成物质的物相结构与发光性质.在286 nm(Tb3+∶7 F6→5D)紫外光激发下,观察到了Tb3∶5D4→7Fj(J=6,5,4,3)可见波段特征发射光和Yb3+:2F5/2→2F7/2的近红外光.研究了Yb3+浓度与激发发射光谱和荧光寿命之间的关系,表明Tb3+和Yb3+之间存在能量传递.当Tb3和Yb3+掺杂摩尔浓度分别为15;和2;时,近红外发射最强.计算得知,其最大下转换量子效率为160.74;.     

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.     

MgMoO4∶Tb3+发光材料的制备及发光性能研究

利用燃烧法于900℃制备了一种新型的MgMoO4∶Tb3绿色荧光粉.利用红外光谱(IR)、X射线衍射(XRD)研究了样品的物相和结构,利用漫反射光谱(DRS)、激发(PLE)和发射光谱(PL)研究了样品的发光性能.结果表明:所制备荧光粉为纯相MgMoO4;这种荧光粉可以被355 nm的紫外光有效激发并在545 nm处具有最强发射峰.同时研究了荧光粉的优化工艺条件,即Tb3+的掺杂浓度为0.20,合成温度为900℃,保温时间为5 min,n(CA)∶n(Mg+ Mo)为0.8∶1.CIE色度图分析表明,这种荧光粉的发光位于绿光区域,是一种适用于白光LED的潜在的绿色荧光粉.     

SiO2@Gd2O3∶Tb3+核壳微球的可控合成及发光性能研究

采用简便的尿素辅助沉淀法将Gd2O3∶Tb3+成功包覆在二氧化硅微球表面合成了尺寸均匀的球形SiO2@Gd2O3∶Tb3核壳发光材料,解决了稀土发光材料普遍存在的形貌可控性差和颗粒尺寸不均一等问题.利用XRD、SEM、红外光谱和荧光光谱等表征测试了样品的形貌、结构和发光性能.SEM照片和尺寸分布图显示,SiO2@Gd2O3∶Tb3+粒子呈现均匀球形形貌,分散性良好,粒径约(608 +18) nm.XRD图谱分析表明,600℃煅烧后,壳层Gd(OH)3CO3完全转变为立方相Gd2O3,结晶性良好,无杂相生成.同时,结合红外光谱推测了SiO2@Gd2O3∶Tb3核壳微球的形成机理,并得出Gd2O3∶Tb3+壳层主要以Si-O-Gd键形式连接在二氧化硅微球表面.在240 nm紫外光激发下,SiO2@Gd2O3∶Tb3核壳微球呈现绿光发射,其中,位于540 nm处的主峰归属于Tb3+的5D4→7F5能级跃迁.不同Tb3掺杂浓度下的发射光谱表明,当Tb3+掺杂浓度为4mol;时,SiO2@Gd2O3∶Tb3+核壳微球的发射强度达到最大值,寿命为1.55 ms,色坐标位于绿色区域,展现了良好的绿光发光性能.     

KNaCa2(PO4)2基质中Ce3+ →Tb3+的能量传递与发光特性

采用高温固相法合成了Ce3+,Tb3+激活的KNaCa2(PO4)2发光材料,并对其发光特性进行了研究.荧光光谱测试表明:Ce3+的加入显著增强了Tb3+的发射强度,观察到Ce3+对Tb3+的发光存在明显的敏化现象,且测得KNaCa2(PO4)2∶xCe3,yTb3+的最佳掺杂浓度为x=0.01,y=0.16.根据Forster-Dexter理论判定KNaCa2(PO4)2∶Ce3+,Tb3+中Ce3+对Tb3+的能量传递属于电偶极-电四极相互作用引起的共振能量传递.研究表明,KNaCa2(PO4)2∶Ce3+,Tb3+材料是一种优良的紫外-近紫外激发白光LED用高亮度绿色发光材料.     

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.     

掺铕铽钨酸锶荧光粉的制备与发光性质分析

通过化学共沉淀法制备了Sr0.95WO4∶xEu3+∶(0.05-x)Tb3+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.分别讨论了在不同反应温度下及稀土离子Eu3+和Tb3+共掺比例变化对荧光粉的发光性能和形貌的影响.结果表明:所得SrWO4∶xEu3+∶(0.05-x)Tb3样品是由无规则棒组成的发光材料,它们在800℃时,发光性能最好;样品在223 nm紫外光的激发下,在543 nm和614 nm处,呈现出两个主要发光中心,分别归属于5D4→7F5和5D0→7F2跃迁,说明稀土离子Eu3+和Tb3具有良好的发光性能,同时随着Eu3和Tb3+掺杂比例的改变,荧光体的发光色度也在不断改变.     

YVO4∶Eu3+纳米荧光粉的水热法合成及其光致发光性能的研究

以NaVO3,Y2O3,Eu2O3为原料,采用水热法在不同pH值(pH =6.5,8.2,10.1,13)条件下合成了具有不同形貌与颗粒尺寸的YVO4∶ Eu3+纳米荧光粉.利用XRD,TEM和荧光光谱仪对样品的结构、形貌和光致发光性能进行了研究.实验结果表明:所合成样品均为具有四方锆石结构的YVO4∶Eu3+纳米晶,溶液pH值对所合成样品的形貌与颗粒大小均有明显影响,而且光致发光性能与样品的形貌有关,YVO4∶Eu3棒状纳米荧光粉因具有较高结晶度而具有较高的荧光强度.     

水热法制备不同粒度GdVO4∶Eu3+纳米荧光粉及发光性能研究

采用水热法在不同pH条件下制备出不同晶粒度GdVO4∶ Eu3+荧光粉.利用X射线衍射、扫描电镜和荧光光谱对GdVO4∶ Eu3+的结构、形貌和发光性能进行了研究.讨论了溶液的pH对晶粒尺寸的影响.结果表明:合成的样品均为单一的GdVO4四方晶相,纳米晶的一次性平均粒径分布在19～41 nm.反应溶液pH为6时,合成样品平均晶粒尺寸最小.激发带主要来自于V-O的电荷迁移带,发射光谱的主发射峰来自于5D0→7F2电偶极跃迁,不同pH值条件下制备的样品的电荷迁移带、发光强度、发射峰相对强度有所不同.     

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.     

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)