水热法合成YPO4:Eu及基质的结构研究

利用水热法合成了磷酸钇基质（YPO4）和磷酸钇掺铕（YPO4∶Eu）的纳米颗粒。通过粉末衍射（XRD）、透射电镜（TEM）、红外光谱、拉曼光谱、荧光光谱、热重分析（TG）等手段对合成纳米材料的结构、粒度、表面水的含量以及发光特性进行了表征。结果表明：样品结晶良好,为单一的四方相（I41/AMD）锆石结构,且随着水热温度的降低,晶粒的粒度变小。研究发现,随着YPO4样品粒度的减小,晶格体积膨胀,并通过XRD结合红外和拉曼分析发现晶体对称性提高。利用表面水的偶极模型分析了其内在机制。给出了YPO4∶Eu的荧光光谱,指出其中各个峰对应的跃迁能级,确定为Eu^3＋的发射峰。     

静电纺丝技术制备Gd3Ga5O12:Eu3+多孔发光纳米带

采用静电纺丝技术制备了PVP/[Gd(NO3)3+Ga(NO3)3+Eu(NO3)3]复合纳米带,将其进行热处理,得到了Gd3Ga5O12:Eu3+(简称GGG:Eu3+)多孔发光纳米带.采用XRD,SEM,TEM,TG-DTA,FTIR和荧光光谱等技术对样品进行了表征.PVP/[Gd(NO3)3+Ga(NO3)3+Eu(NO3)3]复合纳米带为非晶态,经800 ℃焙烧8 h后,获得了单相石榴石型的GGG:Eu3+纳米带,属于立方晶系,空间群为Ia3d.复合纳米带表面光滑,尺寸均一,平均宽度约10 μm,厚度约为100 nm,彼此没有交联;经800 ℃焙烧后GGG:Eu3+多孔纳米带平均宽度约2.5 μm,厚度30 nm,长度大于500 μm,呈多孔网状多晶结构.当焙烧温度高于700 ℃时,复合纳米带中DMF、有机物和硝酸盐分解挥发完全,总失重率为93.1%.焙烧温度为800 ℃时,生成了纯净的无机氧化物.在254 nm的紫外光激发下,GGG:Eu3+纳米带发射出主峰位于591 nm的明亮红光,属于Eu3+的 5D0→7F1跃迁.对GGG:Eu3+纳米带形成机理进行了讨论.     

静电纺丝技术制备Gd_3Ga_5O_(12)∶Eu~(3+)多孔发光纳米带

采用静电纺丝技术制备了PVP/[Gd(NO3)3+Ga(NO3)3+Eu(NO3)3]复合纳米带,将其进行热处理,得到了Gd3Ga5O12∶Eu3+(简称GGG∶Eu3+)多孔发光纳米带.采用XRD,SEM,TEM,TG-DTA,FTIR和荧光光谱等技术对样品进行了表征.PVP/[Gd(NO3)3+Ga(NO3)3+Eu(NO3)3]复合纳米带为非晶态,经800℃焙烧8h后,获得了单相石榴石型的GGG∶Eu3+纳米带,属于立方晶系,空间群为Ia3d.复合纳米带表面光滑,尺寸均一,平均宽度约10μm,厚度约为100nm,彼此没有交联;经800℃焙烧后GGG∶Eu3+多孔纳米带平均宽度约2.5μm,厚度30nm,长度大于500μm,呈多孔网状多晶结构.当焙烧温度高于700℃时,复合纳米带中DMF、有机物和硝酸盐分解挥发完全,总失重率为93.1%.焙烧温度为800℃时,生成了纯净的无机氧化物.在254nm的紫外光激发下,GGG∶Eu3+纳米带发射出主峰位于591nm的明亮红光,属于Eu3+的5D0→7F1跃迁.对GGG∶Eu3+纳米带形成机理进行了讨论.     

YVO_4/Eu~(3+)微米棒的固相合成及其发光性能

以Y2O3、Eu2O3和NH4VO3为初始原料,用Na2CO3作助熔剂,采用高温固相法成功制备出棒状YVO4/Eu3+荧光粉;利用X射线粉末衍射仪、透射电镜、扫描电镜、荧光光谱仪等分析了产物的结构、形貌和发光特性,并探讨了其生长机理.结果表明:YVO4/Eu3+属于四方锆石型结构,空间群为I41/amd;其形貌为微米棒状,平均直径约0.20μm,平均长度约1.16μm.在395nm紫外光激发下,YVO4/Eu3+荧光粉能发出Eu3+的特征红色荧光,发射主峰位于616nm,归属于Eu3+离子的5 D0→7F2电偶极跃迁.     

TiO2对ZnO/ZnS:Eu3+荧光粉发光性能的影响

采用溶胶-凝胶-沉淀法制备ZnO/ZnS/2TiO2:Eu3+荧光粉,并采用X射线衍射(XRD)、红外光谱(IR)、透射电镜(TEM)以及荧光光谱技术对其结构、组成、形貌和发光性能进行表征,探讨其发光机理。结果显示,ZnO/ZnS/2TiO2:Eu3+荧光粉的结构在温度高于600℃时趋于稳定状态,呈不规则结构,由ZnO、TiO2和ZnS构成。IR谱图表明,Ti-O-Ti桥氧键网络结构有利于Eu3+之间的能量传递。荧光光谱分析表明,引入TiO2使Eu3+光谱选律禁阻解除,提高了ZnO/ZnS/2TiO2:Eu3+荧光粉的发光性能,且当nZn(NO3)2:nTiO2=1:2时荧光粉的发光性能最好,612 nm处的5D0→7F2电偶极跃迁为最强发射峰,最佳退火温度为600℃。     

Eu3+掺杂纳米羟基磷灰石生物荧光探针的制备、性能与表征

以Ca(NO3)2·4H2O,Eu2O3和(NH4)2HPO4为原料,采用反相微乳液-水热法制备出Eu3+掺杂羟基磷灰石纳米粒子.通过对产物纳米粒子的荧光光谱,TEM、XRD等测试分析,重点考察了Eu3+掺杂量对产物纳米结构和荧光性能的影响,并对荧光性能随其形貌变化的关系等进行了简要讨论.     

EuPO4:Zn@MCM-41的制备和发光性质

通过微波辅助水热法合成MCM-41介孔材料,经溶胶凝胶组装过程将EuPO4:Zn分散到MCM-41表面上和孔道中,制备成以MCM-41为基质的复合发光材料EuPO4:Zn@MCM-41粉末.通过XRD、FTIR、氮吸附、SEM、HRTEM、EDS对该材料进行了表征,用单因素法探究了原料配比(Eu(NO3)3、Zn(NO3)2的加入量和反应条件(煅烧的温度、时间)对EuPO4:Zn@MCM-41在593 am处发光强度的影响,并研究其影响机理.荧光分析发现,EuPO4:Zn基本不发射荧光,而EuPO4:Zn@MCM-41材料具有蓝光段和红光段的荧光发射,主要发光带以468和593 nm为中心.593 nm处的发射归因于Eu3+的4f组内5D0→7F1跃迁,即Eu3+中心离子所在品格格位对称性决定的磁偶极跃迁.研究表明以MCM-41为载体,能够大大降低颗粒的团聚程度,并使EuPO4:Zn颗粒具有更小的粒径:同时EuPO4:Zn@MCM-41中Eu3+发光巾心具有更大的裂分,MCM-41的纳米孔道使Eu3+的发光中心分离,降低了Eu3+之间电子云之间的重叠,大大减小了荧光的猝灭,因此MCM-41能有效降低Eu3+复合物荧光猝灭.     

静电纺丝技术制备Y2O3:Eu3+纳米带及其发光性质

采用静电纺丝技术制备了PVP/[Y(NO3)3+Eu(NO3)3]复合纳米带,将其进行热处理,获得了Y2O3:Eu3+纳米带.采用XRD、FTIR、SEM、TEM、荧光光谱等技术对焙烧后的样品进行了表征.结果表明:600℃焙烧即可获得Y2O3:Eu3+纳米带,800 ℃时结晶更为良好,产物属于立方晶系.纳米带表面光滑,由平均直径为30 nm的小颗粒紧密排列而成,为多品结构.随着温度升高,纳米带宽度减小.焙烧800 ℃获得的Y2O3:Eu3+纳米带的发光性质优于焙烧600℃的Y2O3:Eu3+纳米带.与体材料相比,该纳米带的激发光谱Eu3+-O2-电荷迁移态(CTB)发生红移,发射光谱发生蓝移.     

CeO_2:Eu~(3+)纳米晶的水热合成和光学性能

以硝酸铈(Ce(NO3)3·6H2O)、硝酸铕(Eu(NO3)3·6H2O)、氨水(NH3·H2O)为原料和十六烷基三甲基溴化铵(CTAB)为分散剂,采用水热法制备了CeO2:Eu3+纳米晶,用X射线衍射(XRD)、X射线光电子能谱分析(XPS)、透射电镜(TEM)、傅立叶红外(FT-IR)、拉曼光谱和荧光(FL)等手段对产品的结构和光学性能进行分析和表征。测试结果表明:CeO2:Eu3+是立方萤石结构的纳米晶体,铕以Eu3+形式进入CeO2晶格中致使其晶胞参数略增,晶粒尺寸减小。相比纯CeO2,CeO2:Eu3+的紫外-可见光吸收边发生些许红移,其中CeO2:Eu3+(9.0%)纳米晶的能带隙为2.84 e V。CeO2:Eu3+纳米晶在593,612和632 nm处发橙红光,其中非直接激发(356 nm)的CeO2:Eu3+(1.0%)的磁偶极跃迁(5D0→7F1)占主导,而直接激发(468 nm)的CeO2:Eu3+(5.0%)的电偶极跃迁(5D0→7F2)强度更大,两者均随焙烧温度升高而增强。     

异金属配合物的合成、表征与光谱性质

以多氨羧酸为配体,在水溶液中合成了两个同时含Bi3+和Eu3+两种金属的晶态配合物BiEu(edta)(NO3)2·6.5H2O和非晶态配合物BiEu(dtpa)(NO3)·4(H2O).采用元素分析仪、红外光谱仪、X射线粉末衍射仪等手段对产物进行表征.采用热分析仪对产物的热稳定性进行了研究.室温下采用紫外可见光度计和荧光光谱仪对固态产物的光学性质进行测试,结果显示产物既发Eu3+的线状特征荧光,又发Bi3+的带状荧光.     

Disappearance and recovery of luminescence in Bi3+, Eu3+ codoped YPO4 nanoparticles due to the presence of water molecules up to 800 °C

YPO(4) nanoparticles codoped with Eu(3+) (5 at. %) and Bi(3+) (2-10 at. %) have been synthesized by a simple coprecipitation method using a polyethylene glycol-glycerol mixture, which acts as capping agent. It has been found that the incorporation of Bi(3+) ions into the YPO(4):Eu(3+) lattice induces a phase transformation from tetragonal to hexagonal, and also a significant decrease in Eu(3+) luminescence intensity was observed. This is related to the association of the water molecules in the hexagonal phase of YPO(4) in which the nonradiative process from the surrounding water molecules around Eu(3+) is dominating over the radiative process. On annealing above 800 °C, luminescence intensity recovers due to significant removal of water. 900 °C annealed Bi(3+) codoped YPO(4):Eu(3+) shows enhanced luminescence (2-3 times) as compared to that of YPO(4):Eu(3+). When sample was prepared in D(2)O (instead of H(2)O), 4-fold enhancement in luminescence was observed, suggesting the extent of reduction of multiphonon relaxation in D(2)O. This study illustrates the stability of water molecules even at a very high temperature up to 800 °C in Eu(3+) and Bi(3+) codoped YPO(4) nanoparticles.     

Solvothermal synthesis and characterization of Ln (Eu3+, Tb3+) doped hydroxyapatite

Luminescent Ln (Eu3+, Tb3+) doped hydroxyapatite (Eu:HAp, Tb:HAp) phosphors were successfully fabricated via the cetyltrimethylammonium bromide (CTAB)/n-octane/n-butanol/water microemulsion-mediated solvothermal process. The structure, morphology, and optical properties were systematically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), and photoluminescence (PL) spectra as well as the kinetic decays, respectively. The XRD results reveal that the obtained Eu:HAp and Tb:HAp show the characteristic peaks of hydroxyapatite in a hexagonal lattice structure. It is observed that the as-prepared luminescent samples exhibit rod-like morphology with well dispersed and non-aggregated size distribution. Upon excitation by UV radiation, the phosphors demonstrate the characteristic 5D 0-7F 1-4 emission lines of Eu3+ and the characteristic 5D4-7F 3-6 emission lines of Tb3+. Moreover, the photoluminescence intensities (PL) of Eu3+ and Tb3+ can be tuned by altering the solvothermal temperature and the doping concentration of Eu3+ and Tb3+.     

Highly uniform and monodisperse beta-NaYF(4):Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu3+ (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to 5D0-3 --> 7FJ (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively. When doped with 5% Tb3+ ions, the strong DC fluorescence corresponding to 5D4 --> 7FJ (J = 6, 5, 4, 3) transitions with 5D4 --> 7F5 (green emission at 544 nm) being the most prominent group that has been observed. In addition, under 980 nm laser excitation, the Yb3+/Er3+- and Yb3+/Tm3+-codoped beta-NaYF4 samples exhibit bright green and whitish blue up-conversion (UC) luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.     

白色荧光粉NaGd（MoO4）2:Dy3+,Eu3+的水热合成及发光性能

采用谷氨酸辅助水热法合成了八面体形NaGd(MoO4)2:Dy3+,Eu3+白色荧光粉.X射线衍射结果表明,合成的样品为四方晶系的NaGd(MoO4)2纯相.扫描电子显微镜照片显示所制备的粒子为八面体形,各边长约为2μm.荧光光谱结果表明,在NaGd(MoO4)2:4%Dy3+,yEu3+(y=0,0.5%,0.6%,0.7%,0.8%,0.9%,1.0%)样品中,随着Eu3+掺入量的增加,Dy3+的发射峰逐渐减弱,而Eu3+的发射峰逐渐增强,说明Dy3+-Eu3+之间存在能量传递.通过色坐标图可知,当Eu3+掺杂量y=0.9%时,荧光粉的色坐标(0.338,0.281)与标准的白光色坐标(0.33,0.33)接近,表明NaGd(MoO4)2:4%Dy3+,0.9%Eu3+是很好的近紫外光激发下的白色荧光粉.     

Luminescence functionalization of SBA-15 by YVO4:Eu3+ as a novel drug delivery system

Luminescence functionalization of the ordered mesoporous SBA-15 silica was realized by depositing a YVO4:Eu3+ phosphor layer on its surface via the Pechini sol-gel process, resulting in the formation of the YVO4:Eu3+@SBA-15 composite material. This material, which combines the mesoporous structure of SBA-15 and the strong red luminescence property of YVO4:Eu3+, can be used as a novel functional drug delivery system. The structure, morphology, porosity, and optical properties of the materials were well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, N2 adsorption, and photoluminescence spectra. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the YVO4:Eu3+ layer and the adsorption of ibuprofen (IBU, drug). The IBU-loaded YVO4:Eu3+@SBA-15 system still shows the red emission of Eu3+ (617 nm, 5D0-7F2) under UV irradiation and the controlled drug release property. Additionally, the emission intensity of Eu3+ increases with an increase in the cumulative released amount of IBU in the system, making the extent of drug release easily identifiable, trackable, and monitorable by the change of luminescence. The system has great potential in the drug delivery and disease therapy fields.     

A Cl- anion-responsive luminescent Eu3+ complex with a chiral tripod: ligand substituent effects on ternary complex stoichiometry and anion sensing selectivity

A new series of N3,O-mixed donor tripods was prepared for luminescent Eu3+ complexes, in which the soft quinoline nitrogen, tertiary amine nitrogen, and hard amide oxygen donors were cooperatively involved. The mixed donor tripods formed more stable 1 : 1 complexes with Eu(NO3)3, La(NO3)3 and Tb(NO3)3 than the corresponding N4 donor tripods, and their Eu3+ complexes particularly exhibited anion-responsive luminescence properties. NMR, UV, and luminescence spectroscopic characterizations revealed that -CH3 substitution on the tripod skeleton remarkably altered the preferred stoichiometry of the "tripod-Eu3+-anion" ternary complex and gave anion-dependent europium luminescence. Although the disubstituted tripod preferred to form non-luminescent 2 : 1 (tripod : Eu3+) complexes with Eu(NO3)3 and other salts, it formed a luminescent 1 : 1 complex with EuCl3. Thus, this type of tripod offered Cl- anion-selective luminescence enhancement that was easily observed by the naked eye.     

混合溶剂热合成BaFBr∶Eu~(2+)微纳米晶及其性能表征

通过水和乙醇的混合溶剂热方法制备了不同形貌和粒径的BaFBr∶Eu2+微纳米晶.研究了不同反应条件对产物的影响,初步提出了产物的形成机制.用场发射扫描电镜(FE-SEM)、高分辨透射电子显微镜(HRTEM)、X射线粉末衍射(XRD),荧光光谱(PL)对BaFBr∶Eu2+进行了表征.结果表明:反应温度、时间及十六烷基三甲基溴化铵(CTAB)用量对产物物相、形貌及粒径有显著影响;制备的BaFBr∶Eu2+经退火后有优越的发光性能:用280nm光激发,在390nm处有对应于Eu2+4f65d12(t2g)→4f78(S7/2)跃迁的强发射峰,是计算机辐射成像板(Imaging Plate)中X射线存储荧光粉潜在可应用材料,本文为优质高效X射线存储荧光材料的可控制备提供了简洁的路径.     

在卵磷脂体系中合成EuF3纳米线

利用大豆卵磷脂在水中自发形成的囊泡作模板, 先制备出含有Eu3+的卵磷脂乳液, Eu3+与卵磷脂亲水头部的磷氧键相结合形成Eu—O—P键, 经用NH4F沉淀后制得前驱体, 该前驱体在600 ℃灼烧, 得到EuF3纳米线, 其直径约为10-20 nm. 通过对各阶段产物的荧光光谱、傅里叶变换红外(FTIR)光谱、热重-差热分析(TG-DTA)、透射电镜(TEM)等的对比分析, 确认形成了Eu—O—P键, 所得到的纳米线是多晶相EuF3.