Effect of structure, particle size and relative concentration of Eu(3+) and Tb(3+) ions on the luminescence properties of Eu(3+) co-doped Y(2)O(3):Tb nanoparticles

Eu(3+) co-doped Y(2)O(3):Tb nanoparticles were prepared by the combustion method and characterized for their structural and luminescence properties as a function of annealing temperatures and relative concentration of Eu(3+) and Tb(3+) ions. For Y(2)O(3):Eu,Tb nanoparticles annealed at 600 and 1200?°C, variation in the relative intensity of excitation transitions between the (7)F(6) ground state and low spin and high spin 4f(7)5d(1) excited states of Tb(3+) is explained due to the combined effect of distortion around Y(3+)/Tb(3+) in YO(6)/TbO(6) polyhedra and the size of the nanoparticles. Increase in relative intensity of the 285?nm peak (spin-allowed transition denoted as peak B) with respect to the 310?nm peak (spin-forbidden transition denoted as peak A) with decrease of Tb(3+) concentration in the Y(2)O(3):Eu,Tb nanoparticles heated at 1200?°C is explained based on two competing effects, namely energy transfer from Tb(3+) to Eu(3+) ions and quenching among the Tb(3+) ions. Back energy transfer from Tb(3+) to Eu(3+) in these nanoparticles is found to be very poor.     

Synthesis and luminescence properties of lanthanide (III)-doped YF3 nanoparticles

Synthesis process and luminescence properties of trivalent lanthanide ions (Ln3+) doped YF3 nanoparticles have been investigated. To synthesis Ln(3+)-doped YF3 nanoparticles, the mixture of (YCl3 x nH2O + LnCl3 x nH2O), and NH4F was hydrothermal treated at 180 degrees C in a Teflon-liner auto-clave or heated at higher temperatures (400 degrees C - 600 degrees C) in a stove. The XRD patterns showed that the Ln(3+)-doped orthorhombic YF3 nanoparticles with no second phase have been prepared. The solid solution Y(1-x)Eu(x)F3 (x = 0 - 0.4) nanoparticles have been synthesized. The luminescence concentration quenching resulted from resonance energy transfer between neighboring Eu3+ ions occurred at higher Eu3+ concentrations (30 mol%). The upconversion luminescence of Er(3+)-Yb3+ codoped YF3 nanoparticles under 980 nm excitation has also been observed. With increase of heated temperature, the size of the Er(3+)-Yb3+ codoped YF3 nanoparticles increased gradually, and upconversion luminescence intensity increased significantly.     

Preparation and luminescence of nano-sized In(2)O(3) and rare-earth co-doped SiO(2) thin films

The sol-gel method was used to prepare SiO(2) thin films co-doped with In(2)O(3) nano-particles and Eu(3+). The formation of nano-sized In(2)O(3) particles after annealing at 900?°C was confirmed by the x-ray diffraction technique. A novel phase transition from a hexagonal rhombic centered to a body centered cubic structure of In(2)O(3) nano-particles was observed at around 1100?°C. It is found that the particle size and the particle density of In(2)O(3) can be tuned by changing the annealing temperature and the indium doping concentration, respectively. The characteristic emission bands from Eu(3+) ions can be observed at room temperature and the luminescence intensity is increased 20 times by introducing In(2)O(3) nano-particles into Eu(3+)-doped silica films. The integrated luminescence intensity was gradually enhanced by increasing the In(3+) concentration, suggesting effective energy transfer from nano-sized In(2)O(3) to Eu(3+) ions.     

The two-photon excitation of SiO(2)-coated Y(2)O(3):Eu(3+) nanoparticles by a near-infrared femtosecond laser

In order to improve the photoluminescence property of Eu(3+)-doped nanoparticles, Y(2)O(3):Eu(3+) nanoparticles were synthesized using the Pechini-type sol-gel method, then coated with SiO(2) shells by using the St?ber method for different coating times. The SiO(2)-coated nanoparticles were characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy and Raman spectroscopy, and their photoluminescence spectra were recorded under 800?nm femtosecond laser excitation. The results indicate that a two-photon simultaneous absorption upconversion luminescence is obtained, and their upconversion luminescence intensities are further enhanced after the surfaces of the nanoparticles are coated with different thickness SiO(2) shells. Compared to the upconversion luminescence intensity of non-coated nanoparticles at 611?nm, the upconversion luminescence intensities of SiO(2)-coated Y(2)O(3):Eu(3+) nanoparticles with coating times of 60, 90 and 120?min were enhanced by 3.30, 3.96 and 4.13 times, respectively. This can be attributed to the contributions of the increased amounts of Eu(3+) ions populated at the (5)D(0) level on the surfaces of the nanoparticles because the cooperative ligand fields between the Y(2)O(3) core and non-crystalline SiO(2) shell interfaces activate the 'dormant' Eu(3+) ions near or on the surfaces of the nanoparticles. From a Judd-Ofelt (J-O) theory analysis, the coated shell structures can improve the radiative quantum efficiencies of Eu(3+)-doped nanoparticles. It is therefore concluded that more intense red upconversion luminescence with high radiative quantum efficiencies can enable the SiO(2)-coated Y(2)O(3):Eu(3+) nanoparticles to have the great potential to be used as a fine resolution phosphor.     

Enhanced surface-excitonic emission in ZnO/Al(2)O(3) core-shell nanowires

We report the influence of an Al(2)O(3) shell on the photoluminescence emission of ZnO nanowires. At room temperature, the spectrum of the core-shell nanowires shows a strong reduction of the relative intensity of the green defect emission with respect to the near-band-edge emission. At 5?K an increase of the relative intensity of the surface exciton band with respect to the donor-bound exciton emission is observed. Annealing the core-shell nanowires at 500?°C does not increase the green defect luminescence at 5?K. We propose a model explaining the spectral changes.     

Fabrication of novel luminor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) with core/shell heteronanostructure

A novel polychromic phosphor with core-shell heteronanostructure has been prepared to improve the chromatic index of phosphors. As for the first example, Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+), its synthetic route, structure and optical properties are presented in this paper. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), energy-dispersive x-ray spectra (EDS) and photoluminescence (PL) were all employed to characterize the composite core-shell phosphors. The XRD, FE-SEM and HR-TEM results indicate that the SiO(2) and YVO(4):Eu(3+) layers have been successfully coated on Y(2)O(3):Eu(3+) nanoparticles and SiO(2) layer, respectively: these layers were further verified by the EDS. The PL showed that the red-emitting phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) possessed the independent luminescent properties of both the core Y(2)O(3):Eu(3+) and the shell YVO(4):Eu(3+). The emissions were dominated by [Formula: see text] or [Formula: see text] transitions of Eu(3+) when excited with different wavelengths. Since this broad-band response to excitation in the range of 225-340?nm gave more red/dark red emissions found at 612, 616 and 620?nm, the novel phosphor Y(2)O(3):Eu(3+)@SiO(2)@YVO(4):Eu(3+) could have potential biological labeling applications with wide flexibility.     

Experimental study on the surface modification of Y(2)O(3):Tm(3+)/Yb(3+) nanoparticles to enhance upconversion fluorescence and weaken aggregation

In order to improve the solubility of doped nanoparticles in solutions, Y(2)O(3):Tm(3+)/Yb(3+) nanoparticles were synthesized using the Pechini-type sol-gel method, and their surfaces were modified with amino or carboxylic functional groups using ligand-capped and ligand-exchanging methods. The nanoparticles with modified surfaces were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy and zeta potential (ζ), and their photoluminescence was studied by fluorescence spectrophotometry. The results indicate that the upconversion fluorescence of amine-?and carboxyl-modified nanoparticles was enhanced after the surfaces of nanoparticles were modified. Compared to the upconversion fluorescence intensity of non-modified nanoparticles, the upconversion fluorescence intensities of amine-?and carboxyl-modified nanoparticles were enhanced by 9.4 and 1.4 times, respectively. These results are attributed to the formation of the chemical bonds between Y(2)O(3):Tm(3+)/Yb(3+) core and non-crystalline SiO(2) shell via Y-O-Si bridges, which activate the 'dormant' Tm(3+)/Yb(3+) ions on the surfaces of nanoparticles. The results of the solubility investigations for amine-?and carboxyl-modified nanoparticles indicate that severe aggregation can be weakened by adhering amino or carboxylic functional groups to the surfaces of nanoparticles. It is therefore concluded that the good hydrophilicity resulting from active functional groups in solutions and more intense upconversion fluorescence enable the doped core-shell nanoparticles to have great potential to be used as fluorescence biolabels in the future.     

Enhanced emissions of Eu(3+) by energy transfer from ZnO quantum dots embedded in SiO(2) glass

SiO(2):Eu(3+) based bulk composites containing ZnO quantum dots were synthesized by an in situ sol-gel process. The quantum dots homogeneously distributed among the SiO(2) glass matrix exhibited a broad ultraviolet emission band centered at 385?nm. The ZnO ultraviolet luminescence intensity decreased monotonically with increasing Eu(3+) doping concentration, while the Eu(3+) visible emission was intensified significantly by the precipitation of ZnO quantum dots, ascribed to the energy transfer from ZnO to Eu(3+). The Eu(3+) luminescence at 612?nm for the sample with 20?mol% ZnO was about ten times stronger than that for the sample without ZnO. The influence of ZnO or Eu(3+) concentration on the energy transfer process is discussed.     

Fabrication and luminescent enhancement of Eu3+-doped Y2O3@YOF core-shell nanocrystals

In this paper, a two-step synthesis method for preparing Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals is introduced. Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals were prepared by combining an autocombustion process with a low temperature solid state reaction. X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), photoluminescence (PL) and fluorescence decay were employed to characterize the prepared samples. The results of XRD, TEM and EDS indicated that the products prepared by this method were not a mixture of Y2O3:Eu3+ and YOF:Eu3+ nanocrystals, but Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals. Compared with Y2O3:Eu3+ nanocrystals, a 20% increment in luminescence intensity was observed in the Eu3+ ion-doped Y2O3@YOF core-shell nanocrystals, thus suggesting that coating with a YOF:Eu3+-shell can efficiently block the nonradiative relaxation channels that are induced by surface defect states.     

Luminescent properties and characterization of one dimensional Gd(2)O(3):Eu(3+) phosphor nano-wire for field emission application

Gd(2)O(3):Eu(3+) nano-wire phosphors embedded in SBA-15 silica templates were synthesized using a combination of the sol-gel method and hydrothermal reactions followed by a sintering process at 1000?°C. The crystal structure of Gd(2)O(3):Eu(3+) was confirmed using x-ray diffraction. Observation using transmission electron microscopy shows that the nano-wire diameters were very uniform in the 7-9?nm range. In comparison with bulk Gd(2)O(3):Eu(3+) materials, we found that the photo-luminescent property of the nano-wire was different. The analysis shows that the main nano-wire emission peaks were at 585, 597, 613 and 620?nm. The CIE value (x = 0.62, y = 0.38) indicates that the nano-wire emitted a pink colour and not red as for the bulk material. The field emission experimental results agreed well with the photo-luminescent analysis results.     

Novel molecular precursor of lanthanide complexes with long chain mono cis-butene dicarboxylate to the controlled synthesis of Y2O3:Eu3+ phosphors

Maleic anhydride was modified with long chain alcohols (1-hexadecanol, 1-octadecanol, 1-eicosanol and docosyl) to their corresponding amphiphilic mono-L cis-butene dicarboxylates (L = hexadecyl, octadecyl, eicosyl and docosyl). Subsequently, corresponding amphiphilic lanthanide (Y3+, Eu3+) complexes with these four mono-L cis-butene dicarboxylate ligands [Ln(L')3, Ln = Eu, Y; L' = MAH, MAO, MAE, MAD] were synthesized. Then, under heating at various temperatures (700, 800, 900, 1000, and 1,100 degrees C), twenty kinds of nanosized Y2O3:Eu3+ phosphors were prepared using these four as-derived amphiphilic lanthanide (Y3+, Eu3+) complexes as precursors. All four complexes can form nanosized micelle-like aggregates by special self-assembly. Results show that, under heating at 1,000 degrees C, the four Y2O3:Eu3+ phosphors present more regular dispersion particle-like morphology, and the particle size is in the range of 30-80 nm. They exhibit an especially strong emission at 609 nm, and the luminescence intensity of the sample derived from MAD at 1,000 degrees C is best.     

Fabrication of SiO2@ZrO2@Y2O3:Eu3+ core-multi-shell structured phosphor

ZrO2 interface was designed to block the reaction between SiO2 and Y2O3 in SiO2@Y2O3:Eu coreshell structure phosphor. SiO2@ZrO2@Y2O3:Eu core-multi-shell phosphors were successfully synthesized by combing an LBL method with a Sol-gel process. Based on electron microscopy, X-ray diffraction, and spectroscopy experiments, compelling evidence for the formation of the Y2O3:Eu outer shell on ZrO2 were presented. The presence of ZrO2 layer on SiO2 core can block the reaction of SiO2 core and Y2O3 shell effectively. By this kind of structure, the reaction temperature of the SiO2 core and Y2O3 shell in the SiO2@Y2O3:Eu core-shell structure phosphor can be increased about 200-300 degrees C and the luminescent intensity of this structure phosphor can be improved obviously. Under the excitation of ultraviolet (254 nm), the Eu3+ ion mainly shows its characteristic red (611 nm, 5D0-7F2) emissions in the core-multi-shell particles from Y2O3:Eu3+ shells. The emission intensity of Eu3+ ions can be tuned by the annealing temperatures, the number of coating times, and the thickness of ZrO2 interface, respectively.     

Shells of crystal field symmetries evidenced in oxide nano-crystals

By the use of a point charge model based on the Judd-Ofelt transition theory, the luminescence from Eu(3+) ions embedded in Gd(2)O(3) clusters is calculated and compared to the experimental data. The main result of the numerical study is that without invoking any other mechanisms such as crystal disorder, the pure geometrical argument of the symmetry breaking induced by the particle surface has an influence on the energy level splitting. The modifications are also predicted to be observable in realistic conditions where unavoidable size dispersion has to be taken into account. The emission spectrum results from the contribution of three distinct regions; a cluster core, a cluster shell and the very surface, the latter being almost completely quenched in realistic conditions. Eventually, by detailing the spectra of the ions embedded at different positions in the cluster we get an estimate of about 0.5 nm for the extent of the crystal field induced Stark effect. Due to the similarity between Y (2)O(3) and Gd(2)O(3), these results also apply to Eu(3+) doped Y(2)O(3) nanoparticles.     

Y2O3∶Eu$1纳米晶的尺寸调控与发光性能研究

以尿素为沉淀剂,柠檬酸为表面活性剂,通过水热法得到了非晶态的水合硝酸氧钇前驱体,进一步烧结处理后生成了立方相Y2 O3纳米晶．利用X－射线衍射（ XRD）、扫描电镜（ SEM）、透射电镜（ TEM）、红外光谱（ FTIR）和荧光光谱（ PL）分别对所得样品的相结构、形貌粒度、表面结构以及发光性能进行研究．结果表明：当烧结温度从600℃升高到900℃,Y2 O3∶Eu3＋纳米颗粒的结晶性增强,并实现了粒径调控,由13．0 nm增加至27．9 nm．随着Y2 O3∶Eu3＋纳米颗粒尺寸的增加,比表面积减小会导致发光离子附近的表面晶格缺陷降低,同时纳米晶表面吸附水、硝酸根以及柠檬酸根等杂质离子逐渐被去除,减少了荧光猝灭中心,从而有利于增强荧光发射强度以及延长荧光寿命．     

Fabrication of photoluminescent S doped Y2O3:Eu3+ nanobelts

We have successfully fabricated the S doped Y(OH)3 nanobelts with 15-30 microm in length and 50-300 nm in width and S doped Y(OH)3:Eu3+ nanobelts with 4-15 microm in length and 80-500 nm in width (most between 100 and 200 nm) via a similar process for preparation of Y(OH)3 nanotubes. Photoluminescent (PL) nanobelts of S doped Y2O3:Eu3+ were obtained through dehydration of the S doped Y(OH)3:Eu3+ nanobelts at 450 degrees C in N2. The PL properties of the S doped Y2O3:Eu3+ nanobelts have been studied and evidenced that we have successfully synthesized functional S doped Y2O3:Eu3+ nanobelts with interesting photoluminescence properties.     

Fabrication and up-conversion luminescence of Er3+:Y2O3 nanoparticles

Y2O3 nanoparticles doped with different concentrations of Er3+ were prepared by the co-precipitation method. X-ray diffraction and transmission electron microscopy results show that Er3+ dissolves completely in the Y2O3 cubic phase. The Er3+:Y2O3 nanoparticles are homogeneous in size and nearly spherical, and the average diameter of the particles after being calcined at 1,000 degrees C for 2 h is in the range of 40-60 nm. When Er3+:Y2O3 nanoparticles are excited under a 980 nm diode laser, there are two main emission bands: green emission centered at 562 nm corresponding to the 4S3/2/2H11/2 --> 4115/2 radiative transitions and red emission centered at 660 nm corresponding to the 4F9/2 --> 4I15/2 radiative transitions. By changing the doping concentration of Er3+ ions, the up-conversion luminescence can be gradually tuned from green to red.     

Silica coated, water dispersible and photoluminescent Y (V,P)O(4):Eu(3+),Bi(3+) nanophosphors

We propose an approach for silica encapsulation of YV((0.7))P((0.3))O(4):Eu(3+), Bi(3+) nanophosphors through a microemulsion process. The resulting YV((0.7))P((0.3))O(4):Eu(3+), Bi(3+)@SiO(2) core-shell nanophosphors were characterized by transmission electron microscopy, UV/vis absorption and photoluminescence spectroscopy, energy-dispersive x-ray analysis (EDAX), selected area electron diffraction and zeta-potential measurements. The obtained nanocomposites have quite a uniform spherical shape and diameters of about 15?nm. Zeta-potential measurements show that coated particles are stable at high volume fractions and can endure large variations in pH and electrolyte concentration without coalescence. These core-shell nanophosphors could also be used as ultrasensitive biological labels, because they are obtained in nanoscale and well dispersible in water.     

Synthesis and characterization of [Eu(DBM)3phen]Cl3 @ SiO2-NH2 composite nanoparticles

Fluorescent rare earth complex Eu(DBM)3(phen)]Cl3@SiO2-NH2 nanoparticles were synthesized by combination of solvent precipitation method and St?ber method. The morphologies, structure, surface and optical properties of the samples were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and fluorescence spectrophotometer (FS). The observation from FE-SEM images indicate that the obtained samples are spherical and uniform nanoparticles with a tunable average sizes from 140 nm to 300 nm. TEM results verify a core-shell structure of the nanoparticles. The FTIR spectrum confirms the characteristic vibration absorption peaks of the complex [Eu(DBM)3(phen)]Cl3@SiO2-NH2. TGA result indicates that the complex is stable below 200 degrees C. The photoluminescence analysis shows that the complex has Eu3+ characteristic red luminescence and broader excitation peak from 200 nm to 450 nm that can meet the demands of fluorescent confocal imaging. The amino groups are directly introduced to the [Eu(DBM)3(phen)]Cl3@SiO2-NH2 nanoparticles surface by using APS (3-aminopropyl triethoxysilane). This makes the surface modification and bioconjugation of the nanoparticles easier. The nano-sized spheres could be provided a basis for further expansion of its application in biomedical imaging, biological detection and fluorescent nanoprobes.     

Study on luminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors prepared by co-precipitation

Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors with different concentrations have been prepared by co-precipitation. XRD (X-ray diffraction) and SEM (scanning electron microscopy) were used to investigate the structure and morphology. The emission spectra, excitation spectra and fluorescence decay curves were measured, and partial J-O parameters and quantum efficiencies of Eu3+ 5D0 energy level were calculated. Furthermore, concentration quenching curves of Eu3+ in different hosts were drawn. The photoluminescent properties of Eu3+ doped Gd2WO6, Gd2W2O9 and Gd2(WO4)3 nanophosphors have been studied. The results indicate that Eu3+ 5D0-7F2 red luminescence can be effectively excited by 395 nm and 465 nm in Gd2WO6 and Gd2W2O9 hosts, similar to the familiar Gd2(WO4)3:Eu. Especially Gd2W2O9:Eu has strong red emission and high quenching concentration, so it has potential applications for trichromatic white LED as red fluorescent materials.     

Controllable morphology and high photoluminescence of (Y, Gd)(V, P) O4:Eu3+ nanophosphors synthesized by two-step reactions

Multi-ion doped YVO(4):Eu(3+) nanophosphors with high photoluminescence intensity were successfully prepared by a two-step reaction process for the first time, including YVO(4):Eu(3+) seeds synthesized by hydrothermal reaction and co-doping P(5+) and Gd(3+) in a sol-gel process. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and photoluminescence spectroscopy were adopted to detect the structure, grain size, morphology and optical properties of the nanophosphors, respectively. Owning to the template-induced effect of the seeds, the morphology and size of the nanophosphors could be controlled by adjusting the molar ratios between the seeds and doping ions. The size of these nanophosphors increased as P(5+) and Gd(3+) co-doped. However, most of the samples kept approximately spherical morphology and narrow size distribution. The composition-optimized (Y, Gd)(V, P)O(4):Eu(3+) nanophosphors with spherical morphology in the 80-100 nm range exhibit better red emission and superior color saturation under vacuum ultraviolet excitation compared with that of the commercial phosphor (Y, Gd)BO(3):Eu(3+).