Luminescence properties of YAl3（BO3）4 phosphors doped with Eu^3＋ ions

YAl3 （BO3）4： Eu^3＋ phosphors were prepared by the conventional solid state reaction. The phase structure and morphology were investigated by X-ray diffraction （XRD） and scanning electron microscope （SEM）. Doping YAl3（BO3）4： Eu^3＋ phosphors with concentration of Eu^3＋ ions of 0, 2, 5, 8 and 10 mol% were studied and their luminescent properties at room temperature were discussed. The excitation spectrum of Y0.95Eu0.05Al3（BO3）4 was composed of a broad band centered at about 252 nm and a group of lines in the longer wavelength region. In the emission spectra, the peak wavelength was about 614 nm under a 252 nm UV excitation. The optimal doping concentration of Eu^3＋ ions in YAl3（BO3）4： Eu^3＋ phosphors was 8 mol%.     

Comparative Study on Photoluminescent Properties of CaGdAlO4：Eu3＋ Phosphors Synthesized with Three Methods

CaGdAlO4 ： Eu^3＋ powder phosphors were prepared using citrate sol-gel （CSG）, haft-dry and half-wet （HDW） and solid state （SS） methods, respectively. X-ray diffraction results confirm the formation of CaGdAlO4：Eu^3＋ at 900 % （CSG）, 1200℃ （HDW） and 1400℃ （SS）, respectively. Field emission scan electron microscopy （FE-SEM） images show that the CaGdAlO4：Eu^3＋ powder prepared by the CSG and HDW method has an elliptical shape and that prepared under the SS method has a flaky shape. Upon excitation with 280 nm UV light, all the CaGdAlO4： Eu^3＋ powders show bright red emission on account of the 4f-4f transitions of the Eu^3＋ ions. Moreover, the size of the phosphor particles and the emission intensity increase with the increase of calcined temperature. At the same calcination temperature of 1400 ℃, the ^5D0→^7F2 emission intensity of the sample prepared by HDW method is the highest. Stark components of the ^5D0→^7FJ emission transitions, both at room temperature and at a low temperature, reveal that the Eu^3＋ ions occupy only one site with non-centrosymmetry in the crystals.     

Luminescence investigation of Eu~（3＋）-Bi~（3＋） co-doped CaMoO_4 phosphor

A series of Eu³⁺-Bi³⁺ co-doped CaMoO₄ red phosphors were synthesized via the solid-sate reaction method. The crystal structures of the obtained samples were identified by X-ray powder diffraction (XRD). The photoluminescence property was investigated, and the results showed that the intensity of excitation spectra and emission spectra could be changed with different doping ratios of Bi³⁺/Eu³⁺. The proposed explanation of these changes was from the energy transfer between Bi³⁺ and Eu³⁺ and the unbalanced charge from the substitution of Eu³⁺ and Bi³⁺ for Ca²⁺ in CaMoO₄. The obtained samples are a promising red light emitting phosphor for the needs of different excitation sources with near-UV and blue GaN-based chips.     

Photoluminescent properties of LaF3：Eu^3＋ and GdF3：Eu^3＋ nanoparticles prepared by co-precipitation method

LaF₃:Eu³⁺ and GdF₃:Eu³⁺ nanoparticles were prepared by a co-precipitation method in the presence of the chelating agent, citric acid. The structural properties of the products were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The average crystallite size was estimated from the full-width at half-maximum (FWHM) of the diffraction peaks by the Scherrer equation. The sizes of the nanoparticles were 12 nm for LaF₃:Eu³⁺ and 17 nm for GdF₃:Eu³⁺. The luminescent properties of the nanoparticles were investigated by excitation and emission spectra. Energy transfer from Gd³⁺ to Eu³⁺ was observed.     

Vacuum ultraviolet excited photoluminescence properties of Gd2O2CO3：Eu^3＋ phosphor

The Gd2O2CO3：Eu^3＋ with type-Ⅱ structure phosphor was successfully synthesized via flux method at 400 ℃ and their photoluminescence properties in vacuum ultraviolet （VUV） region were examined. The broad and strong excitation bands in the range of 153-205 nm owing to the CO3^2- host absorption and charge transfer （CT） of Gd^3＋-O2^- were observed for Gd2O2CO3：Eu^3＋. Under 172 nm excitation, Gd2O2CO3：Eu^3＋ exhibited strong red emission with good color purity, indicating Eu^3＋ ions located at low symmetry sites and the chromaticity coordination of luminescence for Gd2O2CO3：Eu^3＋ was （x=0.652, y=0.345）. The photoluminescence quenching concentration of Eu^3＋ excited by 172 nm for Gd2O2CO3：Eu^3＋ was about 5%. Gd2O2CO3：Eu^3＋ would be a potential VUV-excited red phosphor applied in mercury-free fluorescent lamps.     

Synthesis of CaWO4：Eu3＋ phosphor powders via ethylene glycol route and its optical properties

Eu3+ doped CaWO4 with tetragonal system were prepared at comparatively low temperature (125 ?C) in ethylene glycol medium. The phosphor was further investigated by X-ray diffractometer (XRD), photoluminescence spectrophotometer (PL), Fourier transform infra red (FT-IR) spectroscopy and transmission electron microscopy (TEM). XRD analysis indicated a decrease in the unit cell volume of CaWO4 with increasing Eu3+ ion concentration. It indicated the homogeneous substitution of Ca2+ ions in CaWO4 by the Eu3+ ions. TEM images showed that the particle size ranged from 20 to 200 nm and it could extend the application of the nanoparticles. The photoluminescence study showed that the intensity of electric dipole transition (5D0→7F2) at 614 nm dominated over the magnetic dipole transition (5D0→7F1) at 592 nm. The optimum concentration of Eu3+ for the highest luminescence was found to be 20 at.%. The as prepared samples were found to be dis-persible in water and methanol.     

Characterization of Y2O2S： Eu^3＋, Mg^2＋, Ti^4＋ Long-Lasting Phosphor Synthesized by Flux Method

Long-lasting phosphor Y₂O₂S: Eu³⁺, Mg²⁺, Ti⁴⁺ was synthesized by a flux method and their luminescence properties were investigated. The result indicates that the unit cell parameter c is linearly increased with the increase of Eu₂O₃ content in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). On the other hand, the change of unit cell parameter a is not linear dependence. In the Y₂O₂S: Eu³⁺ crystal structure, Eu³⁺ ions only replaced Y³⁺ ions' places in which it posited center position of c axis. With the increase of Eu₂O₃ content, the position of the strongest emission peak changed from 540 nm (⁵D₁→⁷F₂ transition) to 626 nm (⁵D₀→⁷F₂ transition), and the maximum intensity was obtained when x = 0.09 in Y₂O₂S: Eu_x³⁺ (0.01 ≤ x ≤ 0.10). This is due to the environment of trivalent europium in the crystal structure of Y₂O₂S. Doping with Mg²⁺ or Ti⁴⁺ ions alone cannot get the good long-lasting afterglow effect, whereas co-doping with Mg²⁺ and Ti⁴⁺ ions and excited with 365 nm ultraviolet light, a strong thermoluminesence peak appeared, red and orange long-lasting phosphorescence (LLP) was also observed and the phosphorescence lasted nearly 3 h in the light perception of the dark-adapted human eye (0.32 mcd · m⁻²). Thus the LLP mechanism was analyzed.     

Photoluminescent properties of Eu3＋ and Tb3＋ codoped Gd2O3 nanowires and bulk materials

In this paper, the Gd2O3：Eu3＋,Tb3＋phosphors with different doping concentrations of Eu3＋and Tb3＋ions were prepared by a hydrothermal method for nanocrystals and the solid-phase method for microcrystals. The interaction of the doped ions with different concentrations and the luminescent properties of the nanocrystals and microcrystals were studied systematically. Their structure and morphology of Gd2O3：Eu3＋,Tb3＋phosphors were analyzed by means of X-ray powder diffraction （XRD）, transmission electron mi-croscopy （TEM） and scanning electron microscopy （SEM）. The photoluminescence （PL） properties of Gd2O3：Eu3＋,Tb3＋phosphors were also systematically investigated. The results indicated that when the concentration of doped Eu3＋was fixed at 1 mol.%, the emis-sion intensity of Eu3＋ions was degenerating with Tb3＋content increasing, while when the Tb3＋content was fixed at 1 mol.%, the emission intensity of Tb3＋ions reached a maximum when the concentration of Eu3＋was 2 mol.%, implying that the energy transfer from Eu3＋to Tb3＋took place. In addition, Tb3＋could inspire blue-green light and the Eu3＋could inspire red light. Therefore co-doping systems by controlling the doping concentration and the hosts are the potential white emission materials.     

Preparation and photocatalytic activity of La^3＋ and Eu^3＋ co-doped TiO2 nanoparticles： photo-assisted degradation of methylene blue

Rare earth ions La³⁺ and Eu³⁺ co-doped TiO₂ photocatalyst (La-Eu/TiO₂) was prepared by sol-gel method, and characterized by various techniques such as X-ray diffraction (XRD), specific surface area and porosity (BET and BJH), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the La-Eu/TiO₂ was evaluated by the degradation of methylene blue (MB) under UV light irradiation. The catalyst had a relatively uniform particle diameter distribution in the range of 40–60 nm. When calcining at 600°C, the XRD patterns of La-Eu/TiO₂ indicated the anatase phase, while the XPS patterns showed the Ti⁴⁺, La³⁺ and Eu³⁺ ions existence. The DRS spectra showed red shift in the band-gap transition. The experimental results of MB degradation demonstrated that the photocatalytic activity of La-Eu/TiO₂ was significantly enhanced due to better separation of photogenerated electron-hole pairs.     

Luminescent properties of Ca2SiO4：Eu^3＋ red phosphor for trichromatic white light emitting diodes

The luminescent properties of Eu^3＋doped Ca2SiO4 red phosphors synthesized by the flux fusion reaction method were investigated. It was found that the excitation spectrum included two regions： the weak excitation band below 325 nm and strong narrow peaks above 325 nm. The main peak of the excitation band was located at 400 nm. The peaks located at 290 nm were assigned to the combination of the charge transfer transition of O-Eu, peaks above 325 nm （325, 385, 400, 470, 511, and 539 nm） were assigned to the f-f transitions of Eu^3＋. The emission spectrum was dominated by the red peak located at 612 nm due to the electric dipole transition of ^5D0-^7F2. In addition, the effects of the Eu^3＋ content and charge compensators of Li^＋, Na^＋, K^＋, and Cl^- ions on the emission intensity were investigated. The experiment results suggested that the strongest emission was obtained when the concentration of the Eu^3＋ ions was 0.3 mol^-1, and Li^＋ ions gave the best improvement to enhance the emission intensity. Ca2SiO4：Eu^3＋, Li^＋ was thus suitable for low-cost trichromatic white light emitting diodes （WLED） based on UV InGaN chip.     

Nano-preparation promoting effectively luminescent properties of one-dimensional rare earth oxides

Rare earth (La,Nd and Tb) oxides with one-dimensional micro/nanostructures were synthesized hydrothermally under facile and mild conditions with two surfactants, and characterized by X-ray diffraction (XRD), thermal gravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence. The results showed that the synthesized rare earth oxides behaved regular nano-and micro-scale structures. And the morphologies of samples depended on the radii of rare earth ions, with the help of two surfactants of sodium dodecyl sulfonic and PEG 600. Nanocrystalline La2O3:Eu3+ possessed good photoluminescence (PL) property and might be used as a nanosized phosphor, its PL intensity was altered by the doping Eu3+ concentration and the optimum concentration of Eu3+ was 3 mol.%. In comparison with bulk Eu3+/La2O3, Eu3+/nano-La2O3 showed better photoluminescence property, nearly equal to that of nanocrtstal-line La2O3:Eu3+. Tb4O7 microwires showed interesting photoluminescence properties.     

Synthesis, characterization and fluorescence of N,N'-BIS (6-metyl-2-pyridine-carboxylamide-N-oxide)-1,2-ethane and corresponding rare earth (Ⅲ) complexes

A new ligand, N,N-BIS (6-metyl-2-pyridinecarboxylamide-N-oxide)-1,2-ethane (L) and six lanthanide(III) complexes (RE=La, Sm, Eu, Tb, Gd, Yb) were synthesized and characterized in detail. The results indicated that the composition of the binary complexes was determined as [REL(H₂O)(NO₃)₂]NO₃·nH₂O (n=0–2), and the Eu³⁺ complex had bright red fluorescence in solid state. Three complexes of Eu³⁺, Tb³⁺, and Gd³⁺ with 6-methylpicolinic acid N-oxide (L') were also synthesized. The relative intensity of sensitized luminescence for Eu³⁺ increased in the following order: L>L'. The phosphorescence spectra of the Gd³⁺ complexes at 77 K were measured. The energies of excited triplet state for the ligands were 20704 cm⁻¹ (L) and 20408 cm⁻¹ (L'). The facts that the ligands sensitized Eu³⁺ strongly and the order of the emission intensity for Eu³⁺ complexes were explained by ΔE(T-⁵D). This meant that the triplet energy level of the ligand was the main factor to influence RE³⁺ luminescence.     

Combustion synthesis,characterization and luminescence properties of barium aluminate phosphor

The blue-green emitting Eu2+ and Nd3+ doped polycrystalline barium aluminate(BaAl2O4:Eu2+,Nd3+) phosphor, was prepared by a solution-combustion method at 500 oC without a post-annealing process. The characteristic variation in the structural and luminescence properties of the as-prepared samples was evaluated with regards to a change in the Ba/Al molar ratio from 0.1:1 to 1.4:1. The morphologies and the phase structures of the products were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS), while the optical properties were investigated using ultra-violet(UV) and photoluminescence(PL) spectroscopy, respectively. The XRD and TEM results revealed that the average crystallite size of the BaAl2O4:Eu2+,Nd3+ phosphor was about 70 nm. The broad-band UV-excited luminescence of the phosphors was observed at λmax=500 nm due to transitions from the 4f65d1 to the 4f7 configuration of the Eu2+ ion. The PL results indicated that the main peaks in the emission and excitation spectrum of phosphor particles slightly shifted to the short wavelength due to the changes in the crystal field due to the structure changes caused by the variation in the quantity of the Ba ions in the host lattice.     

Enhanced photodegradation activity of ZnO:Eu~(3+)and ZnO:Eu~(3+)@Au 3D hierarchical structures

In this work the flower-like hierarchical structures(HS) based on 3 D pristine ZnO,ZnO:Eu~(3+)and ZnO:Eu~(3+)@Au were successfully obtained by a template-free solvothermal and deposition-precipitation method.The decolorization/photodegradation of these structures towards model organic dye(rhodamine 6 G) was studied.The synthesized ZnO-based HS were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),UV-vis and photoluminescence(PL) spectroscopies.The proposed synthesis approaches allow to obtain highly crystalline 3 D ZnO,ZnO:Eu~(3+) and ZnO:Eu~(3+)@Au composites.Results of scanning microscopy show that ZnO flower-like HS are assemblies from smaller components,forming larger ones,the whole ZnO structure was approximately 3 μm.Au nanoparticles(size～10 nm)are successfully deposited on ZnO HS surface.Luminescent studies show that ZnO is an ideal matrix for incorporation of Eu~(3+)ions in broad concentration range(Eu~(3+)=1.0 at%-5.0 at%) with an efficient red luminescence.The strong UV emission in ZnO,as well as ZnO;Eu~(3+)HS is observed under 325 nm excitation.Doping of ZnO HS matrix by Eu~(3+)ions leads to the red shift of deep level emission peak(DLE).The PL intensity reaches the maximum up to 5 at% Eu~(3+).The photocatalytic properties of ZnO and ZnO:Eu~(3+)@Au HS were investigated under UV-Vis light irradiation towards rhodamine 6 G.The obtained results demonstrate the synergetic effect of the deposited gold nanoparticles and Eu~(3+)doping on photocatalytic activity of ZnO:Eu~(3+)@Au HS in comparison to pristine ZnO and ZnO:Eu~(3+)HS.     

Upconversion luminescence of Y2O3：Er^3＋ ,Yb^3＋ nanoparticles prepared by a homogeneous precipitation method

Y2O3： Er^3＋, Yb^3＋ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3：Er^3＋,Yb^3＋ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to ^2H11/2,^4S3/2→^4I15/2 and ^4F9/2→^4I15/2 transitions of the ion, respectively. The ratio of the intensity of green emission to that of red emission drastically changed with a change in the EDTA 2Na concentration. In the sample synthesized without EDTA, the relative intensity of the green emission was weaker than that of the red emission. The relative intensities of green emission increased with the increased amount of EDTA 2Na used. The possible upconversion luminescence mechanisms were discussed.     

Synthesis,structure and luminescent properties of a new Vernier phase Lu7O6F9 doped by Eu^3＋ as potential scintillator with unique lath tube architecture

To explore novel nano-scintillator with a controllable architecture, pure and Eu3+ doped lutetium oxyfluoride(Lu7O6F9) powder were synthesized by combining mild hydrothermal method and solid state calcination approach. The products were all pure orthorhombic Vernier phase demonstrated by X-ray powder diffraction(XRD). The detailed crystal structure was also studied by Reitveld refinement. Lath-like microcrystals composed of nanoparticles with unique hollow tube of the products were supported by the images of scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Excited by X-ray with W as the target, the pure product showed intense broad emission with the peak at about 400 nm suitable for modern photoelectric multiplier tube(PMT), while the Eu3+ doped sample transferred the incident energy to Eu3+ ions and gave strong 5D0→7Fj(j=0, 1, 2 and 4) emission, which fitted for imaging and labeling measurements. From the luminescent properties, both pure and Eu3+-doped products are potential excellent scintillator for X-ray imaging and other high energy detectors, and the pure product is also a good host candidate for rare earth doping.     

Synthesis and luminescence properties of SrAleO4：Eue＋,Dy3＋ hollow microspheres via a solvothermal co-precipitation method

SrAl2O4:Eu2+,Dy3+ hollow microspheres were successfully prepared through a facile and mild solvothermal co-precipitation combining with a postcalcining process.The structure and particle morphology were investigated by X-ray diffraction(XRD),scanning and transmission electron microscopy(SEM and TEM)pictures,respectively.The mechanism for the formation of spherical SrAl2O4:Eu2+,Dy3+ phosphor was preliminary presented.After being irradiated with ultraviolet(UV)light,the spherical phosphor emitted long-lasting green phosphorescence.Both the photoluminescence(PL)spectra and luminance decay,compared with that of commercial bulky powders,revealed that the phosphors had efficient luminescent and long lasting properties.It was considered that the SrAl2O4:Eu2+,Dy3+ hollow microspheres had promising long-lasting phosphorescence with potential scale-dependent applications in photonic devices.     

Nanosized complex fluorides based on Eu3＋ doped Sr2LnF7 （Ln=La,Gd）

A simple co-precipitation approach taking place between Ln3+, Sr2+ cations and F– anions, led to the formation of nanocrystalline Eu3+ doped Sr2LnF7(Ln=La and Gd) complex fluorides. The reaction was carried out in the presence of polyethylene glycol, PEG 6000 as a surfactant/surface modifier, providing small size and homogeneity of the products. The synthesized compounds were composed of small nanoparticles with an average size of 15 nm. All obtained Eu3+ doped compounds exhibited an intensive red luminescence. In the case of gadolinium based compounds, the energy transfer phenomena could be observed from Gd3+ ions to Eu3+ ions. In order to study the structure and morphology of the synthesized fluorides, powder X-ray diffraction(XRD) and transmission electron microscopy(TEM) measurements were performed. Also FT-IR spectra of the products were recorded, revealing the presence of PEG molecules on the nanoparticles surface. A spectrofluorometry technique was applied to examine optical properties of the synthesized nanoparticles. Excitation and emission spectra as well as luminescence decay curves were measured and analysed. The performed analysis revealed a red luminescence, typical for the Eu3+ ion situated in the inorganic, highly symmetric matrix. Concentration quenching phenomena and lifetimes shortening, together with an increasing of the Eu3+ doping level, were observed and discussed. Judd-Ofelt analysis was also performed for all doped samples, in order to support the registered spectroscopic data and examine in details structural and optoelectronic properties of the synthesized nanomaterials.     

Nanocomposites of CsPbBr3 perovskite quantum dots embedded in Gd2O3:Eu3+ hollow spheres for LEDs application

Gd₂O₃:Eu³⁺@CsPbBr₃ quantum dots (QDs) mesoporous hollow nanocomposites with good luminescent properties and high stability were built. Among which, the hollow Gd₂O₃:Eu³⁺ spheres and CsPbBr₃ QDs were prepared by urea homogeneous precipitation and hot-injection method, respectively. Finally, the Gd₂O₃:Eu³⁺@CsPbBr₃ QDs shell–core compounds were constructed through mechanical stirring. The structure, morphology, stability and luminescent properties were studied by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry/thermogravity (DSC/TG), X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence excitation/photoluminescence (PLE/PL) and life decay tools. Compared to the original CsPbBr₃ QDs, Gd₂O₃:Eu³⁺@CsPbBr₃ QDs display better photostability, thermal stability and current stability. The resulting Gd₂O₃:Eu³⁺@CsPbBr₃ QDs composite exhibits good yellow emission. The Gd₂O₃:Eu³⁺@CsPbBr₃ QDs mixed silicone resin was directly coated on the blue LED chip, then the w-LED device with the color coordinate of (0.31, 0.32) was successfully assembled. The Gd₂O₃:Eu³⁺@CsPbBr₃ QDs compounds with excellent luminescent properties and stability are expected to be widely used in lighting and display areas.     

Preparation and Characterization of Red Luminescent Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ Nanophosphor

Nanophosphor with the nominal composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ （CZTOPN） was synthesized at relatively low temperature by the sol-gel method. Metal ions were dispersed by citric acid in ethylene glycol solvent and then react with Ti（OC4H9）4 to form sol and gel. The decomposition process of the precursor, and crystallization and particle size of CZTOPN were examined by thermal analysis （TG-DSC）, powder X-ray diffraction （XRD）, and scan election microscopy （SEM）. Results of TG-DSC and XRD reveal that the composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ changes with the sintering temperature. SEM data indicate that the diameter of particles is under 50 nm even if the sintering temperature increases to 1000 ℃. In contrast to a solid state reaction, the excitation spectra of samples synthesized by the sol-gel method shift blue about 10 nm and the emission intensity at 617 nm increases significantly.