Synthesis and luminescent properties of Y6W2O15:Eu phosphors

In this paper, a novel phosphor, Y₆W₂O₁₅:Eu³⁺ was synthesized by thermal decomposition and phase transition of its decatungstate gel precursor. With stepwise increase of temperature to 750 °C, a crystalline phase of Y₆W₂O₁₅:Eu³⁺forms that gives intense red emission when excited at 466 nm, the emission is attributed to the Eu³⁺ ions transitions from ⁵D₀ excited states to ⁷F_J (J=0-4) ground states. The long excitation wavelength proves the Eu³⁺ transition follows the photoexcitation of the oxygen-metal (O→W lmct) charge transfer bands in yttrium tungstate. Some structural information regarding Y₆W₂O₁₅ provided by luminescence is in accord with that characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The long-wavelength excitation properties of this material may find application in the production of red phosphors for white light-emitting diodes (LEDs).     

Preparation and luminescent properties of cubic Eu:Y2O3 nanocrystals and comparison to bulk Eu:Y2O3

Y₂O₃:Eu³⁺ nanocrystals were prepared by combustion synthesis. The particle size estimated by X-ray powder diffraction (XRD) was about 10 nm. A blue-shift of the charge-transfer (CT) band in excitation spectra was observed in Y₂O₃:Eu³⁺ nanocrystals compared with bulk Y₂O₃:Eu³⁺. The electronic structure of Y₂O₃ is calculated by density functional method and exchange and correlation have been treated by the generalized gradient approximation (GGA) within the scheme due to Perdew-Burke-Ernzerhof (PBE). The calculated results show that the energy centroid of 5d orbital in nanocrystal has increasing trend compared with that in the bulk material. The bond length and bond covalency are calculated by chemical bond theory. The bond lengths of Y₂O₃:Eu³⁺ nanocrystal are shorter than those of the bulk counterpart and the bond covalency of Y₂O₃:Eu³⁺ nanocrystal also has an increasing trend. By combining centroid shift and crystal-field splitting, the blue-shift of the CT band is interpreted.     

发光二极管用SrWO4:Eu3+红光荧光粉激发谱强度的调控

采用化学共沉淀法制备了Eu³⁺掺杂摩尔分数不同、煅烧温度不同的SrWO₄:Eu³⁺系列发光粉体, 所制备的粉体均具有Eu³⁺特征的强室温红光荧光发射. 通过调节煅烧温度和掺杂摩尔分数来调控近紫外和蓝光吸收强度, 进而调控用395 nm的近紫外光和465 nm的蓝光激发样品所得红光发光强度. 研究结果表明, 所制备的SrWO₄:Eu³⁺红光荧光粉可以被紫外和蓝光发光二极管有效激 关键词： 稀土掺杂 4:Eu³⁺')" href="#">SrWO₄:Eu³⁺ 光致发光 白光发光二极管     

Effect of Eu,Tb codoping on the luminescent properties of Y2O3 nanorods

Red-emitting Y₂O₃:Eu³⁺ and green-emitting Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺, Tb³⁺ nanorods were synthesized by hydrothermal method. Their structure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The photoluminescence (PL) property of Y₂O₃:Eu³⁺,Tb³⁺ phosphor was investigated. In the same host (Y₂O₃), upon excitation with ultraviolet (UV) irradiation, it is shown that there are strong emissions at around 610 and 545 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺ and ⁵D₄-⁷F₅ transition of Tb³⁺, respectively. Different qualities of Eu³⁺and Tb³⁺ ions are induced into the Y₂O₃ lattice. From the excitation spectrum, we speculate that there exists energy transfer from Tb³⁺ to Eu³⁺ ions .The emission color of powders reveals regular change in the separation of light emission. These powders can meet with the request of optical display material for different colors or can be potentially used as labels for biological molecules.     

Novel green-emitting Na2CaPO4F:Eu phosphors for near-ultraviolet white light-emitting diodes

In this study, green-emitting Na₂CaPO₄F:Eu²⁺ phosphors were synthesized by solid-state reactions. The excitation spectra of the phosphors showed a broad hump between 250 and 450 nm; the spectra match well with the near-ultraviolet (NUV) emission spectra of light-emitting diodes (LEDs). The emission spectrum showed an intense broad emission band centered at 506 nm. White LEDs were fabricated by integrating a 390 nm NUV chip comprising blue-emitting BaMgAl₁₀O₁₇:Eu²⁺, green-emitting Na₂CaPO₄F:0.02 Eu²⁺, and red-emitting CaAlSiN₃:Eu²⁺ phosphors into a single package; the white LEDs exhibited white light with a correlated color temperature of 5540 K, a color-rendering index of 90.75, and color coordinates (0.332, 0.365) close to those of ideal white light.     

Enhanced luminescence of Dy in Y3Al5O12 by Bi co-doping

In the present paper, phosphors with the composition Y_3−x−yAl₅O₁₂:Bi³⁺_x, Dy³⁺_y were synthesized with solid state reactions. The luminescence properties of Bi³⁺ and Dy³⁺ in Y₃Al₅O₁₂(YAG) and the energy transfer from Bi³⁺ to Dy³⁺ were investigated in detail. Bi³⁺ in YAG emits one broad band peaking at 304 nm which can be ascribed to the transition from excited states ³P_{0, 1} to ground state ¹S₀. Dy³⁺ in YAG emits two groups of peaks around 484 and 583 nm, respectively, which can be ascribed to the transitions from excited state ⁴F_9/2 to ground states ⁶H_15/2 and ⁶H_13/2. The co-doping of Bi³⁺ enhances the luminescent intensity of Dy³⁺ by ∼7 times because Bi³⁺ can transfer the absorbed energy to Dy³⁺ efficiently. The mechanism of energy transfer was also discussed.     

The up-conversion properties of Yb and Er doped Y4Al2O9 phosphors

Er³⁺ doped and Yb³⁺/Er³⁺ co-doped Y₄Al₂O₉ phosphors are prepared by the sol-gel method. The effect of dopant concentration on the structure and up-conversion properties is investigated by X-ray diffraction (XRD) and photoluminescence, respectively. XRD pattern indicates that the sample structure belongs to monoclinic. Under 980 nm excitation, the green and red up-conversion emissions are observed and the emission intensities depended on the Yb³⁺ ion concentration. The green up-conversion emissions decrease with the increase of Yb³⁺ concentration, while red emission increases as Yb³⁺ concentration increases from 0 to 8 at% and then decreases at high Yb³⁺ concentration. The mechanisms of the up-conversion emissions are discussed and results shows that in Er³⁺ and Yb³⁺/Er³⁺ co-doped system, cross-relaxation (CR) and energy transfer (ET) processes play an important role for the green and red up-conversion emissions.     

Photoluminescent properties of Y2O3:Eu phosphors prepared via urea precipitation in non-aqueous solution

Europium-doped yttrium oxide phosphors were obtained by firing precursors prepared by urea precipitation in ethanol and ethylenediamine. The precipitation in non-aqueous solution was carried out in an autoclave at 150°C to allow the decomposition of urea. The photoluminescent intensities of the phosphors prepared in ethanol and ethylenediamine increased by about 30% compared to that of the phosphor prepared by the conventional urea homogeneous precipitation in aqueous solution. Amorphous carbonates and amorphous hydroxides/carbonates mixtures were identified as precursors from ethanol and ethylenediamine, respectively. The morphology and particle size were studied by SEM and dynamic laser scattering method.     

Abnormally enhanced Eu emission in Y2O2SO4:Eu inherited from their precursory dodecylsulfate-templated concentric-layered nanostructure

A new nanostructure-mediated approach was demonstrated to synthesize Eu³⁺-doped yttrium oxysulfates Y₂O₂SO₄:Eu³⁺ giving rise to abnormally enhanced Eu³⁺ emission. Yttrium and europium salts, sodium dodecylsulfate (SDS), and urea at various Eu³⁺ concentrations were reacted in aqueous solution at 80, 85, and 87 °C to yield Eu³⁺-doped dodecylsulfate-templated yttrium oxide mesophases with straight-layered (S-type), concentric-layered (C-type) and layer-to-hexagonal transient-layered (T-type) structures, respectively. On calcination at 1000 °C, all of these mesophases were converted into Y₂O₂SO₄:Eu³⁺ to exhibit luminescence bands including the ⁵D₀-⁷F₂ transition with a tendency in intensity to saturate or reach a maximum at 10-12 mol% Eu doping. The Eu³⁺ emissions for Y₂O₂SO₄:Eu³⁺ mediated by the T- and C-type mesophases were enhanced in intensity by a factor of about two and three times, respectively, stronger than those for not only compositionally the same sulfate Y₂O₂SO₄:Eu³⁺ obtained from yttrium-based sulfates but also Y₂O₃:Eu³⁺ obtained in the SDS-free system. In contrast, the emission intensities for the S-type-mesophase-mediated Y₂O₂SO₄:Eu³⁺ were close to those for the latter sulfates. The abnormally enhanced emission is likely based on specific deformation of sulfate groups induced through the conversion of concentric dodecylsulfate-layers to straight sulfate-layers in the oxysulfate framework upon calcination.     

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

Quantum-chemical ab initio study of the crystal-field and charge transfer energies of nanocrystalline Y2O3: Eu

The 4f energy levels and crystal-field parameters for several clusters representing the local coordination surroundings of Eu³⁺ in the bulk and nanocrystalline cubic Y₂O₃: Eu³⁺ crystals are obtained by using a method based on the combination of the DV-X_α calculation and the effective Hamiltonian method initialized by M.F. Reid et al. (J. Phys.: Condens. Matter, 2011, 23: 045501). The results are in reasonable agreement with the measured energy levels and the crystal-field parameters obtained from the least-square fitting. The charge transfer energies are also obtained for all the clusters from the DV-X_α calculation. The results indicate that, compared with the bulk Y₂O₃: Eu³⁺ crystal, the charge transfer band in the excitation spectra is red-shifted in the nanocrystal.     

Phosphorescent and thermoluminescent properties of SrAl2O4:Eu,Dy phosphors prepared by solid state reaction method

Long persistent SrAl₂O₄:Eu²⁺ phosphors co-doped with Dy³⁺ were prepared by the solid state reaction method. The main diffraction peaks of the monoclinic structure of SrAl₂O₄ were observed in all the samples. The broad band emission spectra at 497 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ were observed and the emission is attributed to the 4f⁶5d¹ to 4f⁷ transition of Eu²⁺ ions. The samples annealed at 1100–1200 °C showed similar broad TL glow curves centered at 120 °C. The similar TL glow curves suggest that the traps responsible for them are similar. The long afterglow displayed by the phosphors annealed at different temperatures, may be attributed to the Dy³⁺ ions acting as the hole trap levels, which play an important role in prolonging the duration of luminescence.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

Synthesis of Gd2Ti2O7:Eu, V phosphors by sol-gel process and its luminescent properties

A red-emitting phosphor material, Gd₂Ti₂O₇:Eu³⁺, V⁴⁺, by added vanadium ions is synthesized using the sol-gel method. Phosphor characterization by high-resolution transmission electron microscopy shows that the phosphor possesses a good crystalline structure, while scanning electron microscopy reveals a uniform phosphor particle size in the range of 230-270 nm. X-ray photon electron spectrum analysis demonstrates that the V⁴⁺ ion promotes an electron dipole transition of Gd₂Ti₂O₇:Eu³⁺ phosphors, causing a new red-emitting phenomenon, and CIE value shifts to x=0.63, y=0.34 (a purer red region) from x=0.57, y=0.33 (CIE of Gd₂Ti₂O₇:Eu³⁺). The optimal composition of the novel red-emitting phosphor is about 26% of V⁴⁺ ions while the material is calcinated at 800  °C. The results of electroluminescent property of the material by field emission experiment by CNT-contained cathode agreed well with that of photoluminescent analysis.     

Luminescence properties of Ceand Tb ions codoped strontium borate phosphate phosphors

The Ce³⁺-activated, Tb³⁺-activated, and Ce³⁺ and Tb³⁺ co-activated phosphors 2SrO-nB₂O₃-(1−n)P₂O₅ were synthesized by the solid-state reaction. The structures, photoluminescent spectra and dynamics of them were systemically studied. The results demonstrate that the structure of the samples with n=0.10-0.50 belongs to the hexagonal phase. When n is beyond this range, the structures are the mixed phases of α-Sr₂P₂O₇ and Sr₂B₂O₅. The optimum composition is determined to be n=0.25 for the 2SrO-nB₂O₃-(1−n)P₂O₅ phosphors. As n varies from 0.01 to 0.50, the lifetime of Ce³⁺ ion increases gradually, while the lifetime of Tb³⁺ ion decreases, indicating that the energy transfer efficiency decreases with the increase of n. The ET efficiency between Ce³⁺ and Tb³⁺ in the optimum composition reaches to 70%. The present results demonstrate that the Ce³⁺ and Tb³⁺ co-activated hexagonal 2SrO-0.25B₂O₃-0.75P₂O₅ powders can possibly be applied as the newly developed green efficient phosphors in the field of lighting and display.     

PL and CL degradation and characteristics of SrAl2O4: Eu,Dy phosphors

Strontium aluminate phosphors are ideal for luminescent infrastructure materials. Their brightness and persistent glow time are much higher than previously used sulphide phosphors. Strontium aluminates prepared by the sol–gel and combustion methods are compared with commercially available strontium aluminate. High luminescent efficient SrAl₂O₄:Eu²⁺,Dy³⁺ pulsed laser deposited (PLD) thin films were also produced using the commercially available powder. Photoluminescence (PL) degradation studies showed that the phosphor intensity decreased about 20% over a period of 2 weeks under ultraviolet (UV) irradiation. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) showed that cathodoluminescence (CL) degradation is due to the formation of SrO due to electron stimulated surface reactions. The light output mechanism of the phosphor is also discussed in more detail.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Enhanced photoluminescence of Sm/Bi co-doped Gd2O3 phosphors by combustion synthesis

Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ powders were prepared by a combustion method. Their structures were determined using X-ray diffraction. UV-visible absorption and photoluminescence spectra were investigated for Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ at different annealing temperatures and different doping concentrations. The emission spectra of all samples presented the characteristic emission narrow lines arising from the ⁴G_5/2→⁶H_J transitions (J=5/2, 7/2, and 9/2) of Sm³⁺ ions upon excitation with UV irradiation. The emission intensity of Sm³⁺ ions was largely enhanced with introducing Bi³⁺ ions into Gd₂O₃:Sm³⁺ and the maximum occurred at a Bi³⁺ concentration of 0.5 mol%. The relevant mechanisms were discussed with the sensitization theory by Dexter and the aggregation behavior of Bi³⁺ ions.     

Synthesis and properties of colloidal ternary ZnGa2O4:Eu nanocrystals

A nonhydrolytic hot solution synthesis technique was used to grow monodisperse ternary oxide nanocrystals of ZnGa₂O₄:Eu³⁺. The shape of ZnGa₂O₄:Eu³⁺ nanocrystals was a function of the type of precursor, and their size was controlled by changing the concentration ratio of Zn precursor to surfactant. The crystal structure of synthesized ZnGa₂O₄ nanocrystals was a cubic spinel with no detectable secondary phases. Photoluminescence of red-emitting ZnGa₂O₄:Eu³⁺ nanocrystals resulted in a high (⁵D₀-⁷F₂)/(⁵D₀-⁷F₁) intensity ratio, suggesting that the Eu³⁺ ions occupy tetrahedral Zn²⁺ sites or distorted octahedral Ga³⁺ sites with no inversion symmetry in ZnGa₂O₄ nanocrystals.