New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Synthesis and photoluminescence of CeO2:Eu phosphor powders

The crystalline structure and photoluminescence (PL) properties of europium-doped cerium dioxide synthesized by the solid-state reaction method were analyzed. CeO₂:Eu³⁺ phosphor powders exhibit the pure cubic fluorite phase up to 10 mol% doping concentration of Eu³⁺. With indirect excitation of CeO₂ host at 373 nm, the PL intensity quickly increases with increasing Eu³⁺ concentration, up to about 1 mol%, and then decreases indicating the concentration quenching. While with direct excitation (467 nm), much more stronger PL emissions, especially the electric dipole emission ⁵D₀-⁷F₂ at 612 nm, are observed and no concentration quenching occurs up to 10 mol% doping concentration of Eu³⁺. The nature of this behavior and the cause of the concentration quenching were discussed.     

Eu red long afterglow in Y2O2S:Ti, Eu phosphor through afterglow energy transfer

Eu,Ti co-doped Y₂O₂S:0.03Ti,0.03Eu phosphors and single Eu or Ti doped Y₂O₂S phosphors were prepared and their luminescent properties were investigated in detail by photoluminescence (PL) spectra, long afterglow spectra and thermoluminescence spectra measurements. The results showed that Y₂O₂S:Ti,Eu phosphors possess orange-red afterglow color with afterglow time above 5 h. The reddish afterglow color, which corresponds to a set of linear Eu³⁺ emissions at low-energy range (540-630 nm), was demonstrated to come from the energy transfer process from yellow Ti afterglow emissions, the proposed energy transfer mechanism may well explain the Eu³⁺ afterglow emission.     

Luminescence properties of red-emitting praseodymium-activated BaTi4O9 phosphor

The photoluminescence and low-voltage cathodoluminescence characteristics of BaTi₄O₉:Pr³⁺ were investigated. The excitation band of intervalence charge transfer (IVCT) of BaTi₄O₉:Pr³⁺ emerged distinctly at 330 nm. The resultant emissions appeared at 606-643 nm corresponding to the ¹D₂→³H₄ transition. In BaTi₄O₉:Pr³⁺, the emission of ³P₀→³H₄ transition at 490 nm was not observed. The results were in a pure red color emission.     

Decay pathway and high-temperature luminescence of Eu in Ca2Gd8Si6O26

The temperature-dependent luminescence of Eu:Ca₂Gd₈Si₆O₂₆ and its decay pathways are investigated in order to assess the utility of the material as a thermometric phosphor. Non-radiative decays are found to compete with radiative processes even at room temperature. A decay pathway involving decay through charge-transfer states is proposed based on the decay profiles of emissions from ⁵D₁ and ⁵D₀ levels and on the temperature sensitivity of the spectra as observed after excitation by several wavelengths. The implications of this on solid-state lighting are also discussed.     

Eu substitution and particle size control of Y2O2S for the excitation by UV light emitting diodes

Yttrium oxysulfide doped with europium (Y₂O₂S:Eu³⁺) red phosphor is used in UV light emitting diodes (LEDs) by mixing with blue and green phosphors to generate white light which are important for the application in general lighting. Here, we demonstrate the effect of shape and size and the concentration of activator (Eu) of red Y₂O₂S phosphor.     

Photoluminescence studies of red-emitting NaEu(WO4)2 as a near-UV or blue convertible phosphor

Sodium europium double tungstate [NaEu(WO₄)₂] phosphor was prepared by the solid-state reaction method. Its crystal structure, photoluminescence properties and thermal quenching characteristics were investigated aiming at the potential application in the field of white light-emitting diodes (LEDs). The influences of Sm doping on the photoluminescence properties of this phosphor were also studied. It is found that this phosphor can be effectively excited by 394 or 464 nm light, which nicely match the output wavelengths of near-ultraviolet (UV) or blue LED chips. Under 394 or 464 nm light excitation, this phosphor exhibits stronger emission intensity than the Y₂O₂S:Eu³⁺ or Eu²⁺-activated sulfide phosphor. The introduction of Sm³⁺ ions can broaden the excitation peaks at 394 and 464 nm of the NaEu(WO₄)₂ phosphor and significantly enhance its relative luminance under 400 and 460 nm LEDs excitation. Furthermore, the relative luminance of NaEu(WO₄)₂ phosphor shows a superior thermal stability compared with the commercially used sulfide or oxysulfide phosphor, and make it a promising red phosphor for solid-state lighting devices based on near-UV or blue LED chips.     

Optical and structural properties of nanosized ZnGa2O4:Cr phosphor

Nanosized ZnGa₂O₄:Cr³⁺ powder is synthesized through hydrothermal method. The average particle size is 20 nm and they are spherical in shape. The excitation band from the charge transfer between Cr³⁺-O²⁻ shows a blueshift behavior due to quantum confinement effect. X-ray diffraction pattern, Fourier transform-infrared spectrum, and electron paramagnetic resonance signal indicate that nanosized ZnGa₂O₄:Cr³⁺ phosphor shows many defect-related energy states and heavy lattice distortion in comparison with bulk ZnGa₂O₄:Cr³⁺ phosphor. Many defect states result in more nonradiative loss and shorter decay time.     

Potential PDP phosphors with strong absorption around 172 nm: Rare earth doped NaLaP2O7 and NaGdP2O7

NaLaP₂O₇ and NaGdP₂O₇ powder samples are prepared by solid-state reactions at 750 and 600 °C, respectively, and the VUV-excited luminescence properties of Ln³⁺ (Ln=Ce, Pr, Tb, Tm, Eu) in both diphosphates are studied. Ln³⁺ ions in both hosts show analogous luminescence. For Ce³⁺-doped samples, the five Ce³⁺ 5d levels can be clearly identified. As for Pr³⁺ and Tb³⁺-doped samples, strong 4f-5d absorption band around 172 nm is observed, which matches well with Xe-He excimer in plasma display panel (PDP) devices. As a result, Pr³⁺ can be utilized as sensitizer to absorb 172 nm VUV photon and transfer energy to appropriate activators, and Tb³⁺-doped NaREP₂O₇(RE=La, Gd) are potential 172 nm excited green PDP phosphors. For Tm³⁺ and Eu³⁺-doped samples, the Tm³⁺-O²⁻ charge transfer band (CTB) is observed to be at 177 nm, but the CTB of Eu³⁺ is observed at abnormally low energy position, which might originate from multi-position of Eu³⁺ ions. The similarity in luminescence properties of Ln³⁺ in both hosts indicates certain structural resemblance of coordination environment of Ln³⁺ in the two sodium rare earth diphosphates.     

Preparation and spectroscopic properties of Nb2O5 nanorods

Nb₂O₅ nanorods have been prepared using water/ethanol media. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible absorption and photoluminescence spectroscopy. The as-prepared Nb₂O₅ nanorods appeared to be single pseudohexagonal (TT-Nb₂O₅) phase. From the photoluminescence spectrum, two emission bands at 407 and 496 nm, respectively, were observed. The origin of the luminescence was discussed in detail.     

Photophysical analysis of the organic complex [Eu(C12H8N2)2](NO3)3

We have determined the photophysical properties of [Eu(C₁₂H₈N₂)₂](NO₃)₃, (EuPhen), a complex which is very promising for photonic and optoelectronic applications, because of its easy synthetic procedure and high thermal stability (up to 300 °C) combined with large sensitization efficiency and good emission quantum yield. Available experimental absorption and emission data have been analyzed by using Judd-Ofelt analysis. Moreover, semi-empirical calculations have been used to determine the structure of the complex and to interpret the convoluted shape of the absorption spectrum.     

Highly enhanced photoluminescence and X-ray excited luminescence of Li doped Gd2O3:Eu thin films

Transparent Li-doped Gd₂O₃:Eu³⁺ thin-film phosphors were prepared by a modified sol-gel method. The effect of the Li⁺ ions on luminescent properties of the thin film was investigated. The results indicated that incorporation of Li⁺ ions into Gd₂O₃ lattice could result in a remarkable increase on photoluminescence or X-ray excited luminescence, and the strongest emission was observed from Gd_1.84Li_0.08Eu_0.08O_3−δ film, in which the intensity was increased by a factor of 1.9 or 2.3 in comparison with that of Gd_1.92Eu_0.08O₃ film. And it could be achieved the highest intensity for sintering the Gd_1.84Li_0.08Eu_0.08O_3−δ film at 700 °C. Such a temperature is much lower than the typical solid-state reaction temperature for its powder phosphors. This kind of transparent thin-film phosphors may promise for application to micro X-ray imaging system.     

Luminescent characterization of CaAl2S4:Eu powder

The photoluminescent (PL) emission and excitation behaviour of green-emitting CaAl₂S₄:Eu²⁺ powder phosphor is reported in detail. CaAl₂S₄:Eu²⁺ emission provides good CIE colour coordinates (x=0.141; y=0.721) for the green component in display applications. Powder with a dopant concentration of 8.5 mol% shows the highest luminescence efficiency. Temperature dependence of the radiative properties, such as luminescence intensity and decay time, was investigated. In particular, the Stokes shift, the mean phonon energy, the redshift, the energy of the f→d and d→f transition and the crystal field splitting of the CaAl₂S₄:Eu²⁺ emission were determined. The thermal quenching of the emission was examined.     

Quenching of thermo-stimulated photo-ionization by energy transfer in CaAl4O7: Tb, Ce

Crystal fibers of Ce³⁺ and Tb³⁺ singly doped and co-doped CaAl₄O₇ were grown by the LHPG method. Photoluminescence, excitation spectra and photoconduction were measured. Thermo-stimulated photo-ionization (delocalization) of electrons from the lowest field component of the 5d excited state of Ce³⁺ was observed in the Ce³⁺ singly doped sample under excitation at 355 nm. The 5d sublevel was found to locate at 0.3 eV below the conduction band of the host. However, the thermo-stimulated photo-ionization was greatly quenched due to the fast energy transfer from the 5d sublevel to Tb³⁺ ions in the Ce³⁺/Tb³⁺ double doped sample.     

Luminescent mechanism of Y2SiO5:Ce phosphor powder

A luminescent mechanism was constructed for the broad band emission spectra of the X₁ phase of the Y₂SiO₅:Ce phosphor powder. Four Gaussian peaks fit to the cathodoluminescent (CL) and photoluminescent (PL) spectra were attributed to the two different sites (A1 and A2) of the Ce³⁺ ion in the host matrix and the difference in orientation of the neighbour ions in the complex crystal structure. Each Ce³⁺ site gives rise to transitions from the 5d to the two (therefore two peaks) 4f energy levels (²F_5/2 and ²F_7/2 due to crystal field splitting). Energy transfer from other defect levels in the matrix was also observed.     

Novel ultraviolet photoluminescence of ZnO/ZnGa2O4 composite layers

ZnO/ZnGa₂O₄ composite layers were synthesized by simple thermal oxidation of ZnS substrates with gallium in the air. The continuous-wave and time-resolved photoluminescence measurements for the composites were performed at room temperature. It is found that the visible deep level emission from ZnO in ZnO/ZnGa₂O₄ composite layer was almost suppressed. In addition, the UV emission with long lifetime was also observed in comparison with that of pure ZnO layer without ZnGa₂O₄.     

Laser-excited spectra of Lu2SiO5:Ce scintillator

The emission spectra of Lu₂SiO₅:Ce single crystal under the excitation of 266 nm laser were investigated. The emission spectra of LSO single crystal show no temperature quenching from 20 to 300 K, under the excitation of 266 nm laser with 2 mJ pulse energy. With rising temperature, the Ce1 emission is slightly decreased, while the Ce2 emission is slightly increased. These results show the emissions of Ce1 and Ce2 is not only dependent on the concentration ratio but also influenced by the possible energy transfer processes, including Ce1 to Ce2, intrinsic STHs to Ce2 and the phonon-assisted transfer processes. The spectral thermal broadening and the spectral overlap become evident at high temperature, leading to the enhancement of energy transfer. When the excitation power lowers, the ratio of Ce1 and Ce2 emission increases, and is close to the Xe lamp ultraviolet (UV) excitation, suggesting that the energy transfer from Ce1 center to Ce2 center may be also dependent on the excitation power.     

An efficient co-doping of Eu and Er in CaAl2O4 aluminate phosphor

CaAl₂O₄:Eu²⁺ co-doped with varying concentrations of Er³⁺ was prepared by solid-state reaction method. Prepared materials with 1 mol% Eu²⁺ and 2-10 mol% of Er³⁺ were investigated for their photoluminescence properties. Phase, morphology and crystalline structure were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Broad band UV-excited luminescence was observed for CaAl₂O₄:Eu²⁺, Er³⁺ in the blue region (λ_max=440 nm) due to transitions from 4f⁶5d¹ to the 4f⁷ configuration of the Eu²⁺ ion. The Er³⁺ ion co-doping generates deep traps, which results in longer decay time for phosphorescence.     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.