Origin of PL intensity increase of CaMgSi2O6:Eu phosphor after baking process for PDPs application

We have synthesized blue-emitting CaMgSi₂O₆:Eu²⁺ (CMS) and evaluated its thermal stability after baking process. To evaluate its thermal stability, CMS was baked in air at 500 and 600 °C for 20 min, respectively, and compared with BaMgAl₁₀O₁₇:Eu²⁺ (BAM) treated in the same condition. After baking process, CMS showed somewhat increased photoluminescence (PL) intensity with baking temperature. To investigate the reasons behind the increase of PL intensity after baking process, vacuum ultraviolet (VUV)/PL, electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) techniques were applied. From the ESR and the XPS analyses, it is noted that spectral intensity of Eu²⁺ ion somewhat increased. It was believed that due to charge balance Eu³⁺ ions reduced to Eu²⁺ ions during the baking process in air. It is clear that the concentration of Eu²⁺ increased after the baking process in air and it leads to slight increase of the VUV/PL intensity of CMS phosphor.     

A novel blue magnesium strontium aluminate-based phosphor for PDP application

A novel blue light-emitting phosphor, Eu²⁺-doped magnesium strontium aluminate (MgSrAl₁₀O₁₇:Eu²⁺), for plasma display panel (PDP) application was developed. X-ray diffraction (XRD) patterns disclosed that the phosphor annealed at 1500 °C for 5 h was a pure MgSrAl₁₀O₁₇ phase. Field emission scanning electron microscopy (FE-SEM) images showed the particle size of the phosphor was less than 3 μm. The phosphor shows strong and broad blue emission under vacuum ultraviolet (VUV) light excitation. After baking at 400-600 °C and irradiation with VUV light for 300 h, the phosphor still keep excellent VUV luminescence properties exhibiting good stability against high temperature baking and VUV irradiation. The decay time was short as 1.09 μs and the quantum yield was high to 0.77±0.02. All the characteristics indicated that MgSrAl₁₀O₁₇:Eu²⁺ would be a promising blue phosphor for PDP application.     

The effects of substrate temperature on the structure, morphology and photoluminescence properties of pulsed laser deposited SrAl2O4:Eu,Dy thin films

In this study, SrAl₂O₄:Eu²⁺,Dy³⁺ thin film phosphors were deposited on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique. The films were deposited at different substrate temperatures in the range of 40-700 °C. The structure, morphology and topography of the films were determined by using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Photoluminescence (PL) data was collected in air at room temperature using a 325 nm He-Cd laser as an excitation source. The PL spectra of all the films were characterized by green phosphorescent photoluminescence at ∼530 nm. This emission was attributed to 4f⁶5d¹→4f⁷ transition of Eu²⁺. The highest PL intensity was observed from the films deposited at a substrate temperature of 400 °C. The effects of varying substrate temperature on the PL intensity were discussed.     

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.     

Synthesis and luminescence investigation of RE (Eu, Tb and Ce)-doped lithium silicate (Li2SiO3)

Synthesis and photoluminescence (PL) investigations of lithium metasilicate doped with Eu³⁺, Tb³⁺ and Ce³⁺ were carried out. PL spectra of Eu-doped sample showed peaks corresponding to the ⁵D₀→⁷F_j (j=1, 2, 3 and 4) transitions under ultraviolet excitation. Strong red emission coming from the hypersensitive ⁵D₀→⁷F₂ transition of Eu³⁺ ion suggested the presence of the dopant ion in structurally disordered environment. Tb³⁺-doped silicate sample showed blue-green emission corresponding to the ⁵D₄→⁷F_j (j=6, 5 and 4) transitions. Ce-doped sample under excitation from UV, showed a broad emission band in the region 350-370 nm with shoulders around 410 nm. The fluorescence lifetimes of Eu³⁺ and Tb³⁺ ions were found out to be 790 and 600 μs, respectively. For Ce³⁺, the lifetime was of the order of 45 ns. PL spectra of the europium- and terbium-doped samples were compared with commercial red (Y₂O₃:Eu³⁺) and green (LaPO₄:Tb³⁺) phosphors, respectively. It was found that the emission from the doped silicate sample was 37% of the commercial phosphor in case of the Tb-doped sample and 8% of the commercial phosphor in case of the Eu-doped sample.     

Preparation and characterization of long persistence strontium aluminate phosphor

Long afterglow green phosphor SrAl₂O₄:Eu²⁺,Dy³⁺ is synthesized by a solid-state reaction method at 1350 °C under mild reducing atmosphere of activated carbon. The effects of B₂O₃ flux on the sintering dynamic process and the optimum concentrations of Eu²⁺ and Dy³⁺ for long-lasting bright luminescence property have been investigated. The effect of a small amount of charge compensators like Mg²⁺, Zn²⁺, Na⁺, and K⁺ on long persistence has also been studied. TG/DTA, SEM, and XRD have been used to characterize the synthesized phosphor.     

Temperature dependence of persistent luminescence in β-irradiated SrAl2O4:Eu, Dy phosphor

SrAl₂O₄:Eu²⁺, Dy³⁺ is a phosphor characterized by a long persistent luminescence (PLUM) when excited with UV-vis light and ionizing radiation exhibiting intensity variation in the 10-320 K temperature range and maximum intensity around 320 K. In this work, we study the PLUM behavior of SrAl₂O₄:Eu²⁺, Dy³⁺ as a function of temperature from room temperature to 670 K in samples exposed to β irradiation. The room-temperature irradiation followed by PLUM readout revealed an integrated PLUM maximum at 323 K decreasing later. In contrast, irradiation and PLUM readout at temperatures above room temperatures produced integrated PLUM intensities maxima around 425 and 625 K. Successive cycles of preheating followed by irradiation and PLUM readout produced an increasing of the PLUM intensity as a function of cycle number. The observed phenomenon was ascribed to trapped electrons at the multiple trapping states related to the 425 and 625 K defects levels and electron transfer from one trap to another (electron hopping). Eventually, there is a return to the 5d level of Eu³⁺ cations with the characteristic PLUM emission by thermal energy supplied at room temperature (lattice vibrations) or by a preheating-irradiation-readout cycle. This property may allow keeping up the PLUM properties of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors through background radiation self exposure and adequate heating processes.     

Enhanced luminescence of GdTaO4:Eu thin-film phosphors by K doping

The effect of K⁺ ions on GdTaO₄:Eu³⁺ thin-film phosphors was investigated in order to improve their luminescent properties. The GdTaO₄:Eu_0.1, K_x thin films were synthesized by sol-gel process, and characterized through measuring their microstructure and luminescence. The results indicated that photoluminescence (PL) intensity of GdTaO₄:Eu³⁺ film was improved remarkably by K doping. There were two maxima in the curve of PL intensity against K⁺ dopant concentration, where one was improved up to 2.1 times at x = 0.001 and the other was enhanced up to 2.7 times at x = 0.05. The first maximum was regarded as the alteration of the local environment surrounding the Eu³⁺ activator by incorporation of K⁺ ions, and the second maximum was due to the flux effect. Additionally, the luminescence increased with the increase of firing temperature from 800 °C to 1200 °C.     

Eu luminescence in tellurite glasses with gold nanostructures

Luminescence properties of Eu³⁺ doped TeO₂-PbO-GeO₂ glasses containing gold nanoparticles (NPs) were investigated. The emission spectra of the samples exhibited enhancement of Eu³⁺ luminescence due to the presence of gold NPs. The emission at 614 nm, due to the Eu³⁺ hypersensitive transition ⁵D₀-⁷F₂, is much influenced by the gold NPs and increases by ≈100% for samples heat-treated at 350 °C during 41 h.     

Enhanced luminescent characteristics of laser-ablated GdVO4:Eu thin films by Li-doping

Li-doping has been used to improve luminescent characteristics of thin films. Influence of Li-doping on the crystallization, surface morphology and luminescent properties of GdVO₄:Eu³⁺ films have been investigated. Crystallinity and surface morphology of thin films have been very important factors to determine luminescent characteristics and depended on the deposition conditions. The GdVO₄:Eu³⁺ and Li-doped GdVO₄:Eu³⁺ thin films have been grown using pulsed laser deposition method on Al₂O₃ (0 0 0 1) substrates at a substrate temperature of 600 °C under an oxygen pressure of 13.33-53.33 Pa. The crystallinity and surface morphology of the films were investigated using X-ray diffraction (XRD) and atomic force microscope (AFM), respectively. A broadband incoherent ultraviolet light source with a dominant excitation wavelength of 310 nm and a luminescence spectrometer have been used to measure photoluminescence spectra at room temperature. The emitted radiation was dominated by the red emission peak at 619 nm radiated from the transition of ⁵D₀-⁷F₂ of Eu³⁺ ions. Particularly, the peak intensity of Li-doped GdVO₄ films was increased by a factor of 1.7 in comparison with that of GdVO₄:Eu³⁺ films. The enhanced luminescence results not only from the improved crystallinity but also from the reduced internal reflections caused by rougher surfaces. The luminescent intensity and surface roughness exhibited similar behavior as a function of oxygen pressure.     

Photoluminescence of Y2O3:Eu thin film phosphors by sol-gel deposition and rapid thermal annealing

Y₂O₃:Eu³⁺ phosphor films have been developed by using the sol-gel process. Comprehensive characterization methods such as Photoluminescent (PL) spectroscopy, X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize the Y₂O₃:Eu³⁺ phosphor films. In this experiment, the XRD profiles show that the Y₂O₃:Eu³⁺ phosphor films crystallization temperature and optimum annealing temperature occur at about 650 and 750 °C, respectively. The optimum dopant concentration is 12 mol% Eu³⁺ and the critical transfer distance (R_c) among Eu³⁺ ions is calculated to be about 0.84 nm. Vacuum environment is more efficient than oxygen and nitrogen to eliminate the OH content and hence yields higher luminescent phosphor films. The PL emission intensity of Y₂O₃:Eu³⁺ phosphor films is also dependent on the annealing time. It was found that the H₂O impurities were effectively eliminated after annealing time of 25 s at 750 °C in vacuum environment. From the experiment results, the schematic energy band diagram of Y₂O₃:Eu³⁺ phosphor films is constructed.     

Photoluminescence and phosphorescence properties of MAl2O4:Eu, Dy (M=Ca, Ba, Sr) phosphors prepared at an initiating combustion temperature of 500 °C

Eu²⁺ and Dy³⁺ co-doped calcium aluminate, barium aluminate and strontium aluminate phosphors were synthesized at an initiating combustion temperature of 500 °C using urea as an organic fuel. The crystallinity of the phosphors was investigated by using X-ray diffraction (XRD) and the morphology was determined by a scanning electron microscope (SEM). The low temperature monoclinic structure for both CaAl₂O₄ and SrAl₂O₄ and the hexagonal structure of BaAl₂O₄ were observed. The effect of the host materials on the photoluminescence (PL) and phosphorescence properties were investigated by using a He-Cd Laser and a Cary Eclipse fluorescence spectrophotometer, respectively. The broad band emission spectra observed at 449 nm for CaAl₂O₄:Eu²⁺, Dy³⁺, 450 nm (with a shoulder-peak at 500 nm) for BaAl₂O₄:Eu²⁺, Dy³⁺ and 528 nm for SrAl₂O₄:Eu²⁺, Dy³⁺ are attributed to the 4f⁶5d¹ to 4f⁷ transition in the Eu²⁺ ion in the different hosts.     

Synthesis and luminescent properties of europium-activated Ca2SnO4 phosphors by sol-gel method

In this paper, the Ca₂SnO₄:Eu³⁺ phosphor was prepared by low-temperature sol-gel method. The influence of calcined temperature and time on structure of Ca₂SnO₄:Eu³⁺ was investigated by using X-ray powder diffraction (XRD). The experimental results show that the dried gel was crystallized to the pure orthorhombic phase after calcination at 900 °C in air for 6 h. These phosphors have displayed bright red color under a UV source. The richness of the red color has been verified by determining their color coordination from the CIE standard charts, and this red emission has been assigned to ⁵D₀→⁷F₂ electric dipole transition at 616 and 620 nm. The excellent luminescence properties make it possible as a good candidate for plasma display panel (PDP) application.     

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.     

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.     

Synthesis and luminescence properties of needle-like SrAl2O4:Eu, Dy phosphor via a hydrothermal co-precipitation method

Needle-like SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had been prepared by calcining the precursors obtained from hydrothermal process at the temperature of 1100 °C in a weak reductive atmosphere of active carbon. The crystal structure, morphology and optical properties of the composites were characterized. X-ray diffraction (XRD) patterns illustrated that the single-phase SrAl₂O₄ was formed at 1100 °C, which is much lower than that prepared by the traditional method. The transmission electron microscope (TEM) observation revealed the precursors and the resulted SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had well-dispersed distribution and needle-like morphology with an average diameter about 150 nm at the center and the length up to 1 μm. After irradiation by ultraviolet radiation with 350 nm for 5 min, the phosphors emit green color long-lasting phosphorescence corresponding to the typical emission of Eu²⁺ ion, both the PL spectra and luminance decay revealed that the phosphors had efficient luminescent and long lasting properties.     

Characterization and photoluminescence properties of some MLn2(1−x)O4:2xEu or 2xTb systems (M=Ba or Sr, Ln=Gd or La)

BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ powders doped with different concentrations of Eu³⁺ or Tb³⁺ are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 900 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction and scanning electron microscopy. It is remarkable that all the samples of BaGd₂O₄, BaLa₂O₄ and SrLa₂O₄ have similar morphology. The SEM images show homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small elliptical shaped crystallites with an average diameter of about 0.5-3.0 μm. Photoluminescence for all materials increases with increase of temperature and shows a maximum for the samples heated to 900 °C with 4 mole% doping of Eu³⁺ or Tb³⁺ ions. The luminescence is almost same for all powders when doped with same concentration of Eu³⁺.     

Preparation and luminescent properties of europium-doped yttria fibers by electrospinning

Sub-micrometer-sized fibers of europium-doped yttria (Y₂O₃:Eu³⁺) were prepared by electrospinning followed by high-temperature calcinations for the first time. The fibers were with diameters of 200-400 nm and lengths of several 10 μm and cubic in phase. The spectral properties of the Y₂O₃:Eu³⁺ fibers were studied, in contrast with those of bulk powders. The results indicated that in the present Y₂O₃:Eu³⁺ fibers the excited charge transfer band had slightly blue shift in comparison with that in the bulk due to weaker covalence of Eu-O bonds. In addition, both of the lifetimes of the ⁵D₁ and ⁵D₀ states in the fibers became shorter than that in the bulk due to improved nonradiative transition rates.     

Luminescence properties of Euβ-diketonates incorporated in cubic mesoporous silica

Luminescent materials have been prepared by wet impregnation of Europium (III) dibenzoylmethane complexes in either non-silylated or silylated mesoporous MCM-48 silica. Silylation and incorporation of the Eu (III) complex were confirmed by Nuclear Magnetic Resonance, N₂-sorption, X-ray diffraction and Infrared spectroscopy. The luminescence properties were investigated at room and high temperatures up to 200 °C. Information on host-guest interactions were collected by analyzing the optical characteristics of the Eu (III) ions in the different media. In particular, the intensity parameter Ω₂ is confirmed to be a useful spectroscopic probe for Eu (III) first coordination shell interaction. The role of the O²⁻—Eu³⁺ charge transfer band and the impact of the silylation on the luminescence properties at room and high temperatures is demonstrated.     

Enhanced emission of Er from alternately Er doped Si-rich Al2O3 multilayer film with Si nanocrystals as broadband sensitizers

Alternately Er doped Si-rich Al₂O₃ (Er:SRA) multilayer film, consisting of alternate Er-Si-codoped Al₂O₃ (Er:Si:Al₂O₃) and Si-doped Al₂O₃ (Si:Al₂O₃) sublayers, has been synthesized by co-sputtering from separated Er, Si, and Al₂O₃ targets. The dependence of Er³⁺ related photoluminescence (PL) properties on annealing temperatures over 700-1100 °C was studied. The maximum intensity of Er³⁺ PL, about 10 times higher than that of the monolayer film, was obtained from the multilayer film annealed at 950 °C. The enhancement of Er³⁺ PL intensity is attributed to the energy transfer from the silicon nanocrystals in the Si:Al₂O₃ sublayers to the neighboring Er³⁺ ions in the Er:Si:Al₂O₃ sublayers. The PL intensity exhibits a nonmonotonic temperature dependence: with increasing temperature, the integrated intensity almost remains constant from 14 to 50 K, then reaches maximum at 225 K, and slightly increases again at higher temperatures. Meanwhile, the PL integrated intensity at room temperature is about 30% higher than that at 14 K.