New red phosphor for near-ultraviolet light-emitting diodes with high color-purity

New red phosphors, Na₅Eu(MoO₄)₄ doped with boron oxide were prepared by the solid-state reaction. Their structure and photo-luminescent properties were investigated. With the introduction of boron oxide, the red emission intensity of the phosphors under 395 nm excitation is strengthened, with high color-purity (x = 0.673, y = 0.327). The single red light-emitting diode was obtained by combining InGaN chip with the red phosphor, bright red light can be observed by naked eyes from the red light-emitting diodes under a forward bias of 20 mA.     

Disorder in layered hydroxides: synthesis and DIFFaX simulation studies of Mg(OH)2

Powder X-ray diffraction (PXRD) patterns of magnesium hydroxides precipitated under different conditions exhibit characteristic non-uniform broadening of Bragg peaks which cannot be explained merely on the basis of Scherrer broadening. The broadening is shown to arise due to interstratification and turbostratic disorder.     

Luminescent properties of long lasting phosphor Ca2MgSi2O7:Eu

Long afterglow phosphors (Ca_1−xEu_x)₂MgSi₂O₇ (0.002 ≤ x ≤ 0.02) were prepared by solid-state reactions under a weak reductive atmosphere. X-ray diffraction pattern, photoluminescence spectra, decay curve, afterglow spectra and thermoluminescence curves were investigated. The phosphors showed two emission peaks when they were excited by 343 nm, due to two types of Eu²⁺ centers existing in the Ca₂MgSi₂O₇ lattice. However, only one emission peak can be found in their afterglow spectra. Energy transfer between Eu²⁺ ions in inequivalent sites was found. A possible mechanism was presented and discussed. The afterglow decay time of Ca_1.998MgSi₂O₇:Eu_0.002 was nearly 12.5 h which means it was a good long lasting phosphor.     

Enhanced long persistence of Sr2SnO4:Sm red phosphor by co-doping with Dy

We report the observation of long lasting red phosphorescence in Sr₂SnO₄:Sm³⁺ and Sr₂SnO₄:Sm³⁺, Dy³⁺ phosphors. The decay patterns of afterglow curves demonstrate that the afterglow time of Sr₂SnO₄:Sm³⁺ could be prolonged by the incorporation of Dy³⁺. The remarkable changes in the thermoluminescence glow curve exhibited that the first band responsible for the origin of the afterglow becomes the most prominent feature when Dy³⁺ added. In other words, the enhancement of the red afterglow in Sr₂SnO₄:Sm³⁺, Dy³⁺ compared with Sr₂SnO₄:Sm³⁺ could be ascribed to more appropriate traps (the hole-traps V^″Sr) created by the incorporation of Dy³⁺.     

Europium-doped yttrium silicate nanophosphors prepared by flame synthesis

Europium-doped yttrium silicate (Y₂SiO₅:Eu³⁺) nanophosphors were successfully synthesized by flame spray pyrolysis method. The effect of silicon concentration on the crystal structure and morphology of the Y₂SiO₅:Eu³⁺ phosphors were investigated. As-prepared phosphor consists of spherical nanoparticles with filled morphology, high crystallinity, narrow size distribution, and intense photoluminescence. The crystal structure and photoluminescence intensity of Y₂SiO₅:Eu³⁺ nanophosphors are strongly affected by the ratio of silicon to yttrium in the precursor solution, and the maximum photoluminescence intensity is obtained from particles prepared from the silicon to yttrium ratio of 1.25. A concentration quenching limit is observed at 30 mol% Eu of yttrium. The photoluminescence intensity also increases with the increase of the concentration of precursor solution. This work demonstrates the advantages of flame spray pyrolysis method for the preparation of multi-component nanophosphor, which can be found potential application in lamp and display industries.     

Structural characterization and photocatalytic properties of novel Bi2YVO8

Bi₂YVO₈ was prepared by solid-state reaction for the first time. The structural and photocatalytic properties of Bi₂YVO₈ were studied. The results showed that this compound has the tetragonal crystal system with space group I4/mmm. The band gap of Bi₂YVO₈ was estimated to be about 2.09 eV by plotting (αhν)² versus hν and obtaining the hν axis intercept value according to Tauc's equation. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water with Bi₂YVO₈ as the photocatalyst under ultraviolet light irradiation (wavelength = 390 nm). Degradation of aqueous methylene blue photocatalyzed by this compound was investigated under visible light irradiation. Bi₂YVO₈ showed higher photocatalytic activity compared to Bi₂YTaO₇, Bi₂InTaO₇ or TiO₂ (P-25). Complete removal of aqueous methylene blue was achieved after visible light irradiation for 170 min. The decrease of the total organic carbon and the formation of inorganic products such as SO₄²⁻ and NO₃⁻ revealed the continuous mineralization of aqueous methylene blue during photocatalytic reaction.     

The effects of cerium doping on the size,morphology, and optical properties of α-hematite nanoparticles for ultraviolet filtration

Metal oxide nanoparticles have potential use in energy storage, electrode materials, as catalysts and in the emerging field of nanomedicine. Being able to accurately tailor the desirable properties of these nanoceramic materials, such as particle size, morphology and optical bandgap (E_g) is integral in the feasibility of their use. In this study we investigate the altering of both the structure and physical properties through the doping of hematite (α-Fe₂O₃) nanocrystals with cerium at a range of concentrations, synthesised using a one-pot co-precipitation method. This extremely simple synthesis followed by thermal treatment results in stable Fe_2−xCe_xO_y nanoceramics resulting from the burning of any unreacted precursors and transformation of goethite-cerium doped nanoparticle intermediate. The inclusion of Ce into the crystal lattice of these α-Fe₂O₃ nanoparticles causes a significantly large reduction in mean crystalline size and alteration in particle morphology with increasing cerium content. Finally we report an increase optical semiconductor bandgap, along with a substantial increase in the ultraviolet attenuation found for a 10% Ce-doping concentration which shows the potential application of cerium-doped hematite nanocrystals to be used as a pigmented ultraviolet filter for cosmetic products.     

The photoluminescence properties of Y2O3:Eu prepared by surfactant assisted co-precipitation-molten salt synthesis

Y₂O₃:Eu³⁺ red phosphors were prepared by surfactant assisted co-precipitation-molten salt synthesis method. The effects of surfactant content and annealing temperature on the structure and luminescence were investigated by X-ray diffraction and fluorescence spectrophotometer. The use of surfactant reduces the impurities on the surface of particles and promotes the reaction. The color purity of as-prepared Y₂O₃:Eu³⁺ red phosphors is improved with the presence of surfactant. In the excitation spectra, two strong bands at 394 and 466 nm are attributed to ⁷F_0,1-⁵L₆, ⁷F_0,1-⁵D₂ transitions of Eu³⁺ ions respectively. With the excitation of 394 or 466 nm, the as-fabricated samples reveal excellent red emission as high as that of samples monitored by 254 nm. Thus, the Y₂O₃:Eu³⁺ is a promising red phosphor for ultraviolet-visible light-emitting diodes.     

Synthesis of non-stoichiometric Bi2O4−x by oxidative precipitation

Bi₂O_4−x, a Bi mixed-valence phase was prepared at 95 °C, by a precipitation process, in a basic medium with a highly oxidizing K₂S₂O₈/Na₂S₂O₈. This phase has a low thermal stability as it decomposes below 400 °C in a multiple step process by some O₂ losses prior to finally transforming into γ-Bi₂O₃. The as-prepared powders are 50-60 nm in size with a narrow size distribution. Optical spectra of Bi₂O_4−x exhibit a broad absorption band with a band gap of ∼1.4 eV as compared to 2.61 eV for Bi₂O₃. The composition of this non-stoichiometric phase, which crystallizes in cubic fluorite related structure with a cell parameter of 5.538(3) Å, is Bi₂O_{3.65 ± 0.10}.     

High pressure optical studies of α-ZnAl2S4:Cr

The effect of hydrostatic pressure (varying up to 91 kbar) at room temperature emission spectra and fluorescence lifetime of the Cr³⁺ R1 line (²E → ⁴A₂ transition) in tiospinel ZnAl₂S₄ was studied for the first time. The studies performed reveal the shift of the R1 line with increasing pressure. Such a red shift was accompanied by a significant change of the fluorescence lifetime. Both trends were successfully explained by a simple model, which resulted in adequate agreement between the calculated and the observed.     

Enhanced luminescence by charge compensation in red-emitting Eu-activated Ca3Sr3(VO4)4

The effects of charge compensation on the luminescence behavior of a red-emitting phosphor, Ca₃Sr₃(VO₄)₄:Eu³⁺, were investigated. It has been observed that charge compensated by monovalent ions, especially Na⁺, shows greatly enhanced red emission under ultraviolet excitation. It is found that Na₂CO₃ addition acts as a fluxing agent and plays a role in charge compensation, which clearly improves the emission intensity of Eu³⁺-activated Ca₃Sr₃(VO₄)₄. Enhanced emission intensity of the corresponding charge compensated phosphors under ultraviolet radiation may find application in the production of red phosphors for white light-emitting diodes.     

Optimum IV-group ion concentrations in ZnGa2O4−xMx (M=S, Se, Te) phosphors for enhancement of luminescence

The ZnGa₂O_4−xM_x (M=S, Se, and Te ) samples with varying S, Se, and Te concentrations are synthesized through solid-state reactions. The X-ray diffraction patterns of ZnGa₂O_4−xM_x (M=S, Se, and Te) show that the positions of the (4 0 0) diffraction peak gradually shift to lower angles due to the doping of VI-group ions (S, Se, and Te) with larger ionic radius than oxygen. For ZnGa₂O_4−xS_x samples, the solubility limit is found to be about x=0.30. The cathodoluminescence measurements on ZnGa₂O_4−xM_x samples show that the optimized S, Se, and Te concentrations with the highest cathodoluminescence intensities are 0.10, 0.05, and 0.03, respectively. The luminous intensity of ZnGa₂O_3.95Se_0.05 is four times higher than that of ZnGa₂O₄. Thus, ZnGa₂O_3.95Se_0.05 can be a promising candidate phosphor for FED applications.     

Unusual intrinsic luminescence of the host and energy transfer process in YVO4:Er phosphors

YVO₄:Er³⁺ phosphors were prepared by solid state reaction method. The X-ray diffraction results testify the pure tetragonal YVO₄ crystalline phase. The emission spectra of the samples show the obvious intrinsic luminescence of the hosts even though the concentration of the dopants has reached nominal 6 mol%, which is unusual since it is believed that the energy transferring from VO₄³⁻ to rare-earth ions occurs efficiently, thus the intrinsic luminescence of the host disappears when the concentration of the dopants is higher than ∼1 mol%. The comparison of the photoluminescence excited at 320 nm (the absorption of vanadate host) and 380, 490, 525 or 532 nm (the absorption of erbium ions) in visible and infrared range has revealed that energy transfer process has occurred in the system. The study of decay times has revealed that the energy transfer efficiency of the doped YVO₄:Er samples is very low. The low efficiency might be one important reason for the unusual intrinsic emission of the host.     

The reaction of ceria coatings on mica with H2S: An in-situ X-ray diffraction study

Thin layers of ceria were deposited on the surface of mica platelets in solution. The reaction of such particles with hydrogen sulfide yields a red colored special effect pigment. The ceria layer reacts with H₂S to produce a variety of sulfide and oxysulfide phases. The reaction path discovered in situ by time and temperature resolved X-ray diffraction is CeO₂→CeS₂→C-Ce₂S₃→Ce₁₀S₁₄O. The reaction itself is extremely variable depending on gas flow, heating rates and decomposition atmospheres. Effects on the thin film are recorded by scanning electron microscopy (SEM) and revealed a destruction of the layer once red Ce₁₀S₁₄O was formed. The product layer then reveals the typical nonwetting behaviour of a liquid on a surface.     

A novel broadband emission phosphor Ca2KMg2V3O12 for white light emitting diodes

A novel broadband emission phosphor Ca₂KMg₂V₃O₁₂ was first synthesized by solution combustion method. The X-ray diffraction showed that Ca₂KMg₂V₃O₁₂ phase can be obtained at 600-900 °C through combustion route. The crystal structure of this material was refined by Rietveld method using powder X-ray diffraction. It crystallizes in cubic system and belongs to space group Ia3d with z = 8, a = 0.12500 nm. The excitation band of Ca₂KMg₂V₃O₁₂ peaks at 320 nm in a region between 260 nm and 425 nm, and the emission spectrum exhibits an intense band centered at about 528 nm covering from 400 nm to 800 nm. The colour coordinates of samples prepared at different ignition temperatures are in a range of x = 0.323-0.339, y = 0.430-0.447.     

Effect of solubility YAG:Nd nanocrystals in glass matrix

The nanocomposites of Y₃Al₅O₁₂:Nd³⁺ (YAG:Nd) incorporated in borate glass were obtained. The single phase of YAG:Nd nanocrystals were obtained by sol-gel method. The borate glass was melted first and ground up then mixed with the nanocrystals. The samples were formed into pellets under pressure and were annealed in temperatures from the range 550-800 °C. The X-ray diffraction patterns show that together with increasing the temperature the contribution of Y₃Al₅O₁₂ phase decreases and the new YBa₃B₉O₁₉ phase is observed. The luminescence measurements indicates that the band structures and distribution of band intensities of glass-YAG:Nd nanocrystal composites depends crucially on annealing temperature.     

Synthesis and photoluminescence properties of SrLu2O4:Eu superfine phosphor

Superfine powder SrLu₂O₄:Eu³⁺ was synthesized with a precursor prepared by an EDTA - sol-gel method at relatively low temperature using metal nitrate and EDTA as starting materials. The heat decomposition mechanism of the precursor, formation process of SrLu₂O₄:Eu³⁺and the properties of the particles were investigated by thermo-gravimetric (TG) - differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) analyses. The results show that pure SrLu₂O₄:Eu³⁺ superfine powder has been produced after the precursor was calcinated at 900 °C for 2 h and has an elliptical shape and an average diameter of 80-100 nm. Upon excitation with 250 nm light, all the SrLu₂O₄:Eu³⁺ powders show red and orange emissions due to the 4f-4f transitions of Eu³⁺ ions. The highest photoluminescence intensity at 610 nm was found at a content of about 6 mol% Eu³⁺. Splitting of the ⁵D₀-⁷F₁ emission transition revealed that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite by substituting Lu³⁺ ions.     

Structural study and luminescence of TlSrLa(AsO4)2

This work presents the crystal structure and luminescent properties of TlSrLa(AsO₄)₂. In this phase Tl⁺ ions are located in large tunnels delimited by chains of alternating (AsO₄) and (Sr,La)O₈ polyhedra. Thallium atoms are eightfold coordinated with C₁ symmetry. Large TlO distances are observed revealing a low stereochemical activity of the 6s² lone pair. Excitation and emission spectra of Tl⁺ in TlSrLa(AsO₄)₂ showed broad bands at lower energy than those observed in previous works. Excitation spectra are decomposed into multiple Gaussian bands and a theoretical analysis is made to explain the number of observed components. Two Gaussian components are revealed for emission spectra.     

Controllable synthesis and optical properties of NdOHCO3 dodecahedral microcrystals

NdOHCO₃ dodecahedral microcrystals with an orthorhombic structure have been successfully synthesized by the hydrothermal method used urea as the precipitator. Experimental parameters, such as the reaction temperature, the reaction time, and the molar ratio of the starting reagents were examined. The as-synthesized products were characterized by powder X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence. The possible growth process of NdOHCO₃ dodecahedral microcrystals was discussed.     

Luminescence properties of Ca1−xSrxSe:Ce phosphors and their potential application for GaN-based LEDs

A series of solid solution phosphors Ca_1−xSr_xSe:0.02Ce³⁺ were prepared using high-temperature solid-state reaction technique. Their diffuse reflectance and luminescent spectra at room temperature were investigated and discussed. The optical band gap E_g energies of CaSe and SrSe were derived. Because of its broad band absorption in the range of 400-500 nm, Ca_1−xSr_xSe:Ce³⁺ can suit the application requirements for GaN-based light-emitting diodes (LEDs). The emission wavelength and the coordinates systematic shift from yellowish green to bluish green with an increase in x of Ca_1−xSr_xSe:Ce³⁺. Using Dorenbos's empirical equation, the values of energies of the lowest f-d transition absorption E, redshift D and Stokes shift ΔS for Eu²⁺ in the same host were predicted. The results were in good agreement with the experimental data.