Preparation and luminescent characteristics of Sr3RE2(BO3)4:Dy (RE = Y, La, Gd) phosphors for white LED

Dysprosium-activated Sr₃RE₂(BO₃)₄ (RE = Y, La, Gd) phosphors were synthesized by a high temperature solid-state reaction method. The phase uniformity of the phosphors was characterized by X-ray powder diffraction (XRD) and the luminescence characteristics were investigated. The excitation spectra at 575 nm emission show strong spectral bands in the region of 300-500 nm. The emission spectra of the phosphors with 365 nm excitation show three bands centered at 484 nm, 575 nm and 680 nm, which originate from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2 of Dy³⁺, respectively. The effect of Dy³⁺ concentration on the emission intensity of the phosphors was investigated. The fluorescence decay curves for ⁴F_9/2 → ⁶H_13/2 excited at 365 nm and monitored at λ_em of 575 nm were measured. The decay times decreased slowly with increasing Dy³⁺ doping concentration due to a trap capturing to resonance fluorescence transfer of the activated ions and due to the exchange interactions between activated ion pairs. In order to determine the type of interaction between activated ions, the concentration dependence curves (lg(I/x) versus lg x) of Sr₃RE₂(BO₃)₄:Dy³⁺ (RE = Y, La, Gd) were plotted. The concentration quenching mechanism of the ⁴F_9/2 → ⁶H_13/2 (575 nm) transition of Dy³⁺ is the d-d interaction. All results indicate these phosphors are promising white-color luminescent materials.     

Preparation of Dy-activated strontium orthosilicate (Sr2SiO4:Dy) phosphors and its photoluminescent properties

Dy³⁺-activated β/α′-Sr₂SiO₄ phosphors were successfully prepared by solid-state reaction method with ammonium chloride (NH₄Cl) as the flux. The influences of calcination temperatures, amounts of NH₄Cl and the concentrations of Dy³⁺ on phase composition, morphology and the photoluminescent properties of as-prepared powders were investigated in detail. The β and α′ phases of Sr₂SiO₄ were obtained with 1 wt% and 2-5 wt% NH₄Cl, respectively, as the sintered condition was at 1000 °C for 4 h. With increasing the amount of NH₄Cl, the morphology of phosphors changed from needlelike to regular polyhedron shape and the colors of the Sr₂SiO₄:Dy³⁺ phosphors changed from blue-green to white. The luminescence intensity of ⁴F_9/2 → ⁶H_15/2 transition was slightly higher than that of ⁴F_9/2 → ⁶H_13/2 (ΔL = 2, ΔJ = 2) transition owing to the low-symmetry around Dy³⁺ ions. The optimum concentration of Dy³⁺ was 2.0 mol% and the concentration quenching were caused by the d-d interaction and a cross relaxation. The yellow-to-blue intensity ratio (Y/B) of Dy³⁺ emission did not to change with varying the Dy³⁺ concentration using Li⁺ ions for charge compensation. These indicate that this phosphor can be used as a potential candidate for the phosphor-converted white LEDs with a UV chip.     

Preparation and luminescent properties of Eu doped Sr3La(PO4)3 phosphor

Eu²⁺-doped Sr₃La(PO₄)₃ phosphors were synthesized by solid-state reaction method. Their luminescent properties were investigated. The phosphor could be excited by ultraviolet light effectively. The emission spectra exhibit two emission peaks located at 418 nm and 500 nm, respectively. These two peaks originated from two different luminescent centers, respectively. One is nine-coordinated Eu(I) center, other is six-coordinated Eu(II) center. It was found that the doping concentration of Eu²⁺ ions affected the shape of emission spectra. As the doping concentration increasing, Eu²⁺ ions are more likely to form Eu(I) luminescent centers and emit purple light.     

Synthesis and phosphorescence properties of Mn, La and Ho in MgAl2Si2O8

Mn⁴⁺, La³⁺ and Ho³⁺ doped MgAl₂Si₂O₈-based phosphors were first synthesized by solid state reaction. They were characterized by thermogravimetry (TG), differential thermal analysis (DTA), X-ray powder diffraction (XRD), photoluminescence (PL) and scanning electron microscopy (SEM). The phosphors were obtained at about 1300 °C. They showed broad red and fuchsia-pink emission bands in the range of 610-715 nm and had a different maximum intensity when activated by UV illumination. Such a fuchsia-pink emission can be attributed to the intrinsic d-d transitions of Mn⁴⁺.     

Luminescence of complex ion WO12 in Dy doped nanocrystal Gd6WO12 phosphor

Nanocrystal Gd₆WO₁₂ phosphor doped with Dy³⁺ was prepared by a co-precipitation method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and selected area electron diffraction (SAED) were used to characterize the structure and morphology of the resultant phosphor. It was found that the phosphor exists in tetragonal phase and the phosphor particles show sphere-like shape with an average size of 31 nm. In aid of excitation and emission spectra, the energy levels of the complex ion WO₁₂¹⁸⁻ were confirmed, and that the possible luminescent mechanisms for various wavelengths excitation were analyzed. The cross relaxation and energy transfer between complex ion and Dy³⁺ were discussed. The dependence of luminescent intensity and color coordinates on the excitation wavelength was also investigated.     

Synthesis and characterization of YNbTiO6:Dy phosphor

A novel yellow phosphor of Dy³⁺ activated YNbTiO₆ has been prepared by high temperature solid-state reaction, and its luminescence properties have been investigated. The excitation spectra monitored at 575 nm have several strong peaks from 350 to 480 nm. Under 365 nm excitation, the emission spectra of composition-optimized (Y_0.9Dy_0.1)NbTiO₆ phosphor exhibit a dominant peak located at about 575 nm with the Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of (0.385, 0.411). The energy transfer between Dy³⁺ is found to be through exchange interaction.     

Photoluminescence and thermoluminescence studies of Mg2SiO4:Eu nano phosphor

Nanoparticles of Eu³⁺ doped Mg₂SiO₄ are prepared using low temperature solution combustion technique with metal nitrate as precursor and urea as fuel. The synthesized samples are calcined at 800 °C for 3 h. The Powder X-ray diffraction (PXRD) patterns of the sample reveled orthorhombic structure with α-phase. The crystallite size using Scherer's formula is found to be in the range 50-60 nm. The effect of Eu³⁺ on the luminescence characteristics of Mg₂SiO₄ is studied and the results are presented here. These phosphors exhibit bright red color upon excitation by 256 nm light and showed the characteristic emission of the Eu³⁺ ions. The electronic transition corresponding to ⁵D₀ → ⁷F₂ of Eu³⁺ ions (612 nm) is stronger than the magnetic dipole transition corresponding to ⁵D₀ → ⁷F₁ of Eu³⁺ ions (590 nm). Thermoluminescence (TL) characteristics of γ-rayed Mg₂SiO₄:Eu³⁺ phosphors are studied. Two prominent and well-resolved TL glows with peaks at 202 °C and 345 °C besides a shoulder with peak at ∼240 °C are observed. The trapping parameters-activation energy (E), order of kinetics (b) and frequency factor (s) are calculated using glow curve shape method and the results obtained are discussed.     

Luminescence studies of Ba1−xMg2−y(PO4)2:xEu, yMn phosphor

The phosphors BaMg₂(PO₄)₂ doped with Eu²⁺ and Mn²⁺ solely or doubly were prepared by solid state reaction, and their luminescent properties were also investigated. Under the excitation of 322 nm, it has been observed a broad blue emission band centered at 417 nm and a red emission band centered at about 665 nm, resulting from Eu²⁺ and Mn²⁺, respectively. Resonance-type energy transfers from Eu²⁺ to Mn²⁺ were discovered by directly overlapping the emission spectra of Eu²⁺ and the excitation spectra of Mn²⁺. According to the changes of relative intensities of Eu²⁺ and Mn²⁺ emission, efficiencies of energy transfer were calculated. Based on the principle of energy transfer, the relative intensities of blue and red emission could be tuned by adjusting the contents of Eu²⁺ and Mn²⁺.     

Synthesis and luminescence properties of Bi-doped YVO4 phosphors

YVO₄:Bi³⁺ phosphors have been prepared by a convenient high-temperature solid-state method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) technologies are used to study the luminescence properties of YVO₄:Bi³⁺ phosphors. The emission and excitation spectra of Bi³⁺ in the YVO₄ lattice have been investigated at room temperature. The excitation band peaks at 330 nm in a region among 250-400 nm, and the emission spectrum exhibits an intense yellowish-white broad emission centered at about 543 nm covering from 400 nm to 800 nm. The full width at half maximum (FWHM) is about 144 nm. The color coordinates of the as-synthesized YVO₄:Bi³⁺ phosphors are in a range of x = 0.358-0.374, y = 0.482-0.496. The dependence of the luminescence intensity on Bi³⁺ concentrations and heat treatment condition has also been discussed. In addition, we found that a little amount of flux NH₄Cl could enhance the Bi³⁺ luminescence intensity.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Sol-gel preparation and characterization of uniform core-shell structured LaInO3:Sm/Tb@SiO2 phosphors

The core-shell structured LaInO₃:Ln³⁺@SiO₂ (Ln³⁺ = Sm³⁺, Tb³⁺) phosphors were realized by coating LaInO₃:Ln³⁺ phosphors on the surface of silica microspheres via a modified Pechini sol-gel process. The phase, structure, morphology, and fluorescent properties of the materials were well characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FT-IR), photoluminescence (PL) spectra, cathodoluminescence (CL) spectra, and the kinetic decays, respectively. The results reveal that the obtained core-shell structured phosphors consist of amorphous silica core and crystalline LaInO₃:Ln³⁺ shell, which keep the uniform spherical morphology of pure silica spheres with narrow size distribution. Upon excitation by ultraviolet (UV) irradiation or electron beam, the phosphors show the characteristic emission lines of Sm³⁺ (⁴G_5/2-⁶H_5/2,7/2,9/2, orange) in LaInO₃:Sm³⁺@SiO₂ and characteristic emissions of Tb³⁺ (⁵D₄-⁷F_6,5,4,3, green) in LaInO₃:Tb³⁺@SiO₂, respectively. This kind of phosphors may have potential applications in field emission displays (FEDs) based on their uniform shape, low-cost synthetic route, and diverse luminescent properties.     

Luminescence properties of SrIn2O4:Eu incorporated with Gd or Sm ions

The photoluminescence (PL) properties of SrIn₂O₄:Eu³⁺,Gd³⁺ and SrIn₂O₄:Eu³⁺,Sm³⁺ are investigated in this work. When the Gd³⁺ ions are introduced in this compound, the average distance metal-oxygen is increased, and then the vibration of lattice is decreased. It results in that the nonradiation of Eu³⁺ is decreased. Therefore, the emissions of SrIn₂O₄:Eu³⁺ are increased. However, little of energy transfer occurs from Gd³⁺ to Eu³⁺ ions. When the Sm³⁺ ions are introduced into SrIn₂O₄:Eu³⁺, the energy transfers occur from the CTS of O²⁻-Sm³⁺ to Sm³⁺ and Eu³⁺ ions, from the host absorption to Eu³⁺ ions, and from Sm³⁺ to Eu³⁺ ions, but not from the host absorption to Sm³⁺ ions.     

Enhanced photoluminescence of GdPO4:Tb under VUV excitation by controlling ZnO content and annealing temperature

High-quality Zn-free and added GdPO₄:Tb³ green phosphors, i.e., fine size as well as smooth and spherical morphologies, were synthesized by ultrasonic spray pyrolysis. The influence of Zn²⁺ content and annealing temperature on the photoluminescence properties of the GdPO₄:Tb³ phosphors annealed at 800-1100 °C was investigated. The addition of Zn²⁺ for Gd³⁺ was highly effective for improving the photoluminescence properties of GdPO₄:Tb³. The Zn added GdPO₄:Tb³ phosphors with Zn/Gd = 0.045/0.805 showed the strongest emission of the prepared phosphors. The emission intensity at 544 nm for the GdPO₄:Tb³ phosphors with Zn/Gd = 0.045/0.805 annealed at 900 °C was 496% stronger than that at 800 °C.     

Vacuum ultraviolet spectroscopic properties of KSrPO4:Tb

KSrPO₄:Tb³⁺ phosphors were prepared by a solid-state method and their photoluminescence properties were investigated under vacuum ultraviolet excitation. In the excitation spectrum monitoring at 544 nm, the band in the region of 120-162 nm can be attributed to be the overlap of host absorption and charge transfer transition of O²⁻ → Tb³⁺, and the band ranging from 162 to 300 nm was assigned to the f-d transition of Tb³⁺. The photoluminescence spectrum shows that the phosphors exhibited a strong green emission around 544 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺ under the excitation of 147 nm. Optimal emission intensity was obtained when x = 7% in KSr_1-xPO₄:xTb³⁺ and the luminescent chromaticity coordinates were calculated to be (x = 0.317, y = 0.522) for KSr_0.93PO₄:7%Tb³⁺.     

Luminescent and magnetic properties of YVO4:Ln@Fe3O4 (Ln = Eu or Dy) nanocomposites

A series of core-shell bifunctional magnetic-optical YVO₄:Ln³⁺@Fe₃O₄ (Ln³⁺ = Eu³⁺ or Dy³⁺) nanocomposites have been successfully synthesized via two-step method. The nanocomposites have the advantage of high magnetic responsive and unique luminescence properties. The structure, luminescent and magnetic properties of the nanocomposites were investigated by XRD, TEM, PL and VSM. The maximum emission peaks of the nanocomposites are at 618 nm (doping Eu³⁺), 574 nm (doping Dy³⁺). The special saturation magnetization of the nanocomposites is 54 emu/g. The diameter of the nanocomposites is 400-900 nm.     

A study on microstructure and luminescent properties of oxyfluoride silicate glass-ceramics with (Ho,Yb):NaYF4 crystallites

Glass-ceramics containing NaYF₄ nanocrystals were prepared by heat-treatment from oxyfluoride silicate-based glass doped with Ho³⁺ and Yb³⁺ ions. The formation of crystalline fluoride phase was confirmed by X-ray diffraction and transmission electron microscopy. Absorption and emission spectra revealed that a fraction of Ho³⁺ and Yb³⁺ ions is incorporated into the NaYF₄ ordered lattice influencing spectroscopic features of glass-ceramics in comparison with those of precursor glass. Green up-conversion emission (545 nm) originating in the ⁵S₂ level in glass-ceramics and up-converted red emission (650 nm) originating in the ⁵F₅ level in as-melted glass were observed under optical pumping into Yb³⁺ absorption band and analyzed. Although both emissions in both materials are achieved by two-photon excitations, the relation between green and red emission intensity in glass-ceramics and glass implies that processes relevant to up-conversion phenomena are different. Based on a careful analysis of relaxation dynamics of Ho³⁺ and Yb³⁺ excited states, the mechanisms involved in conversion of the infrared radiation into the visible emission in these materials are proposed and discussed.     

Polarized spectral analysis of Er ions in Er:LiGd(MoO4)2 crystal

The Er³⁺:LiGd(MoO₄)₂ crystal with Ø21 × 33 mm³ was grown by the Czochralski technique, and the absorption spectra, the fluorescence spectra and the fluorescence decay curves were measured at room temperature. Some spectroscopic parameters, such as the parameters of oscillator strengths, the spontaneous transition probabilities, the fluorescence branching ratios, the radiative lifetimes and the emission cross-sections were estimated based on Judd-Ofelt theory and Füchtbauer-Ladenburg method. The infrared emission at 1450-1650 nm, due to ⁴I_13/2 → ⁴I_15/2 transition and the visible emission at 520-569 nm corresponding to ²H_11/2,⁴S_3/2 → ⁴I_15/2 transition were observed in Er³⁺:LiGd(MoO₄)₂ crystals under 979 nm excitation at room temperature. The emission cross-sections are 4.37 × 10⁻²⁰ cm² at 553 nm and 0.584 × 10⁻²⁰ cm² at 1561 nm for π-polarization, and the following measured lifetimes are 4.57 ms and 10.74 μs. The upconversion emissions were attributed to energy transfer between Er³⁺ ions and the excited state absorption.     

Photoluminescence and energy transfer studies on Eu and Ce co-doped SrCaSiO4 for white light-emitting-diodes

The luminescence of SrCaSiO₄:Eu²⁺, Ce³⁺ is studied as a potential ultraviolet light-emitting diodes (UV-LEDs) phosphor that is capable of converting the ultraviolet emission of a UV-LED into green light with good luminosity. There are two emissions peaks peaking at 420 and 500 nm, respectively. The two emissions come from d-f transitions of Ce³⁺ and Eu²⁺, respectively. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped SrCaSiO₄ due to a part of spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺. The Ce³⁺/Eu²⁺ energy transfer, thoroughly investigated by the diffuse reflection emission and excitation spectra, photoluminescence decay curves, is demonstrated to be in the mechanism of electric dipole-dipole interaction.     

Blue and green emissions with high color purity from nanocrystalline Ca2Gd8Si6O26:Ln (Ln = Tm or Er) phosphors

Blue and green light emissive nanocrystalline Ca₂Gd₈Si₆O₂₆ (CGS):Tm³⁺ and CGS:Er³⁺ phosphors with high color purity were prepared by solvothermal reaction method. The structural and morphological properties of these phosphors were evaluated by the powder X-ray diffraction (XRD) and scanning electron microscopy, respectively. From the XRD results, Tm³⁺:CGS and Er³⁺:CGS phosphors had the characteristic peaks of oxyapatite in the hexagonal lattice structure. The visible luminescence properties of phosphors were obtained by ultraviolet (UV) or near-UV light and low voltage electron beam (0.5-5 kV) excitation. The photoluminescence and cathodoluminescence properties were investigated by changing the variation of Tm³⁺ or Er³⁺ concentrations and the acceleration voltage, respectively. The CGS:Tm³⁺ phosphors exhibited the blue emission due to ¹D₂→³F₄ transition, while the CGS:Er³⁺ phosphors showed the green emission due to ⁴S_3/2→⁴I_15/2 transition. The color purity and chromaticity coordinates of the fabricated phosphors are comparable to or better than those of standard phosphors for lighting or imaging devices.     

Synthesis and photoluminescence of Eu by co-doping Eu and Cl in Sr2P2O7 under air atmosphere

A novel phosphor Sr₂P₂O₇ co-doped with europium ion and chlorine ion was firstly synthesized by solid state reaction under air atmosphere. Its properties were systematically analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and fluorescence spectra. The introduction of chlorine into the system was helpful and necessary to Eu³⁺ substitute Sr²⁺ site and subsequently to reduce Eu³⁺ to Eu²⁺, XPS results confirmed that some amount of Eu³⁺ ions could be reduced to Eu²⁺ ions under air atmosphere at high temperature. The reduction tendency of Eu³⁺ depends not only on the doping Cl⁻ content, but also on the sintering temperature and time. Photoluminescence spectra also revealed that europium ions were present in divalent as well as trivalent oxidation states, the emission peak at 415 nm is ascribed to the typical 5d-4f transition of Eu²⁺, 592 nm and 613 nm assigned to the characteristic transitions of ⁵D₀-⁷F_1,2 of Eu³⁺. Such abnormal reduction was attributed to the electronegative defects formed by nonequivalent substitution of Eu³⁺ on the Sr²⁺ sites in the investigated phosphors.