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⁺.     

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.     

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.     

Eu/Sm ions co-doped white light luminescence SrSiO3 glass-ceramics phosphor for White LED

Eu²⁺/Sm³⁺ co-doped silicate glass was prepared by high temperature melting under reducing atmosphere and the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics were obtained after heat-treatment. X-ray diffraction (XRD) and Raman spectra confirmed the formation of SrSiO₃ nano-crystals in the glass matrix. The photoluminescence excitation (PLE) spectra and photoluminescence (PL) spectra of the samples were measured. A broad emission band from 400 nm to 550 nm due to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ was observed, as well as several sharp emission peaks at 563 nm, 600 nm, 646 nm and 713 nm ascribed to the 4f → 4f transitions of Sm³⁺. The luminescence properties of the glass ceramics with different molar ratio of Eu²⁺/Sm³⁺ were studied and the corresponding chromaticity coordinates were calculated. The ultraviolet light-emitting diode (UV-LED) excitable glass-ceramics emitting white light were obtained by tuning the relative emission intensity of Eu²⁺ and Sm³⁺. The results indicate that the Eu²⁺/Sm³⁺ co-doped SrSiO₃ transparent glass-ceramics can be used as a potential matrix material for White LED under UV-LED excitation.     

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.     

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⁺.     

Synthesis and photoluminescence properties of color-tunable BaLa2WO7:Eu phosphor

Color-tunable phosphors BaLa_2−xEu_xWO₇ were synthesized via a solid-state reaction. The absorption, excitation, emission and decay curves were obtained to study the luminescence properties. The experimental results indicate that BaLa_2−xEu_xWO₇ phosphors have two regions in the excitation spectra: one is assigned to the charge-transfer state (CTS) band at about 338 nm, and the other is assigned to the intra-4f transitions at 360-600 nm. The emission spectra of BaLa_2−xEu_xWO₇ phosphors excited at 395 nm exhibit a series of sharp peaks, which are attributed to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions. Luminescence from higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed at low Eu³⁺ concentration. The optimal emission intensity of ⁵D₀ → ⁷F₂ red emission is at x = 0.4 (BaLa_1.6Eu_0.4WO₇). The chromaticity coordinates of BaLa_2−xEu_xWO₇ phosphors vary with Eu³⁺ content from white, orange-red, to red, making it a candidate for a white-light-emitting phosphor in UV-LEDs.     

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.     

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.     

Enhanced red emission in LiAl5O8:Fe phosphor by B doping

Fe³⁺, B³⁺ co-doping LiAl₅O₈ phosphor has been successfully synthesized by a solid-state reaction method assisted with wet chemical mixing route. Photoluminescence emission peak is observed at around 672 nm excited at both 290 nm ultraviolet and 565 nm green light. With introduction of a small amount of boric acid, the red emission intensity can be enhanced by 2.62 times under 290 nm excitation and 2.31 times under 565 nm excitation, respectively. It is believed that the substitution of B³⁺ ions for Al³⁺ sites decreases the symmetry of the luminescence center, intensifying the red emission.     

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⁺.     

Photoluminescent properties of LiSrxBa1−xPO4:RE (RE = Sm, Eu) f-f transition phosphors

Rare-earth ions (Sm³⁺ or Eu³⁺) doped LiSr_xBa_1−xPO₄ (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) f-f transition phosphor powders were prepared by a high temperature solid-state reaction. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the phase structure of the sample changes from LiBaPO₄ to LiSrPO₄ when x changes from 0 to 1.0. The excitation spectra indicate that only direct excitation of rare earth ions (Sm³⁺ or Eu³⁺) can be observed. The doped rare earth ions show their characteristic emission in LiSr_xBa_1−xPO₄, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Sm³⁺⁴G_5/2 → ⁶H_J (J = 5/2, 7/2, 9/2, 11/2), respectively. The dependence of the emission intensities of the LiSr_xBa_1−xPO₄:Sm³⁺ and LiSr_xBa_1−xPO₄:Eu³⁺ phosphors on the x value and Ln³⁺ (Ln³⁺ = Sm³⁺, Eu³⁺) concentration is also investigated.     

Luminescence properties of Eu and Eu doped calcium-deficient hydroxyapatite prepared in air

Eu-doped calcium-deficient hydroxyapatite Ca_8.95Eu_0.05HPO₄(PO₄)₅OH (designated CDHA:Eu) was prepared via the coprecipitation method and calcined in air. Phase purity, crystal structure and morphology of the CDHA:Eu were characterized using X-ray diffraction spectrometer and scanning electron microscopy. The photoluminescence excitation and emission spectra of Eu²⁺ and Eu³⁺ ions were measured using luminescence spectrometer. The emission spectra showed a broad emission band centered at 450 nm corresponded to the typical 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions, and sharp peaks corresponded to the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ ions. This research was focused on the site-distribution of Eu³⁺ ions. The Eu³⁺ in different sites had different spectroscopic features and the charge compensation mechanisms were also discussed.     

Reddish orange long afterglow phosphor Ca2SnO4:Smprepared by sol-gel method

A reddish orange light emissive long afterglow phosphor, Ca₂SnO₄:Sm³⁺ was prepared by sol-gel method at lower temperature. The synthesized phosphors were characterized by X-ray diffraction, scanning electron micrograph images, photoluminescence spectra, afterglow decay curves and thermoluminescence spectra. Three emission peaks locate at 565 nm, 609 nm and 655 nm corresponding to CIE chromaticity coordinates of x = 0.53 and y = 0.47, which indicates the reddish orange light emitting. The fluorescent intensity and the afterglow characteristic depends on the concentration of Sm³⁺ and the optimized concentration is 1.5 mol%. The afterglow decay curves are well fitted with triple-exponential decay models. The thermoluminescence glow curves show that the Sm³⁺ induces suitable trap depth and result in the long afterglow phenomenon, and the corresponding increase or decrease in afterglow is associated with trap concentration, nearly no change in trap depth. The 1.5 mol% Sm³⁺-doped Ca₂SnO₄ sample has the biggest trap concentration and exhibit the best afterglow characteristic, its’ afterglow time is about 1 h. The phosphorescence mechanism of this long afterglow phosphor was discussed.     

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.     

Enhancement of upconversion luminescence of Y2O3:Er nanocrystals by codoping Li-Zn

The upconversion (UC) luminescence in sol-gel synthesized Li⁺, Zn²⁺, or Li⁺-Zn²⁺ codoped Y₂O₃:Er³⁺ nanocrystals were investigated under the excitation of a 970 nm diode laser. Compared to undoped Y₂O₃:Er³⁺ samples, proper doping of Li⁺-Zn²⁺ leads to an drastic increase of the UC luminescence centered at 560 nm by a factor of 28. The UC luminescence enhancement is a result of the increased lifetime of the intermediate state ⁴I_11/2 (Er). The intensity ratio of the green over red emissions (green/red) is also affected by the codoping of Zn²⁺, Li⁺ and Li⁺-Zn²⁺ ions. Our results demonstrated that the Li⁺-Zn²⁺ codoping in Y₂O₃:Er³⁺ phosphors produced remarkable enhancement of the UC luminescence and green/red ratio, making this nanocrystal a promising candidate for photonic and biological applications.     

Enhanced mid-IR emission in Yb-Tm co-doped oxyfluoride glass ceramics

Tm³⁺-Yb³⁺ co-doped transparent oxyfluoride glass ceramics were prepared through thermal treatment of the as-prepared glasses. The precipitation of nanocrystals and the incorporation of Tm³⁺ and Yb³⁺ into the nanocrystals were confirmed by X-ray diffraction and absorption spectra. Based on the Judd-Ofelt theory, the J-O parameters Ω_λ (λ = 2, 4, 6), spontaneous radiative transition rates, radiative lifetimes and fluorescence branching ratios of Tm³⁺ in both as-prepared glasses and glass ceramics were calculated. Intense mid-IR emission and upconversion luminescence in the Tm³⁺ and Yb³⁺ co-doped glass ceramics were observed under 980 nm excitation. Especially, compared with that of the as-prepared glasses, mid-IR luminescence intensity of Tm³⁺ in the glass ceramics was greatly enhanced. Desirable spectroscopic characteristics suggest that these oxyfluoride glass ceramics may be promising mid-IR laser active medium.     

Preparation and characteristics of Fe3O4@YVO4:Eu bifunctional magnetic-luminescent nanocomposites

A facile direct precipitation method has been developed for the synthesis of bifunctional magnetic-luminescent nanocomposites with Fe₃O₄ nanoparticles as the core and YVO₄:Eu³⁺ as the shell. Transmission electron microscopy (TEM) images revealed that the obtained bifunctional nanocomposites had a core-shell structure and a spherical morphology. The average size was ∼150 nm, and the thickness of the shell was ∼15 nm. The X-ray diffraction (XRD) patterns showed that a cubic spinel structure of Fe₃O₄ core and a tetragonal phase of YVO₄ shell were obtained. Fourier transform infrared (FT-IR) spectra confirmed that the YVO₄:Eu³⁺ had been successfully deposited on the surface of Fe₃O₄ nanoparticles. Photoluminescence (PL) spectra indicated that the nanocomposites displayed a strong red characteristic emission of Eu³⁺. Magnetic measurements showed that the obtained bifunctional nanocomposites exhibited superparamagnetic behavior at room temperature. Therefore, the bifunctional nanocomposites are expected to develop many potential applications in biomedical fields.     

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.     

White light emission in Tm/Er/Yb tri-doped Y2O3 transparent ceramic

Tm³⁺/Er³⁺/Yb³⁺ triply doped Y₂O₃ transparent ceramics were fabricated by solid state reaction and characterized from the point of view of white light upconversion luminescence. All the samples exhibited high transparency not only in near-infrared band but also in visible region. Strong red (Er³⁺: ⁴F_9/2 → ⁴I_15/2), green (Er³⁺: ²H_11/2, ⁴S_3/2 → ⁴I_15/2) and blue (Tm³⁺: ¹G₄ → ³H₆) upconversion emissions have been observed under 980 nm excitation at room temperature. By varying the concentration of Er³⁺ ion, various colors of upconversion luminescence (pure blue, bluish green, pure green and yellowish green), including white light with CIE-X = 0.295 and CIE-Y = 0.312, can be easily achieved.