Effects of Li<Superscript>+</Superscript> co-doping on the concentration quenching threshold and luminescence of GdVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> nanophosphors

Europium ions (Eu³⁺) and Lithium ions (Li⁺) codoped gadolinium orthovanadate with a tetragonal phase had been successfully synthesized by an efficient hydrothermal method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) were utilized to characterize the microstructure, morphology, and luminescent properties of as-prepared samples. The various concentrations (0～14 at.%) of Li ions were applied to investigate the effect of Li⁺ co-doping concentration on the crystalline structure, microstructure, and emission intensity of GdVO₄:Eu³⁺, Li⁺ nanophosphors. The results demonstrated that Li⁺ ion co-doping changes the lattice parameters in two different ways. Moreover, the optical photoluminescent property was obtained when the Li⁺ co-doping concentration is 10 at.%. The influence of Li⁺ co-doping on the concentration quenching effect of Eu³⁺ was discussed as well. The concentration quenching threshold of Eu³⁺ was increased distinguishably. The potential mechanism was proposed in this paper.     

Photoluminescence properties of blue-emitting Li4SrCa(SiO4)2:Eu2+ phosphor for solid-state lighting

Blue-emitting Li₄SrCa(SiO₄)₂:Eu²⁺ phosphors have been synthesized by solid-state reaction. The photoluminescence (PL) excitation spectrum shows broad-band absorption and matches well with the emission of a near-UV (n-UV) chip. The PL emission spectrum exhibits a broad-band emission peaking at 430 nm, which is the characteristic emission of the f–d transition of the Eu²⁺ ion. The diffuse reflection spectra, temperature-dependent emission spectra, fluorescence decay, and mechanism of concentration quenching are also studied in detail. Li₄SrCa(SiO₄)₂:Eu²⁺ is a candidate blue phosphor for n-UV excited solid-state lighting.     

Synthesis and luminescence properties of Eu3+,Bi3+-doped BaWO4 phosphors

BaWO₄:Eu³⁺,Bi³⁺ phosphors have been prepared by the conventional high-temperature solid-state reaction and chemical precipitation. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) technologies. When the phosphors are prepared by the high-temperature solidstate reaction, Bi³⁺ doping into BaWO₄:Eu³⁺ can increase the emission intensity of 613 nm. However, maximum emission at about 595 nm was observed in Eu³⁺,Bi³⁺-doped BaWO₄ phosphors prepared by the chemical precipitation. The decay constants (monitored at 595 and/or 613 nm) are within 45–100 s. The color purity of the Ba_0:865WO₄: Eu_0:11,Bi_0:025 phosphor (prepared by chemical precipitation) was 100%. The emission mechanism of Eu³⁺,Bi³⁺ in the BaWO₄ phosphors is briefly discussed.     

Correlation of photoluminescence of (Y, Ln)VO4:Eu (Ln=Gd and La) phosphors with their crystal structures

We have studied the photoluminescence (PL) of (Y, Ln)VO₄:Eu³⁺ (Ln=La and Gd) phosphors and the correlation of the PL of those phosphor with their crystal structure. It is found that (Y, Gd)VO₄:Eu³⁺ phosphors have the same crystal structure as YVO₄:Eu³⁺, which is tetragonal with a little different lattice parameters. In the case of (Y, La)VO₄:Eu³⁺ phosphors, however, the gradual change from tetragonal to monoclinic structure of host lattice was observed as the amount of La ion increased. To investigate the PL property of (Y, Ln)VO₄:Eu³⁺ (Ln=La and Gd) phosphors, vacuum ultraviolet (VUV) and ultraviolet (UV) excitation were used. The favorable crystal structure for the PL intensity of orthovanadate phosphor under 147 and 254 nm excitation was tetragonal containing Gd ion and under 365 nm excitation was monoclinic containing La ion which might have the lowest site symmetry for Eu³⁺ ion.     

Studies in crystal structure and luminescence properties of Eu-doped metal tungstate phosphors for white LEDs

The correlation between the crystal structure and luminescent properties of Eu³⁺-doped metal tungstate phosphors for white LEDs was investigated. Red-emitting A_4−3x(WO₄)₂:Eu_x³⁺ (A=Li, Na, K) and B_(4−3x)/2(WO₄)₂:Eu_x³⁺ (B=Mg, Ca, Sr) phosphors were synthesized by solid-state reactions. The findings confirmed that these phosphors exhibited a strong absorption in the near UV to green range, due to the intra-configurational 4f-4f electron transition of Eu³⁺ ions. The high doping concentration of Eu³⁺ enhanced the absorption of near UV light and red emission without any detectable concentration quenching. Based on the results of a Rietveld refinement, it was attributed to the unique crystal structure. In the crystal structure of the Eu³⁺-doped metal tungstate phosphor, the critical energy transfer distance is larger than 5 Å so that exchange interactions between Eu³⁺ ions would occur with difficulty, even at a high doping concentration. The energy transfer between Eu³⁺ ions, which causes a decrease in red emission with increasing concentration of Eu³⁺, appears to be due to electric multi-polar interactions. In addition, the Eu-O distance in the host lattice affected the shape of emission spectrum by splitting of emission peak at the ⁵D₀→⁷F₂ transition of Eu³⁺.     

Crystallinity and morphology dependent luminescence of Li-doped Y2−xGdxO3:Eu thin film phosphors

The influence of lithium doping on the crystallization, the surface morphology, and the luminescent properties of pulsed laser deposited Y_2−xGd_xO₃:Eu³⁺ thin film phosphors was investigated. The crystallinity, the surface morphology, and the photoluminescence (PL) of films depended highly on the Li-doping and the Gd content. The relationship between the crystalline and morphological structures and the luminescent properties was studied, and Li⁺ doping was found to effectively enhance not only the crystallinity but also the luminescent brightness of Y_2−xGd_xO₃:Eu³⁺ thin films. In particular, the incorporation of Li and Gd into the Y₂O₃ lattice could induce remarkable increase in the PL. The highest emission intensity was observed Li-doped Y_1.35Gd_0.6O₃:Eu³⁺ thin films whose brightness was increased by a factor of 4.6 in comparison with that of Li-doped Y₂O₃:Eu³⁺ thin films.     

Luminescent properties of Eu3+ and Sm3+ activated M2SiO4 (M=Ba,Sr and Ca) red-emitting phosphors for WLEDs

Eu³⁺ and Sm³⁺ activated M₂SiO₄ (M=Ba, Sr and Ca) red-emitting phosphors were synthesized by a solid state reaction. The results of XRD and SEM measurements show that the samples are single phase and have irregular shape. The excitation and emission spectra indicate that these phosphors were effectively excited by ultraviolet (395 nm) and blue (466 nm) light and exhibited red performance. The charge compensator R⁺ (R⁺=Li⁺, Na⁺ and K⁺) injecting into the host efficiently enhanced the luminescence intensity of the M₂SiO₄: Eu³⁺ and M₂SiO₄: Sm³⁺ phosphors. The emission intensity of M₂SiO₄: Eu³⁺ and Sm³⁺ doping Li⁺ were higher than that of Na⁺ or K⁺.     

Sol-gel method and luminescence properties of the ZrO<Subscript>2</Subscript>:Eu<Superscript>3+</Superscript> phosphors with different charge compensation

Eu³⁺-doped ZrO₂ phosphors with different charge compensators (Li⁺, Na⁺, K⁺) were prepared by the sol-gel method. The properties of the as-obtained samples are characterized by X-ray diffraction, scanning electron microscope, photoluminescence spectra, and decay curve. The results show that ZrO₂:Eu³⁺ phosphors with different charge compensation are mixed phase of tetragonal and monoclinic phase, and the volume fraction of tetragonal phase of ZrO₂:Eu³⁺/Na⁺ phosphor is bigger than the other phosphors. The phosphors can emit strong red light at 606~616 nm (⁵D₀ → ⁷F₂) excited by ultraviolet light (395 nm). Compared with two charge compensation patterns in the ZrO₂:Eu³⁺, it has been found that ZrO₂:Eu³⁺ phosphors used Na⁺ as charge compensator show greatly enhanced red emission under 395 nm excitation and longer luminescence lifetime.     

Preparation and photoluminescence properties of the Eu2+, Sm3+ co-doped Li2SrSiO4 phosphors

A series of Eu²⁺ and Sm³⁺ co-doped Li₂SrSiO₄ phosphors are prepared by the high temperature solid-state reaction. The morphology, structure and spectroscopic properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, diffuse reflection spectra, photoluminescence spectra and electron paramagnetic resonance spectra, respectively. The effect of Sm³⁺ doping concentration on the photoluminescence intensity of the prepared samples is also investigated. The results indicate that the crystal structure of Li₂SrSiO₄ is not changed with the Eu²⁺, Sm³⁺ co-doping. The spherical-like particle size of the obtained product is about 20–30 nm in diameter. When the Sm³⁺ concentration is 0.3 mol% and the Eu²⁺ concentration is 0.7 mol%, the phosphors show the maximum emission intensity, which is 50% higher than that of Eu²⁺ doped Li₂SrSiO₄. Excited at 420 nm, the phosphor presents a single broad emission band peaking at 558 nm, which is ascribed to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ and ⁴G_5/2 → ⁶H_5/2 and ⁴G_5/2 → ⁶H_7/2 transitions of Sm³⁺. The Commission International de I′Eclairage chromaticity coordinates of Li₂SrSiO₄:0.7 mol% Eu²⁺, 0.3 mol% Sm³⁺ are x = 0.28, y = 0.28.     

Luminescence studies of thallium co-doped KBr:Eu2+ powder phosphors

In this study, photoluminescence (PL) and photostimulated luminescence (PSL) properties in KBr:Eu²⁺, Tl⁺ powder phosphors are reported. PL emission spectra of these Tl⁺ co-doped KBr:Eu²⁺ phosphors show four overlapping bands around 310, 325, 360 and 375 nm in addition to the characteristic of Eu²⁺ ions at 420 nm. These additional short wavelength bands were attributed to centres involving Tl⁺ ions. The decrease in PSL intensity of γ-irradiated KBr:Eu²⁺, Tl⁺ powder phosphors with Tl⁺ concentration and the absence of thallium emission bands in PSL were attributed to the efficient electron trapping by Tl⁺ ions during irradiation.     

Enhancement of up-conversion luminescence in Zn2SiO4:Yb3+, Er3+ by co-doping with Li+ or Bi3+

Yb³⁺/Er³⁺ co-doped Zn₂SiO₄ ceramics are rapidly synthesized by the microwave radiation method. Green and red up-conversion emissions are observed in Zn₂SiO₄: Yb³⁺, Er³⁺ ceramics under 980 nm excitation. The influence of co-doped Li⁺ or Bi³⁺ ion on luminescence intensity for the phosphors has been investigated. At Li⁺ or Bi³⁺ doping concentration of 1 mol%, up-converted green emission can be increased by 6 times and 20 times, respectively. It is believed that co-doped Li⁺ or Bi³⁺ ion results in the local distortion of Er³⁺ in Zn₂SiO₄, increasing the intra-4f transitions of Er³⁺ ions. The local distortion is proved by spectral probing method with Eu³⁺.     

The effect of flux materials on the physical and optical properties of Eu-activated yttrium oxide phosphors

A flux fusion method was used to obtain the various sizes of Eu³⁺-activated Y₂O₃ red phosphors. The flux material was selected as an independent variable to control the physical properties of phosphor particles and their effects on the morphology and size distribution of phosphors were examined by scanning electron microscopy. The concentration of the flux materials and synthetic temperature were optimized for maximal photoluminescence intensity. Fluoride-based flux materials were found to work for the crystal formation of Eu³⁺-activated Y₂O₃. In particular, when a BaF₂ flux was used during the reaction at 1450 °C for 3 h, the photoluminescence (PL) intensity of Eu³⁺-activated Y₂O₃ was 25% higher than that without a flux and spherical phosphors had a mean particle size of 4-5 μm. The morphology and size distribution of the synthesized Eu³⁺-activated Y₂O₃ phosphor were predominantly dependent upon the type and concentration of flux material and synthetic temperature.     

UV-induced photoluminescence and thermally stimulated luminescence of CaSO4:Eu and CaF2:Tb3+ phosphors

Ultraviolet radiation induced changes in photoluminescence (PL) and thermally stimulated luminescence (TSL) of europium activated calcium sulphate (CaSO₄:Eu³⁺, Eu²⁺) and terbium doped calcium fluoride (CaF₂:Tb³⁺) phosphors have been studied. PL measurements suggest conversion of Eu³⁺ to Eu²⁺ on 254 nm irradiation corresponding to charge transfer band of Eu³⁺ ions and reduction of Eu²⁺ ions with 365 nm illumination representing a f–d transition of Eu²⁺ ions. Similar studies carried out on CaF₂:Tb³⁺ phosphor, however, do not show any significant wavelength specific changes. The integrated TSL output appears to be rate-dependent for both phosphors. The wavelength dependent changes in TSL output observed for CaSO₄:Eu phosphor have been correlated with those obtained in PL studies. The changes in TSL and PL characteristics of CaF₂:Tb³⁺ phosphor have been explained on the basis of stabilisation of traps based on matrix specific charge similarities.     

Luminescent properties of Li2 (Ca0.99, Eu0.01) SiO4: B3+ particles as a potential bluish green phosphor for ultraviolet light-emitting diodes

In our study, the 1% mol Eu²⁺ doped Li₂CaSiO₄: B³⁺ phosphors were prepared by the combustion method as fluorescent material for ultraviolet, light-emitting diodes (UV-LEDs) used as a light source. The properties of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ phosphors with urea concentration, doping boric acid and a series of initiating combustion temperature were investigated. The crystallization and particle sizes of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ has been investigated by using powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). Luminescence measurements showed that the phosphors can be efficiently excited by UV to the visible region, and exhibited bluish green light with a peak of 480 nm. The results showed that the boric acid was effective in improving the luminescence intensity of Li₂ (Ca_0.99, Eu_0.01) SiO₄: B³⁺ and the optimum molar ratio of boric acid to calcium nitrate was about 0.06. The optimized phosphors Li₂ (Ca_0.99, Eu_0.01) SiO₄: B _0.06 ³⁺ showed 180% improved emission intensity compared with that of the Li₂ (Ca_0.99, Eu_0.01) SiO₄ phosphors under ultraviolet (λ_ex =287 nm) excitation.      

Improved luminescence of Y2MoO6:Eu3+ by doping Li+ ions for light-emitting diode applications

The photoluminescence (PL) property of Y₂MoO₆:Eu³⁺ doped with Li⁺ is investigated in this paper. The red luminescence of Eu³⁺ in Y₂MoO₆ lattice has greatly enhanced by codoping monovalent alkali metal ions Li⁺ into the lattice. The drastic increase in the luminescence intensity of Y_2?xLi_xMoO₆:Eu³⁺ originates from the reason that the Li⁺ ions may serve as a self-promoter for better crystallization to reduce the defect or as a lubricant for the complete incorporation of the Eu³⁺ ions into the Y₂MoO₆ host.     

Solvothermal synthesis and luminescent properties of Y2Ti2O7:Eu3+ spheres

Pyrochlore‐structured yttrium titanate phosphors activated by trivalent europium ions (Y₂Ti₂O₇(YT):Eu³⁺), with spherical morphology, were synthesized at different pH values by a solvothermal process. From the structural and morphological measurements, the annealing temperature had no effect on the spherical morphology of the YT:Eu³⁺ sample. The photoluminescence excitation and emission spectra were taken by activating the Eu³⁺ ions in the YT host lattice as functions of Eu³⁺ ion concentration and annealing temperature. The optimal doping concentration was found to be 4 mol%, exhibiting an excellent orange–red emission due to the highest intensity of the ⁵D₀ → ⁷F₁ transition. When the YT:Eu³⁺ phosphor was mixed with YAG:Ce³⁺ phosphor, a brilliant white light emission was achieved. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Luminescent properties of R doped Sr2SiO4:Eu(R=Li, Na and K) red-emitting phosphors for white LEDs

Sr₂SiO₄:Eu³⁺ and Sr₂SiO₄:Eu³⁺ doped with R⁺(R⁺=Li⁺, Na⁺ and K⁺) phosphors were prepared by conventional solid-state reaction and investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and photoluminescence spectroscopy. XRD patterns and SEM reveal that the optimal firing condition for Sr₂SiO₄:Eu³⁺ was 1300 °C for 4 h. The excitation and emission spectra indicate that the phosphor can be effectively excited by ultraviolet (395 nm) and blue (466 nm) light and emits intense red light peaked at around 614 nm corresponding to the ⁵D₀→⁷F₂ transitions of Eu³⁺. In the research work, the effect of R⁺ contents on luminescence property and the Eu³⁺ concentration quenching process have also been investigated. The Eu³⁺ concentration quenching mechanism was verified to be a multipole-multipole interaction and the critical energy-transfer distance was calculated to be around 14.6 Å. The dopant R⁺(R⁺=Li⁺, Na⁺ and K⁺) as charge compensator in Sr₂SiO₄:Eu³⁺ can further enhance luminescence intensity, and the emission intensity of Sr₂SiO₄:Eu³⁺ doping Li⁺ is higher than that of Na⁺ or K⁺.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

Synthesis and characterization of novel red emitting nanocrystal Gd6WO12:Eu phosphors

Novel nanosized Gd₆WO₁₂:Eu³⁺ phosphors were synthesized via a co-precipitation reaction. The crystal structure and morphology of the phosphors were characterized by using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). It was found that the resultant powders show a regular and sphere-like shape with average particle size of 60 nm. Intrinsic red emission originating from Eu³⁺ was observed while excited at the W⁶⁺→O²⁻ and Eu³⁺→O²⁻ charge transfer bands or f-f absorption bands. The color coordinates of the phosphors were calculated to be x=0.625, y=0.375. The concentration dependence of the luminescence was studied, and optimum doping concentration for obtaining maximum emitting intensity was confirmed to be around 12 mol%. It was also found that the electric dipole-dipole interaction plays an important role for quenching luminescence of Eu³⁺.     

Photoluminescence of Rare Earth Phosphors Na0.5Gd0.5WO4: RE3+ and Na0.5Gd0.5(Mo0.75W0.25)O4: RE3+ (RE=Eu, Sm, Dy)

Two series of phosphors, Na_0.5Gd_0.5WO₄: RE³⁺ and Na_0.5Gd_0.5(Mo_0.75W_0.25)O₄: RE³⁺ (RE?=?Eu, Sm, Dy) have been synthesized by hydrothermal process to obtain the high purity, which have been characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM). The results suggest that Na_0.5Gd_0.5(Mo_0.75W_0.25)O₄: RE³⁺ phosphors are more easily to crystallize than Na_0.5Gd_0.5WO₄: RE³⁺ ones. Both of them present the characteristic luminescence of Eu³⁺, Sm³⁺ and Dy³⁺. Especially the photoluminescent properties of Na_0.5Gd_0.5WO₄: x%Eu³⁺ (Sm³⁺) can be obtained to show white luminescence as the suitable doping concentration of Eu³⁺ or Sm³⁺.