Luminescent properties of R2(MoO4)3:Eu (R=La, Y, Gd) phosphors prepared by sol-gel process

A series of red phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) have been synthesized by sol-gel method. The crystallization processes of the phosphor precursors were characterized by X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA), and the properties of these resulting phosphors have also been characterized by photoluminescence (PL) spectra and reflectance spectra. Field emission scanning electron microscopy (FE-SEM) was also used to characterize the shape and the size of the samples. The results of TG-DTA and XRD indicated that all of the R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors crystallized completely at 650 °C. Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ have two structures, monoclinic and orthorhombic, while La_0.8Eu_1.2(MoO₄)₃ only adopts monoclinic structure. The luminescent properties of phosphors R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) are dependent on their structures to some extent. The orthorhombic Y_0.8Eu_1.2(MoO₄)₃ and Gd_0.8Eu_1.2(MoO₄)₃ phosphors show very similar luminescent properties, which differ from those of phosphors with monoclinic structure. For all of R_0.8Eu_1.2(MoO₄)₃ (R=La, Y, and Gd) phosphors, intense red emission is obtained by exciting at ∼394 and ∼465 nm which are owing to the sharp ⁷F₀→⁵L₆ and ⁷F₀→⁵D₂ lines of Eu³⁺. Two strongest lines at 394 and 465 nm in excitation spectra of these phosphors match well with the two popular emissions from near-UV and blue GaN-based LEDs, so they could be used as red components for white light-emitting diodes.     

A potential red phosphor LiGd(MoO4)2:Eu for light-emitting diode application

Eu³⁺-doped LiGd(MoO₄)₂ red phosphor was synthesized by solid-state reaction, and its photoluminescent properties were measured. The effect of Eu³⁺ doping concentration on PL intensity was investigated, and the optimum concentration of Eu³⁺ doped in LiGd(MoO₄)₂ was found to be 30 mol%. Compared with Y₂O₂S:0.05Eu³⁺, Na_0.5Gd_0.5MoO₄:Eu³⁺ and KGd(MoO₄)₂:Eu³⁺, the LiGd(MoO₄)₂:Eu³⁺ phosphor showed a stronger excitation band around 395 nm and a higher intensity red emission of Eu³⁺ under 395 nm light excitation. For the first time, intensive red light-emitting diodes (LEDs) were fabricated by combining phosphor and a 395 nm InGaN chip, confirming that the LiGd(MoO₄)₂:Eu³⁺ phosphor is a good candidate for LED applications.     

NaEu0.96Sm0.04(MoO4)2 as a promising red-emitting phosphor for LED solid-state lighting prepared by the Pechini process

NaEu_0.96Sm_0.04(MoO₄)₂ was prepared by the Pechini method (P phosphor) and as a comparison, also by solid-state reaction technique (S phosphor). The photo-luminescent properties, the morphology and the grain size were investigated. The phosphors show broadened excitation band around 400 nm, high intensity of Eu³⁺⁵D₀→⁷F₂ emission upon excitation around 400 nm, and appropriate CIE chromaticity coordinates. Intensive red light-emitting diodes (LEDs) were fabricated by combining the phosphor and a 400 nm InGaN chip for the first time, which confirm that the phosphor is a good candidate for near UV LED. The luminescent intensity of P phosphor prepared at 700 °C is near that of S phosphor prepared at 800 °C. In addition, P phosphor shows advantages of lower calcining temperature, shorter heating time, and smaller grain size. Considering all these factors, the suitable method for preparing the promising near UV LED phosphor NaEu_0.96Sm_0.04(MoO₄)₂ is recommended to be the Pechini process at 700 °C.     

Synthesis and luminescence properties of red-emitting phosphors NaY0.87Eu0.13(WO4)1.2(MoO4)0.8

A series of NaY_1−yEu_y(WO₄)_2−x(MoO₄)_x (x=0−2 and y=0.06−0.15) phosphors have been prepared by a combustion route. X-ray powder diffraction, photoluminescence excitation and emission spectra were used to characterize the resulting samples. The excitation spectra of these phosphors show the strongest absorption at about 396 nm, which matches well with the commercially available n-UV-emitting GaN-based LED chip. Their emission spectra show an intense red emission at 616 nm due to the ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. As the Mo content increases, the intensity of the ⁵D₀→⁷F₂ emission of Eu³⁺ activated at wavelength of 396 nm increases and reaches a maximum when the relative ratio of Mo/W is 2:3. The intense red-emission of the tungstomolybdate phosphors at near-UV excitation suggests that the material is a potential candidate for white light emitting diode (WLEDs).     

Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.     

Emission color variation of M2SiO4:Eu (M=Ba, Sr, Ca) phosphors for light-emitting diode

The luminescent properties of alkaline earth orthosilicates M₂SiO₄ (M=Ba, Sr, Ca) doped with Eu²⁺ ions are investigated. Two emission bands are assigned to the f-d transitions of Eu²⁺ ions doped into two different cation sites in host lattices confirmed by electron paramagnetic resonance signal. Two emission bands show the different emission color variation with substituting M²⁺ cations with smaller cations. This behavior is discussed in terms of two competing factors of the crystal field strength and covalence. Also the decay times are in order of 600-1000 ns. These phosphors with maximum excitation of around 370 nm can be applied as a color-tunable phosphor for light-emitting diode based on ultraviolet chip/phosphor technology.     

Combustion synthesis and luminescence properties of NaY1−xEux(WO4)2 phosphors

The red phosphors NaY_1−xEu_x(WO₄)₂ with different concentrations of Eu³⁺ were synthesized via the combustion synthesis method. As a comparison, NaEu(WO₄)₂ was prepared by the solid-state reaction method. The phase composition and optical properties of as-synthesized samples were studied by X-ray powder diffraction and photoluminescence spectra. The results show that the red light emission intensity of the combustion synthesized samples under 394 nm excitation increases with increase in Eu³⁺ concentrations and calcination temperatures. Without Y ions doping, the emission spectra intensity of the NaEu(WO₄)₂ phosphor prepared by the combustion method fired at 900 °C is higher than that prepared by the solid-state reaction at 1100 °C. NaEu(WO₄)₂ phosphor synthesized by the combustion method at 1100 °C exhibits the strongest red emission under 394 nm excitation and appropriate CIE chromaticity coordinates (x=0.64, y=0.33) close to the NTSC standard value. Thus, its excellent luminescence properties make it a promising phosphor for near UV InGaN chip-based red-emitting LED application.     

Eu activated M6AlP5O20 (M=Sr/Ba/Mg) novel red phosphors

Eu³⁺ activated M₆AlP₅O₂₀ (where M=Sr/Ba/Mg) phosphors prepared by combustion synthesis and the completion of the synthesis was confirm by XRD (X-ray diffraction) patterns. The surface morphology studied by scanning electron microscopy (SEM) and photoluminescence (PL) properties has been reported in this paper. The Eu³⁺ PL emission spectrum was observed in M₆AlP₅O₂₀ phosphors (where M=Sr/Ba/Mg) at 592 (orange) and 618 nm (red) region, the spectrum due to ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions at mercury free excitation, respectively. Its considerable emission intensity under 350 nm excitations makes it possible candidate materials as red component of tricolor luminescence materials and for near ultra violet light emitting diode (n-UVLED) phosphors.     

Dy3+ emission in M5(PO4)3F (M = Ca, Ba) phosphor

Ultrafine M₅(PO₄)₃F:Dy³⁺ (M = Ca, Ba) phosphors were prepared via combustion process using metal nitrates as precursors. The formation of crystalline phosphate was confirmed by X-ray diffraction pattern. The PL excitation spectra show the excitation peaks observed at 250 to 400 nm due to f → f transition of Dy³⁺ ion, which are useful for solid-state lighting purpose (mercury free excitation). The PL emission of Dy³⁺ ion by 348 nm excitation gave an emission at 489 nm (blue), 582 nm (yellow) and 675 nm (red). All the characteristics of BYR emissions like BGR indicate that Dy doped Ca₅(PO₄)₃F and Ba₅(PO₄)₃F phosphors are good candidates that can be applied in solid-state lighting phosphor (mercury free excited lamp phosphor) and white light LED.      

Sol-gel growth of Gd2MoO6:Eu nanocrystalline layers on SiO2 spheres (SiO2@Gd2MoO6:Eu) and their luminescent properties

SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors were prepared by the sol-gel process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as kinetic decays were used to characterize the resulting SiO₂@Gd₂MoO₆:Eu³⁺ core-shell phosphors. The XRD results demonstrate that the Gd₂MoO₆:Eu³⁺ layers on the SiO₂ spheres begin to crystallize after annealing at 600 °C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 600 nm), are not agglomerated, and have a smooth surface. The thickness of the Gd₂MoO₆:Eu³⁺ shells on the SiO₂ cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀-⁷F₂ red emission at 613 nm) under the excitation of 307 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles.     

Luminescence optimization of Eu-doped LnAl3(BO3)4 (Ln=Y, Gd) red phosphor using spray pyrolysis

LnAl₃(BO₃)₄:Eu³⁺ (Ln=Y, Gd) red phosphor particles were prepared by spray pyrolysis and the luminescent intensity under vacuum ultraviolet (VUV) excitation was investigated by changing Eu³⁺ content, Y/Gd molar ratio, and boron content. The concentration quenching for Eu³⁺ activator was observed at 5 at%. The highest luminescent intensity at 615 nm due to the ⁵D₀→⁷F₂ transitions of Eu³⁺ was achieved when the ratio of Gd to Y was 0.55. The R/O ratio (obtained by dividing the red emission intensity at 615 nm with the orange one at 592 nm), however, was not influenced by the G/Y ratio. Using excess boron, up to 135% of the stoichiometric quantity, improved the emission intensity of LnAl₃(BO₃)₄:Eu³⁺ red phosphor. According to XRD analysis, the sample prepared using boron of a stoichiometric quantity had YBO₃ phase as a minor phase. Such YBO₃ phase progressively disappeared with an increase in the excess quantity of boron, which was responsible for the enhancement of emission intensity. In addition, the R/O ratio became larger and larger by increasing the excess content of boron due to a reduction in the symmetry of Y site. Consequently, both the emission intensity and the color coordinate of LnAl₃(BO₃)₄:Eu³⁺ red phosphors were successfully optimized in terms of the Y/Gd ratio and the excess quantity of boron in spray pyrolysis.     

Intense green/yellow emission in Ca8Zn(SiO4)4Cl2:Eu, Mn through energy transfer for blue-LED lighting

Eu²⁺ and Mn²⁺ co-doped Ca₈Zn(SiO₄)₄Cl₂ phosphors have been synthesized by a high temperature solid state reaction. Energy transfer from Eu²⁺ to Mn²⁺ is observed. The emission spectra of the phosphors show a green band at 505 nm of Eu²⁺ and a yellow band at 550 nm of Mn²⁺. The excitation spectra corresponding to 4f⁷-4f⁶5d transition of Eu²⁺ cover the spectral range of 370-470 nm, well matching UV and/or blue LEDs. The shortening of fluorescent lifetimes of Eu²⁺ followed by simultaneous increase of fluorescent intensity of Mn²⁺ with increasing Mn²⁺ concentrations is studied based on energy transfer. Upon blue light excitation the present phosphor can emit intense green/yellow in comparison with other chlorosilicate phosphors such as Eu²⁺ and Mn²⁺ co-doped Ca₈Mg(SiO₄)₄Cl₂ and Ca₃SiO₄Cl₂, demonstrating a potential application in phosphor converted white LEDs.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

发光二极管用SrWO4:Eu3+红光荧光粉激发谱强度的调控

采用化学共沉淀法制备了Eu³⁺掺杂摩尔分数不同、煅烧温度不同的SrWO₄:Eu³⁺系列发光粉体, 所制备的粉体均具有Eu³⁺特征的强室温红光荧光发射. 通过调节煅烧温度和掺杂摩尔分数来调控近紫外和蓝光吸收强度, 进而调控用395 nm的近紫外光和465 nm的蓝光激发样品所得红光发光强度. 研究结果表明, 所制备的SrWO₄:Eu³⁺红光荧光粉可以被紫外和蓝光发光二极管有效激 关键词： 稀土掺杂 4:Eu³⁺')" href="#">SrWO₄:Eu³⁺ 光致发光 白光发光二极管     

Luminescent properties of a novel red-emitting phosphor: Eu-activated Ca3Sr3(VO4)4

A new luminescent material, Eu³⁺ activated Ca₃Sr₃(VO₄)₄, was investigated. This compound shows a strong red emission centered at 618 nm under near-UV light with two distinct absorption bands; charge transfer state of VO₄³⁻ and f-f transitions of europium ions. As the europium concentration is increased, an additional red-emitting phosphor, EuVO₄, which is known to be a prominent luminescent material in the near-UV region can be traced. The UV excited luminescent properties of this material may find application in the production of red phosphors for white light-emitting diodes.     

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.     

KGd(MoO4)2:Eu as a promising red phosphor for light-emitting diode application

A red phosphor KGd(MoO₄)₂:Eu³⁺ was prepared by solid-state reaction technique at high temperature. Its photoluminescent property was investigated and the optimum concentration of Eu³⁺ doped in the KGd(MoO₄)₂ is 25 mol%. Compared with Y₂O₂S:0.05Eu³⁺, the obtained KGd(MoO₄)₂:Eu³⁺ shows wider excitation band around 400 nm, higher intensity of Eu^{3+ 5}D₀–⁷F₂ emission upon excitation 393 nm, and the CIE chromaticity coordinates (x = 0.655, y = 0.345) are closer to the standard of National Television Standard Committee (NTSC). The optical properties of KGd(MoO₄)₂:Eu³⁺ suggest that it is an efficient red-emitting phosphor for light-emitting diode applications.     

Color tunability of nanophosphors by changing cations for solid-state lighting

X₃MgSi₂O₈: Eu²⁺, Mn²⁺ (X=Ba, Sr, Ca) phosphors with the mean particle size of 200 nm and the spherical shape are synthesized through combustion method. They show three emission colors under near-ultraviolet light: the blue and green colors from Eu²⁺ ions and the red color from Mn²⁺ ions. Three emission bands show the different emission colors with changing X²⁺ cations. These color shifts are discussed in terms of two competing factors of the crystal field strength and the covalency. These phosphors with maximum excitation of around 375 nm can be applied as color-tunable phosphors for white-light-emitting diode based on ultraviolet/phosphor technology.     

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.     

Optical properties of blue emitting Ce activated XMg2Al16O27 (X = Ba, Sr) phosphors

Here we reported that the optical properties of novel blue-emitting Ce³⁺ activated XMg₂Al₁₆O₂₇ (X = Ba, Sr) phosphors were prepared by combustion method successfully. The excitation spectrum shows a broad band extending from 280 to 380 nm, centered at 355 nm, and the emission spectrum shows intense blue emission broad band centering at 441 nm for Ba²⁺ and Sr²⁺ host lattices. XRD pattern indicates crystalline nature of prepared phosphors. SEM analysis shows morphology of the ternary-hexaaluminate based phosphor prepared by combustion method. The Ce³⁺ activated XMg₂Al₁₆O₂₇ (X = Ba, Sr) should be a promising blue phosphor for near ultraviolet-based white-light-emitting diodes.