Surface treatment investigation and luminescence properties of SiO2-coated Ca2BO3Cl:0.02Eu2+ phosphors via sol–gel process

SiO₂-coated Ca₂BO₃Cl:Eu²⁺ phosphors were prepared by the sol–gel method in order to enhance the chemical and thermal stabilities of Ca₂BO₃Cl:Eu²⁺ phosphor. The phase structures, microstructures and luminescence properties were studied by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectrometer, respectively. The emission intensity of SiO₂-coated Ca₂BO₃Cl:Eu²⁺ phosphor decreased a little compared to that of the uncoated phosphor. The moisture resistances of the phosphors were comparatively examined by the aging treatment experiment in the water, and the thermal stability was studied by the temperature dependent photoluminescence spectra. The results indicated that SiO₂ coating on the surface of the phosphor particles improved the moisture-resistance and thermal stability to a large extent.     

Improved moisture resistance of SrS:Eu phosphors with nanoscale SiO2 coating

Orange-emitting SrS:Eu²⁺ phosphors were coated with nanoscale SiO₂ and their photoluminescence (PL) degradation behavior in moist air was investigated. The SiO₂ coating was obtained by sol-gel process using diethoxydimethylsilane (DEDMS) and the coating content was varied from 0.5 to 2 wt%. The coatings were composed of a uniform, continuous, and amorphous SiO₂ layer of 30-50 nm thickness and the coating thickness was not varied significantly with the coating content. No peak shift and no decrease of PL intensity were observed after coating. The PL intensity of the coated phosphors decreased to ∼75% of the original value after 10 h exposure to moist air, while the uncoated phosphor decreased to ∼33%, which indicates the improved moisture resistance of the nanoscale SiO₂ coated SrS:Eu²⁺ phosphors.     

Low thermal quenching and high-efficiency Ce, Tb-co-doped Ca3Sc2Si3O12 green phosphor for white light-emitting diodes

Low thermal quenching and high-efficiency Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSSO:Ce³⁺) phosphors with co-doping Tb³⁺ ion were prepared by a solid state method and the properties of these phosphors were investigated. The results showed that co-doping of Tb³⁺ not only enhances the photoluminescence remarkably and decreases the thermal quenching of the phosphor, but also heightens the performances of the LEDs fabricated with the phosphor. A high-efficiency and low color temperature white LED was fabricated with the prepared CSSO:1%Ce³⁺, 0.5%Tb³⁺ and a red phosphor, indicating that CSSO:1%Ce³⁺,0.5%Tb³⁺ phosphor is a suitable green phosphor for the fabrication of high-efficiency white LEDs.     

Luminescent properties of a new green emitting Eu doped CaZrSi2O7 phosphor for WLED applications

CaZrSi₂O₇ (CZS), a modification of the thortveitite family, was prepared as a polycrystalline powder material by the conventional solid-state reaction method. Structural, thermal and photoluminescence (PL) properties of the prepared material were investigated in order to evaluate its potentiality. XRD patterns confirm the monoclinic phase of CaZrSi₂O₇: Eu²⁺ phosphors.. Emissions arising from transitions between the 5d and 4f orbital gaps of Eu²⁺ are manifested in the broadband excitation and emission spectra with major peaks at 363 and 512 nm, respectively. The excitation wavelength matches well with that of the emission of the ultraviolet-light emitting diode (UV-LED). Concentration quenching occurs when the Eu²⁺ concentration is beyond 0.05 and the dipole-dipole interaction was the reason for the corresponding quenching mechanism. The temperature dependence of emission intensity of CZS: Eu²⁺ phosphor was investigated and it showed better thermal stability than the standard YAG: Ce³⁺ phosphor.     

Investigation of photocatalytic reaction for thetitanium dioxide-phosphor composite

The present study examined the photocatalytic reaction of titanium dioxide (TiO₂)-coated, phosphor composite particles. Nanocrystalline TiO₂ layers were directly coated on the alkaline earth aluminate phosphor (CaAl₂O₄:Eu²⁺,Nd³⁺) particles by a sol-gel processing method and their photocatalytic reaction was analyzed according to the degradation of methylene blue aqueous solution under visible light irradiation. Compared with pure TiO₂, the TiO₂-coated phosphor powders showed a different photocatalytic mechanism and much faster photocatalytic reactivity under visible irradiation than that of pure TiO₂, which was almost negligible. The mechanism of the photocatalytic reactivity for the TiO₂-phosphor composite was discussed in terms of the energy band structure and phosphorescence. In addition, the TiO₂-coated phosphor powders were characterized by X-ray diffraction and transmission electron microscopy.     

Highly luminescent red light phosphor CaTiO3:Eu under near-ultraviolet excitation

The Eu-doped CaTiO₃ particles with a good crystallinity were prepared via sol-gel method. The phosphors showed a strong red emission corresponding to ⁵D₀→⁷F₂ (618 nm) of Eu³⁺ under the near-ultraviolet excitation (400 nm). X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), photoluminescent (PL) analysis and Brunauer-Emmett-Teller (BET) specific surface area measurement were utilized to characterize the CaTiO₃:Eu³⁺ particles. The concentration quenching and thermal quenching of the samples were discussed as well. The optimal concentration and the calcination temperature were 16 mol% of Eu³⁺ and 1400 °C for these phosphors, and the possible reason was discussed as well. CaTiO₃:Eu³⁺ is a promising red phosphor under near-ultraviolet excitation for various applications.     

Preparation and luminescent properties of phosphor MGd2(MoO4)4: Eu (M=Ca, Sr and Ba)

Intense red emitting phosphors MGd₂(MoO₄)₄: Eu³⁺ (M=Ca, Sr and Ba) have been synthesized by the simple sol-gel technique. The formation processes and the phase impurity of phosphors are characterized by thermogravimetry-differential thermal analysis (TG-DTA) and power X-ray diffraction (XRD). The narrower size distribution and the regular shape of the phosphor particles are also measured by Field emission scanning electronic microscopy (FE-SEM). Photo-luminescent properties of the phosphors are performed at room temperature. Their excitation spectra present strong absorption at 395 nm near-UV light and 465 nm blue light, which match well with commercial LED chips. The phosphors exhibit satisfactory and excellent red light dominated by 616 nm and their photoluminescence intensity is about 3-4 times stronger than that of phosphor YAG under the 465 nm excitation. In addition, the optimal concentrations of Eu³⁺ for phosphors MGd₂(MoO₄)₄ (M=Ca, Sr and Ba) have also been determined.     

KBaPO4:Ln (Ln=Eu, Tb, Sm) phosphors for UV excitable white light-emitting diodes

This letter reports the novel three emission bands based on phosphate host matrix, KBaPO₄ doped with Eu²⁺, Tb³⁺, and Sm³⁺ for white light-emitting diodes (LEDs). The phosphors were synthesized by solid-state reaction and thermal stability was elucidated by measuring photoluminescence at higher temperatures. Eu²⁺-doped KBaPO₄ phosphor emits blue luminescence with a peak wavelength at 420 nm under maximum near-ultraviolet excitation of 360 nm. Tb³⁺-doped KBaPO₄ phosphor emits green luminescence with a peak wavelength at 540 nm under maximum near-ultraviolet excitation of 370 nm. Sm³⁺-doped KBaPO₄ phosphor emits orange-red luminescence with a peak wavelength at 594 nm under maximum near-ultraviolet excitation of 400 nm. The thermal stabilities of KBaPO₄:Ln (Ln=Eu²⁺, Tb³⁺, Sm³⁺), in comparison to commercially available YAG:Ce³⁺ phosphor were found to be higher in a wide temperature range of 25-300 °C.     

Low temperature quenching and high efficiency Tm, La or Tb co-doped CaSc2O4:Ce phosphors for light-emitting diodes

Low temperature quenching and high efficiency CaSc₂O₄:Ce³⁺ (CSO:Ce³⁺) phosphors co-doped with Tm³⁺, La³⁺ and Tb³⁺ ions were prepared by a solid state method and the phase-forming, morphology, luminescence and application properties of these phosphors were investigated. The results showed that co-doping of Tm³⁺, La³⁺ and Tb³⁺ ions can improve the luminescence properties and decrease temperature quenching of CSO:Ce³⁺ phosphor remarkably. High efficiency green-light-emitting diodes were fabricated with the prepared phosphors and InGaN blue-emitting (∼460 nm) chips. The good performances of the green-light-emitting LEDs made from co-doped CSO:Ce³⁺ phosphors confirm the luminescence enhancement and indicate that Tm³⁺, La³⁺ and Tb³⁺ co-doped CSO:Ce³⁺ phosphors are suitable candidates for the fabrication of high efficiency white LEDs.     

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.     

Effect of nano-sized SiO2 on the optical properties of YVO4:Eu3+ phosphors

In this paper, YVO₄: 1%Eu³⁺ phosphor was synthesized via solid state method at 1100 °C. Then TEOS was used as the source of silica, to coat the phosphors, using sol–gel approach. HRTEM analysis confirmed the formation of adhered and smooth coating layer with the thickness of 40–50 nm. From the experiments and characterizations, we found that although the amounts of added SiO₂ to the phosphors were not remarkable, but it resulted in enhancement of photoluminescence properties. Interestingly, under the excitation wavelength of 310 nm, the efficiency of the phosphors increased by about 20%. Also, a considerable effect of coating layer on decrease in surface oxygen vacancies was studied using ESR technique. Finally it was found that SiO₂ coating of YVO₄:Eu³⁺ phosphors, improves both chemical stability and thermal quenching, effectively.     

Synthesis and characterization of Ce doped silica (SiO2) nanoparticles

A series of silica doped with different mol percentages of Ce³⁺ concentration was synthesized using a sol-gel method to determine the dependence of photoluminescence wavelengths and intensity on the concentrations of the dopants. Sol-gel glasses are porous networks that have been densified through chemical processing and heat treatment. Rare-earths (REs) are insoluble in silica; due to this insolubility RE ions in silicate glasses enter as network modifiers and compete for non-bridging oxygen in order to complete their coordination. The morphological, structural, thermal and optical properties of the phosphors were characterized by X-ray diffraction, scanning electron microscopy, UV-vis absorption, photoluminescence, thermogravimetric analyses and differential scanning calorimeter. Silica (SiO₂) gel containing Ce³⁺ ions was sputter coated with Au (gold) in order to monitor surface morphology of the samples. The highest emission intensity was found for the sample with a composition of 0.5 mol% Ce³⁺. Cerium doped silica glasses had broad blue emission corresponding to the ²D_3/2-²F_J transition at 448 nm but exhibited apparent concentration quenching above concentrations of 0.5 mol% Ce³⁺.     

Preparation and luminescence of blue-emitting phosphor Ca2PO4Cl:Eu2+ for n-UV white LEDs

A series of blue-emitting Ca_2 ? xEu_xPO₄Cl phosphors were synthesized by a solid state method in a reducing atmosphere. The factors those affect the structure and the photoluminescence (PL) intensities of phosphors, including the dosage of chlorine source CaCl₂, reaction time and annealing temperature, have been investigated in detail. X-ray diffraction (XRD) and photoluminescence measurements were performed to testify the crystal structure and luminescent properties. The optimal Eu²⁺ concentration was determined, and the mechanism of the concentration quenching was predominated by dipole–dipole interaction. The present phosphor exhibits a strong absorption in the near-UV region, emits an intense blue emission centered at 451 nm and presents excellent thermal stability, suggesting that the phosphor is competitive as a promising blue-emitting phosphor for near ultraviolet (n-UV) light-emitting diodes (LEDs).     

Enhanced blue emission and EPR study of LaMgAl11O19:Eu phosphors

Europium doped LaMgAl₁₁O₁₉ phosphor was prepared by the combustion method. The as-prepared and post-treated (1350 °C 10 h 5% H₂+95% N₂) phosphors were investigated by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), photoluminescence (PL) and electron paramagnetic resonance (EPR) techniques. XRD patterns show that LaMgAl₁₁O₁₉:Eu phosphors have hexagonal structure. FT-IR spectrum exhibits absorption bands corresponding to the stretching vibration of AlO₄ and AlO₆. Morphological studies reveal that this phosphor has faceted plates of varying sizes and shapes. The as-prepared LaMgAl₁₁O₁₉:Eu phosphor consists of both Eu³⁺ and Eu²⁺ ions. The phosphor exhibits a bright blue emission at 450 nm (4f⁶5d→4f⁷ transition of Eu²⁺). On post-treating the phosphor we are able to enhance the blue emission efficiency by 330%. The process was detected from the evolution of excitation, emission and EPR spectra and the results are discussed.     

Luminescence of KCaSO4Cl:X, Y (X=Eu or Ce; Y=Dy or Mn) halosulfate material

Polycrystalline KCaSO₄Cl:Eu, Dy, KCaSO₄Cl:Ce, Dy and KCaSO₄Cl:Ce, Mn phosphors prepared by a solid state diffusion method have been studied for its photoluminescence (PL) characteristics. The presence of two overlapping bands at around 400 and 450 nm in the PL emission spectra of the phosphor suggests the presence of Eu²⁺ in the host compound occupying two different lattice sites. The effects of co-doping on the photoluminescence (PL) characteristics of KCaSO₄Cl:Eu or Ce phosphors have been studied. The decrease in peak intensity of the phosphor on co-doping it with Dy gives an insight into the emission mechanism of the phosphors, which involves energy transfer from Eu²⁺→Dy³⁺, Ce³⁺→Dy³⁺ and Ce³⁺→Mn²⁺.     

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.     

Green Eu-doped Ba3Si6O12N2 phosphor for white light-emitting diodes: Synthesis, characterization and theoretical simulation

The Eu²⁺-doped Ba₃Si₆O₁₂N₂ green phosphor (Eu_xBa_3−xSi₆O₁₂N₂) was synthesized by a conventional solid state reaction method. It could be efficiently excited by UV-blue light (250-470 nm) and shows a single intense broadband emission (480-580 nm). The phosphor has a concentration quenching effect at x=0.20 and a systematic red-shift in emission wavelength with increasing Eu²⁺ concentration. High quantum efficiency and suitable excitation range make it match well with the emission of near-UV LEDs or blue LEDs. First-principles calculations indicate that Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor exhibits a direct band gap, and low band energy dispersion, leading to a high luminescence intensity. The origin of the experimental absorption peaks is clearly identified based on the analysis of the density of states (DOS) and absorption spectra. The photoluminescence properties are related to the transition between 4f levels of Eu and 5d levels of both Eu and Ba atoms. The 5d energy level of Ba plays an important role in the photoluminescence of Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor. The high quantum efficiency and long-wavelength excitation are mainly attributed to the existence of Ba atoms. Our results give a new explanation of photoluminescence properties and could direct future designation of novel phosphors for white light LED.     

Synthesis and luminescence properties of YVO4:Eu,Bi phosphor with enhanced photoluminescence by Bi doping

YVO₄:Eu³⁺,Bi³⁺ phosphors have been prepared by the high-temperature solid-state (HT) method and the Pechini-type sol-gel (SG) method. Spherical SiO₂ particles have been further coated with YVO₄:Eu³⁺,Bi³⁺ phosphor layers by the Pechini-type SG process, and it leads to the formation of core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ phosphors. Therefore, the phase formations, structures, morphologies, and photoluminescence properties of the three types of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors were studied in detail. The average diameters for the phosphor particles are 2-4 μm for HT method, 0.1-0.4 μm for SG method, and 0.5 μm for core-shell structured SiO₂/YVO₄:Eu³⁺,Bi³⁺ particles, respectively. Photoluminescence spectra show that effective energy transfer takes place between Bi³⁺ and Eu³⁺ ions in each type of as-prepared YVO₄:Eu³⁺,Bi³⁺ phosphors. Introduction of Bi³⁺ into YVO₄:Eu³⁺ leads to the shift of excitation band to the long-wavelength region, thus the emission intensities of ⁵D₀-⁷F₂ electric dipole transition of Eu³⁺ at 615 nm upon 365 nm excitation increases sharply, which makes this phosphor a suitable red-emitting materials that can be pumped with near-UV light emitting diodes (LEDs).     

Thermally stable deep-blue Ba1.2Ca0.8SiO4:Ce phosphor for white-light-emitting diode

A novel deep-blue phosphor, Ba_1.2Ca_0.8SiO₄:Ce³⁺, has been developed for white-light-emitting diodes. The phosphor exhibits two absorption bands at 280 and 325 nm, and an intense deep-blue emission peaking at 400 nm. With increasing Ce/Li concentrations, the lattice expands, and the emission peak is blueshifted. This correlation is explained in terms of the crystal field effect and the configurational coordinate diagram. This phosphor shows much higher thermal quenching temperature (225 °C) due to a weak electron-phonon interaction. Thus, it can be used as a sensitizer phosphor to excite other green or red phosphors, or a promising deep-blue phosphor for white-light-emitting diodes.     

Blue-emitting long-lasting phosphor, Sr3Al10SiO20:Eu,Ho

A novel blue-emitting long-lasting phosphor Sr₃Al₁₀SiO₂₀:Eu²⁺,Ho³⁺ is prepared by the conventional high-temperature solid-state technique and their luminescent properties are investigated. XRD, photoluminescence (PL) and thermoluminescence (TL) are used to characterize the synthesized phosphors. These phosphors are well crystallized by calcinations at 1500-1600 °C for 3 h. The phosphor emits blue light and shows long-lasting phosphorescence after it is excited with 254/365 nm ultraviolet light. TL curves reveal the introduction of Ho³⁺ ions into the Sr₃Al₁₀SiO₂₀:Eu²⁺ host produces a highly dense trap level at appropriate depth, which is the origin of the long-lasting phosphorescence in this kind of material. The long-lasting phosphorescence lasts for nearly 6 h in the light perception of the dark-adapted human eye (0.32 mcd/m²). All the results indicate that this phosphor has promising potential practical applications.