Synthesis of nano-sized YAG:Eu phosphor in continuous supercritical water system

Luminescent yttrium aluminum garnet (Y₃Al₅O₁₂) nanoparticles doped with Eu (YAG:Eu³⁺) were continuously synthesized by directly feeding potassium hydroxide solution and metal salt solution to supercritical water (SCW). Effects of Eu concentration, pH, and residence time on photo-luminescence were studied using a continuous tubular reactor. Residence time played a key role in producing single-phase YAG:Eu³⁺ nanoparticles. The residence time of 20 s under SCW conditions (400 °C and 280 bar) was enough to form YAG:Eu³⁺ phosphor without any intermediate phases. At this residence time, the Eu concentration and pH condition under SCW contributed to improving the size, morphology and luminescent property of YAG: Eu³⁺ nanoparticles. The average size of the prepared phosphor nanoparticles at 10 at.% and pH of 9.10 was 74 nm and the morphology was identified as nearly uniform and spherical-like in shape. Without further thermal treatment, the phosphor YAG:Eu³⁺ synthesized in the continuous reactor under SCW conditions showed strong luminescence properties and red emission spectra.     

Synthesis and luminescence of Y2O3:Eu inorganic–organic hybrid nanostructures with thenoyltrifluoroacetone

Cubic Y₂O₃:Eu³⁺ nanoparticles with a size about 32 nm were synthesized using a facile hydrothermal method followed by an annealing process. As expected, the Y₂O₃:Eu³⁺ nanoparticles had a broad Eu–O excitation band ranging from 200 nm to 285 nm peaking at about 260 nm. The Y₂O₃:Eu³⁺ nanoparticles were then used to fabricate the inorganic–organic hybrid nanostructures with thenoyltrifluoroacetone (TTA). The Y₂O₃:Eu³⁺–TTA hybrid nanostructures exhibited a new strong excitation band ranging from 280 nm to 390 nm peaking at about 368 nm. This new excitation band was attributed to the energy transfer mechanism of the Y₂O₃:Eu³⁺–TTA hybrid system. It is interesting to note that this energy transfer mechanism had a close interaction with the Eu–O excitation of Y₂O₃:Eu³⁺ nanoparticles. The phase structures, chemical bonding information, microstructural characteristics and luminescence properties were investigated.     

Site construction of Eu2+ and sensitized luminescence of Eu3+ in LaF3:Eu nanophosphor

LaF₃:Eu nanophosphors were prepared by a traditional hydrothermal method with citric acid as a reducing agent. X-ray diffraction, scanning electronic microscopy, and luminescence spectroscopy were used to study the nanophosphors. The formation of three different luminescence centers of Eu²⁺ and two different luminescence centers of Eu³⁺ is attributed to the existence of abundant surface defects in this nanophosphor. Eu³⁺ is effectively excited by energy transfer from Eu²⁺ to Eu³⁺. The excitation wavelength of Eu³⁺ covers a broad spectral range from 250 to 480 nm. The nanophosphor shows a tunable luminescence color varying from blue to white and then to red, which is explained from three aspects of Eu concentration, energy transfer, and concentration quenching. Utilizing the surface defect of nanoparticles to control the reduction of Eu³⁺ is considered a promising strategy for exploring Eu²⁺ and Eu³⁺ codoped phosphor suitable for the lighting and display application.     

Influence of metal ion concentration in the glycol mediated synthesis of Gd2O3:Eu nanophosphor

The solvothermal synthesis of highly luminescent and homogeneous Gd₂O₃:Eu³⁺ nanophosphor using diethylene glycol as medium, followed by controlled combustion with citric acid as fuel is reported. The influence of concentrations of carboxylic acid and metal cations on the structure, morphology and luminescence properties are investigated in detail. The microscopic investigations indicate the nanocrystalline nature and the strong influence of cation concentration on the size, shape and agglomeration of the particles. It is found that increase in concentration of metal cations lead to the reduction in agglomeration of nanophosphors. The large value of intensity parameter Ω_2, suggested that Eu³⁺ ions reside in a more asymmetric environment, resulted in intense emission due to ⁵D₀–⁷F₂ electric dipole transition. Emission decay analysis of the samples exhibited one exponential nature. The samples prepared under optimum conditions showed a quantum efficiency of 78.63% and a moderately high life time of 1.217 ms.     

Synthesis and photoluminescence properties of MgAl(PO4)O:Eu red phosphor for white LEDs

Eu³⁺-activated MgAl(PO₄)O:phosphor has been synthesized by a high temperature solid state reaction and efficient red emission under near-ultraviolet excitation is observed. The emission spectrum shows a dominant peak at 594 nm due to the ⁵D₀→⁷F₁ transition of Eu³⁺. The excitation spectrum is coupled well with the emission of UV LED (350–410 nm). The effect of Eu³⁺ concentration on the luminescent properties of MgAl(PO₄)O:Eu³⁺ and the mechanism of concentration quenching of Eu³⁺ are studied. The results show that MgAl(PO₄)O:Eu³⁺ is a promising red-emitting phosphor for white LEDs.     

Synthesis and optical characterization of novel Sr3Ga2O6:Eu phosphor

Alkaline earth metal gallets have been identified as an important ceramic material. The crystal chemistry of many of these gallets is well explored; however, very rare studies regarding optical properties of rare earth (RE) ions doped in such gallets, particularly in Sr₃Ga₂O₆ host, have been carried out. The present study reports on synthesis and characterization of novel Sr₃Ga₂O₆:Eu³⁺ phosphors. The phosphors have been synthesized using a conventional solid state reaction method. Crystal structure, morphology and luminescence properties (excitation, emission and CIE coordinate) of these phosphors have been studied as a function of sintering temperature and Eu³⁺ concentration. X-ray diffraction study reveals that the phosphor sintered at low temperature (900 °C) contains an impurity phase which is removed at higher sintering temperatures and results into cubic crystalline phase of Sr₃Ga₂O₆. Particle size of the phosphor increases with an increase in sintering temperature which results to a red shift in the peak position of excitation band lying in a broad range from 250 to 370 nm. Optimum emission intensity is attained for 0.12 mol% concentration of Eu³⁺ ions; above this concentration, a quenching in emission intensity is observed.     

Eu-Doped BaTiO3 Powder and Film from Sol-Gel Process with Polyvinylpyrrolidone Additive

Transparent BaTiO₃:Eu³⁺ films were prepared via a sol-gel method and dip-coating technique, using barium acetate, titanium butoxide, and polyvinylpyrrolidone (PVP) as modifier viscosity. BaTiO₃:Eu³⁺ films ~500 nm thick, crystallized after thermal treatment at 700 ºC. The powders revealed spherical and rod shape morphology. The optical quality of films showed a predominant band at 615 nm under 250 nm excitation. A preliminary luminescent test provided the properties of the Eu³⁺ doped BaTiO₃.     

Ultraviolet radiation excited strong red-emitting LaAlO3:Eu3+ nanophosphors: Synthesis and luminescent properties

We synthesized the trivalent europium ions (Eu³⁺) doped lanthanum aluminate (LaAlO₃, LAO) nanophosphors by a solvothermal method. Their structural, morphological, and luminescent properties were systematically investigated. The obtained nanoparticles possessed single nanocrystallinity with a rhombohedral structure. For the excitation originating from the charge transfer band (O^2- to Eu³⁺ ions) under 320 nm illumination, the featured emissions of Eu³⁺ ions were detected in all the compounds. The optimum doping concentration of Eu³⁺ ions in LAO was about 9 mol% and the concentration quenching was dominated by dipole-dipole interaction. Furthermore, the Judd-Ofelt (J-O) theory was used to estimate the J-O intensity parameters. Based on the temperature-dependent PL emission spectra, the thermal stability was analyzed and the activation energy was obtained to be 0.234 eV. Meanwhile, the decay time, color coordinate/purity, and cathodoluminescence behaviors of the synthesized nanophosphors were also studied. These characteristics make the Eu³⁺-doped LAO nanoparticles a promising red-emitting phosphor for both ultraviolet-based white light-emitting diodes and field-emission displays.     

Luminescence properties of Eu activated Ba2Si5N8 red phosphors with various Eu contents

This study was carried out to characterize the crystal structure and luminescence properties of Eu²⁺ doped red-emitting Ba₂Si₅N₈ phosphor. In this research, Ba₂Si₅N₈ phosphors with various Eu compositions were prepared by normal pressure sintering (NPS). Ba₃N₂, Si₃N₄ and Eu₂O₃ were sintered at a high temperature in a mixture of N₂ and H₂. The crystal structure was analyzed by X-ray diffraction(XRD), and the photoluminescence(PL) properties of the Eu²⁺ - activated Ba₂Si₅N₈ phosphors were evaluated as a function of the Eu²⁺ activator concentration. The red-emitting Ba₂Si₅N₈ phosphors showed a broad excitation band range as well as high quantum output.     

Crystalline morphology and photoluminescent properties of YInGe2O7:Eu phosphors prepared from microwave and conventional sintering

This paper describes an investigation of the crystalline morphology and photoluminescent properties of YInGe₂O₇:Eu³⁺ powders using microwave assisted sintering. For comparison, the properties of YInGe₂O₇:Eu³⁺ powders sintered at 1200 °C in conventional furnace for 10 h were also investigated. X-ray powder diffraction analysis confirmed the formation of monoclinic YInGe₂O₇ without second phase or phases of starting materials as YInGe₂O₇:50 mol% Eu powders sintered at 1200 °C in microwave furnace for 1 h. Scanning electron microscopy showed smaller particle size and more uniform grain size distributions are obtained by microwave assisted sintering. In the PL studies, both microwave sintered and conventionally sintered powders emitted a maximum luminescence centered at 620 nm under excitation of 393 nm with similar luminescent intensity. The results show that microwave processing has the potential to reduce the time and required energy input for the production of YInGe₂O₇:Eu³⁺ phosphors without sacrificing the photoluminescence.     

Synthesis of LaOF:Eu3+ Nanoparticles with Strong Luminescence Enhanced by Organic Ligands

LaOF:Eu³⁺ nanoparticles were successfully prepared by annealing LaF₃:Eu³⁺ nanocrytsals which were capped with SiO₂ shell. The SiO₂ shell effectively prohibited the growth of LaF₃:Eu³⁺ nanocrystals during the annealing process, and it was etched off after annealing to obtain the LaOF:Eu³⁺ nanoparticles. The LaOF:Eu³⁺ nanoparticles had a size comparable to the original LaF₃:Eu³⁺ nanoparticles. Inorganic–organic hybrid nanoparticles of LaF₃:Eu³⁺ and LaOF:Eu³⁺ nanoparticles with thenoyltrifluoroacetone (TTA) ligands were prepared. Strong luminescence as a result of the energy transfer from the TTA organic ligands to the LaF₃:Eu³⁺ and LaOF:Eu³⁺ nanoparticles was observed. The LaOF:Eu³⁺‐based hybrid nanoparticles exhibited stronger luminescence intensity and broader excitation spectral range than the LaF₃:Eu³⁺‐based hybrid nanoparticles. Effect of the content of TTA ligands on the luminescence of the LaOF:Eu³⁺ nanoparticles was investigated in detail.     

Preparation of Y2O3:Eu nanopowders via polymer complex solution method and luminescence properties of the sintered ceramics

Herein we presented polymer complex solution method for production of well crystalline europium doped Y₂O₃ nanopowders. Polyethylene glycol (PEG) of five different molecular weights is used both as a fuel and as a nucleation agent for the crystallization. Powders were cold-pressed and sintered to obtain ceramics. SEM images taken from ceramic pellets indicate formation of a dense structure, with a pronounced grain growth and low pore concentration. Luminescence emission spectra of powders and ceramics are similar, and in good agreement with theoretical data. Lifetimes of Eu³⁺⁵D₀ level in nanocrystalline powders are higher compared to one observed in bulk, confirming in this case theory of lifetime lengthening in nanophosphors due to the change of effective refraction index. As expected, lifetime values in ceramic samples decrease toward the value in bulk Y₂O₃. The optical filling factor is calculated from observed decay times, providing a measure of discrepancy between powder and bulk state regarding their luminescent properties.     

Synthesis and Characterization of Electrospun Poly(ethylene oxide)/Europium-Doped Yttrium Orthovanadate (PEO/YVO4:Eu3+) Hybrid Nanofibers

Europium-doped yttrium orthovanadate/polyethylene oxide nanofibers were fabricated by firstly, synthesizing crystalline YVO₄:Eu³⁺ nanoparticles using an aqueous precipitation method followed by electrospinning of PEO/YVO₄:Eu³⁺ polymer composites. X-ray diffraction patterns showed that the nanoparticles exhibited well-defined peaks that were indexed as the tetragonal phase of YVO_4. No additional peaks of other phases were observed indicating that Eu³⁺ ions were effectively built into the YVO₄ host lattice. The photoluminescence spectra for the nanofibers showed peaks at 593, 615, 650, and 698 nm which was ascribed to the ⁵D_0? ⁷F₁, ⁵D_0? ⁷F₂, ⁵D_0? ⁷F₃ and ⁵D_0? ⁷F₄ transitions of Eu³⁺. Due to an efficient energy transfer from vanadate groups to Eu³⁺, the composite nanofibers showed a strong red emission under ultraviolet excitation characteristic of the red luminescence of the europium ion. The results demonstrate that this synthetic approach could prove to be viable for the fabrication of rare earth/polymer composite nanofibers intended for luminescent device applications.     

Structural and spectral properties of red light emitting Eu3+ activated TiO2 nanophosphor for white LED application

The structural and luminescent properties of Eu³⁺ doped TiO₂ nanophosphors synthesized by low cost combustion method were investigated. The X-ray diffraction analysis revealed that crystallite size decreases with doping concentration. Lattice volume expansion occurred due to the substitution of Ti⁴⁺ ions by larger ionic radii ions Eu³⁺. FESEM images showed prepared phosphors to be nano size spherical shaped particles. Energy band gap of 3 mol% Eu³⁺ doped samples decreased to 3.15 eV due to doping effect. The Eu³⁺ doped TiO₂ nanophosphors exhibited main red emission peak centered at 616 nm under 395 nm UV light excitation. Concentration quenching was observed at 3 mol% doping, that has been ascribed to dipole-dipole interaction. The covalent nature of Eu-O bond and environment around Eu³⁺ ions were discussed using Judd-Ofelt (J-O) intensity parameters. Internal quantum efficiency was calculated using excited state lifetime ⁵D₀ state of Eu³⁺ ion and J-O theory. The CIE colour coordinates and colour purity were calculated using the spectral energy distribution function. Low excited state life time indicated that Eu³⁺ doped TiO₂ can be used as red emitting phosphor for white light emitting diode applications.     

Enhanced Luminescence of Eu-Doped TiO2 Nanodots

Monodisperse and spherical Eu-doped TiO₂ nanodots were prepared on substrate by phase-separation-induced self-assembly. The average diameters of the nanodots can be 50 and 70 nm by changing the preparation condition. The calcined nanodots consist of an amorphous TiO₂ matrix with Eu³⁺ ions highly dispersed in it. The Eu-doped TiO₂ nanodots exhibit intense luminescence due to effective energy transfer from amorphous TiO₂ matrix to Eu³⁺ ions. The luminescence intensity is about 12.5 times of that of Eu-doped TiO₂ film and the luminescence lifetime can be as long as 960 μs.     

Novel orange-emitting Ba2LaNbO6:Eu3+ nanophosphors for NUV-based WLEDs and photocatalytic water purification

Energy conservation and environmental safety are the key requirements in the modern world. We report novel orange-emitting double perovskite Ba₂LaNbO₆:Eu³⁺ (BLN:Eu³⁺) nanophosphor fabricated using a citrate sol-gel method for use in general illumination and photocatalysis. After annealing at 800?℃, the particles exhibited a nanorod-like morphology with monoclinic structure. The photoluminescence emission spectra exhibited an intense ⁵D₀→⁷F₁ transition at 594?nm and a moderate ⁵D₀→⁷F₂ transition at 615?nm, demonstrating that the Eu³⁺ ions occupied the La³⁺ sites with inversion symmetry. The optimal concentration of Eu³⁺ ions was found to be about 5?mol% for the BLN host lattice. Energy transfer from the NbO₆^7- octahedrons to the Eu³⁺ ions was clearly witnessed when the BLN:Eu³⁺ nanophosphors were excited with both the characteristic excitation bands of Eu³⁺ (⁷F₀→⁵L₆) and NbO₆^7- octahedrons at 392 and 380?nm, respectively. The thermal quenching temperature of 5?mol% Eu³⁺ ions doped BLN nanophosphors was found to be 183?℃, indicating that these nanophosphors are very stable at high temperatures. In addition, the dye removal efficiency of the proposed BLN nanophosphors was verified using Rhodamine B (RhB) dye as a model pollutant under UV irradiation. Compared to a commercial nano-ZnO catalyst, our synthesized BLN nanophosphors showed superior RhB de-colorization efficiency. Therefore, the proposed BLN:Eu³⁺ nanophosphors are promising multifunctional materials for photocatalysis and general lighting applications.     

Near‐UV activated,photostable nanophosphors for in vitro dosimetry and dynamic bioimaging

Luminescent rare earth nanoparticles exhibit superior optical stability over commonly‐used organic dyes and higher biocompatibility over quantum dots, rendering them advantageous as bioimaging nanoprobes. However, their typical excitation inhibits their broad employment with conventional fluorescence microscopes and, thus, solutions are sought to shift their activation in the long‐wavelength (near‐UV) spectral region. Here, we synthesize YVO₄:Eu³⁺ nanophosphors by flame aerosol technology to systematically study the effect of Bi³⁺ codoping on their luminescence. That way, we identify an optimal Bi‐content for sufficient near‐UV activation. These nanophosphors are highly crystalline and appeared bright red under a conventional fluorescence microscope, facilitating bioimaging with HeLa cells and in vitro dosimetry correlations in the presence and absence of serum. The nanophosphor superiority over organic‐dye‐labeled silica nanoparticles is shown during dynamic imaging for 4 h without photobleaching for the former. These YVO₄:Eu³⁺/Bi³⁺ nanophosphors can provide a non‐photobleaching tool for further dynamic nanoparticle‐cell interaction studies with conventional fluorescence microscopes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2947–2957, 2018     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Color-tunable properties of Eu3+- and Dy3+-codoped Y2O3 phosphor particles

Rare-earth phosphors are commonly used in display panels, security printing, and fluorescent lamps, and have potential applications in lasers and bioimaging. In the present study, Eu³⁺- and Dy³⁺-codoped uniform-shaped Y₂O₃ submicron particles were prepared using the urea homogeneous precipitation method. The structure and morphology of the resulting particles were characterized by X-ray diffraction, field emission scanning electron microscope, and field emission transmission electron microscope, whereas their optical properties were monitored by photoluminescence spectroscopy. The room-temperature luminescence color emission of the synthesized particles can be tuned from red to yellow by switching the excitation wavelength from 254 to 350 nm. The luminescence intensities of red and yellow emissions could be altered by varying the dopant concentration. Strong quenching was observed at high Eu³⁺ and Dy³⁺ concentrations in the Y₂O₃ host lattice.