Y2Si2O7:Eu/SiO2 core shell phosphor particles prepared by flame spray pyrolysis

This paper reports the synthesis of core shell phosphor particles (Y₂Si₂O₇:Eu/SiO₂) produced by flame spray pyrolysis with yttrium and europium nitrates and colloidal silica dispersed precursor solutions. Particles of various structures were produced, including heterogeneous, core shell and non-spherical core shell particles, depending on the synthesis conditions; the ideal core shell structure was obtained under the highest flame temperature and high silicon concentration in the precursor solution. Based on the phase diagram, the formation of the core shell structure was caused by the separation of each component at the liquid phase in the synthesis route. In the energy-dispersive X-ray spectroscopy, yttrium could be detected only at the core part of the particle, while silicon and oxygen could be detected at both the shell and core parts. Under ultraviolet excitation, the ideal core shell particles of Y₂Si₂O₇:Eu showed photoluminescent characteristics. Consequently, it could be concluded that Y₂Si₂O₇:Eu/SiO₂ core shell phosphor particles were successfully synthesized by flame spray pyrolysis.     

Brightness and decay time of Zn2SiO4:Mn phosphor particles with spherical shape and fine size

Green-light-emitting Zn₂SiO₄:Mn phosphor particles were synthesized by modified large-scale spray pyrolysis using a colloidal solution containing fumed silica particles. The particles had a fine size, filled morphology, spherical shape and non-aggregation characteristics even after post-treatment at 1150 °C. The luminescence characteristics of Zn₂SiO₄:Mn phosphor particles having spherical shape, such as brightness and decay time under VUV excitation light, were investigated as a function of Mn content. The luminescence intensity exhibits a maximum at 5 mol% Mn-doped powder. The decay time increases consistently with decreasing Mn content and more saturated color coordinates are obtained with the composition having 12 mol% Mn. As a consequence, the 10 mol% Mn-doped powder proved to provide a good combination of favorable luminance and acceptable decay time. The influence of post-treatment temperature on the decay time and photoluminescence characteristics of Zn₂SiO₄:Mn particles was also investigated. Particles post-treated at 1155 °C had the maximum photoluminescence intensity, which was identical to 113% that of the commercial product, and a comparable decay time of 5.8 ms. PACS 81.20.Rg; 78. 55.Hx; 78.40.Ha; 81.05.Hd; 81.40.Tv     

Y2O3:Eu phosphor particles prepared by spray pyrolysis from a solution containing citric acid and polyethylene glycol

Y₂O₃:Eu phosphor particles were prepared by large-scale spray pyrolysis. The morphological control of Y₂O₃:Eu particles in spray pyrolysis was attempted by adding polymeric precursors to the spray solution. The effect of composition and amount of polymeric precursors on the morphology, crystallinity and photoluminescence characteristics of Y₂O₃:Eu particles was investigated. Particles prepared from a solution containing polyethylene glycol (PEG) with an average molecular weight of 200 had a hollow structure, while those prepared from solutions containing adequate amounts of citric acid (CA) and PEG had a spherical shape, filled morphology and clean surfaces after post-treatment at high temperature. Y₂O₃:Eu particles prepared from an aqueous solution with no polymeric precursors had a hollow structure and rough surfaces after post-treatment. The phosphor particles prepared from solutions with inadequate amounts of CA and/or PEG also had hollow and/or fragmented structures. The particles prepared from the solution containing 0.3 M  CA and 0.3 M  PEG had the highest photoluminescence emission intensity, which was 56% higher than that of the particles prepared from aqueous solution without polymeric precursors. Received: 22 March 2002 / Accepted: 26 March 2002 / Published online: 5 July 2002 RID="*" ID="*"Corresponding author. Fax: +82-42/861-4245, E-mail: yckang@pado.krict.re.kr     

Synthesis of Y2Si2O7:Eu nanocrystal and its optical properties

Nanocrystalline Y₂Si₂O₇:Eu phosphor with an average size about 60 nm is easily prepared using silica aerogel as raw material under ultrasonic irradiation and annealing temperature at 300-600 °C and this nanocrystalline decomposes into Y₂O₃:Eu and silica by heat treatment at 700-900 °C. The excitation broad band centered at 283 and 254 nm results from Eu³⁺ substituting for Y³⁺ in Y₂Si₂O₇ and Y₂O₃/SiO₂, respectively. Compared with Y₂O₃:Eu/SiO₂ crystalline, the PL excitation and emission peaks of Y₂Si₂O₇:Eu nanocrystalline red-shift and lead to the enhance of its luminescence intensity due to the different chemical surroundings of Eu³⁺ in above nanocrystallines. The decrease of PL intensity may be ascribed to quenching effect resulting from more defects in Y₂O₃:Eu/SiO₂ crystalline.     

Continuous nano-coating of Y2O3:Eu phosphor shell on SiO2 core particles and its photoluminescence properties

In order to investigate the effects of the crystallite size on the photoluminescence (PL) properties of a phosphor, monodisperse spherical SiO₂/Y₂O₃:Eu³⁺ phosphor core/shell particles were synthesized. On the surface of the core particles prepared by the Stöber method, the phosphor shell was continuously coated by a heterogeneous precipitation method. Because the growth of the crystallite was restricted by the shell thickness, the crystallite size could be successfully controlled at the same firing conditions. The PL intensity, the asymmetric ratio and thus the color purity were significantly decreased with the decrease of the crystallite size. In addition, the position of charge transfer band in the PL excitation spectrum was red-shifted with the decrease of the crystallite size.     

Influence of polymeric additives on morphology and performance of Y2O3:Eu phosphor synthesized by flame-assisted spray pyrolysis

Fine powder of cubic Y₂O₃:Eu phosphor was synthesized and simultaneously deposited on fused silica slides by low-temperature flame-assisted spray pyrolysis in premixed propane/air flames. By adding ethylene glycol and citric acid to the precursor solution, morphology of phosphor particles could be improved. The intensity of the photoluminescence (PL)-emission of the phosphor screens deposited by the modified technique, when excited by ultraviolet (UV)-light with the wavelength of 254 nm, did not exceed that of the screens deposited without the polymeric additives. However, in vacuum UV, phosphors produced with the addition of polymers perform significantly better than the ordinary “no-polymer” FASP-coatings.     

The synthesis of (Y<Subscript>1-x</Subscript>Gd<Subscript>x</Subscript>)<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu phosphor particles by flame spray pyrolysis with LiCl flux

(Y_1-xGd_x)₂O₃:Eu phosphor particles with dense morphology were prepared by flame spray pyrolysis and the effect of LiCl flux on the crystallinity, morphology, and photoluminescence characteristics of the particles was investigated. All as-prepared particles had monoclinic phase regardless of flux and had different luminescence characteristics from those of commercial Y₂O₃:Eu particles of cubic phase. The addition of LiCl flux reduced the post-treatment temperature by 300 °C for phase transformation from the monoclinic phase to the cubic phase. The post-treatment temperature of (Y_0.75Gd_0.25)₂O₃:Eu particles for phase transformation decreased from 1100 °C to 700 °C when LiCl flux was used. The morphology of the particles was also influenced by the Y/Gd ratio and the LiCl flux. The as-prepared particles had spherical shape and non-aggregation characteristics regardless of Y/Gd ratio and flux. The sphericity of the as-prepared particles prepared without flux was maintained after post-treatment for phase transformation in all Y/Gd ratios. However, LiCl addition promoted the aggregation between product particles. The prepared particles had high photoluminescence intensities comparable to that of the commercial product. PACS 64.70.Kb; 78.55.-m; 81.20.Rg; 75.50.Tt     

Enhanced photoluminescence properties of Zn2SiO4:Mn co-activated with Y/Li under VUV excitation

A series of green phosphors Zn_1.92−2xY_xLi_xSiO₄:0.08Mn²⁺ (0≤x≤0.03) were prepared by solid-state synthesis method. Phase and lattice parameters of the synthesized phosphors were characterized by powder X-ray diffractometer (XRD) and the co-doped effects of Y³⁺/Li⁺ upon emission intensity and decay time were investigated under 147 nm excitation. The results indicate that the co-doping of Y³⁺/Li⁺ has favorable influence on the photoluminescence properties of Zn₂SiO₄:Mn²⁺, and the optimal photoluminescence intensity of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 103% of that of commercial phosphor when the doping concentration of Y³⁺/Li⁺ is 0.01 mol. Additionally, the decay time of phosphor is much shortened and the decay time of Zn_1.90Y_0.01Li_0.01SiO₄:0.08Mn²⁺ is 3.39 ms, shorter by 1.83 ms than that of commercial product after Y³⁺/Li⁺ co-doping.     

One-step synthesis of the green phosphor Ce-Tb-Mg-Al-O system with spherical particle shape and fine size

Spray pyrolysis method was applied to the preparation of Ce_0.6Tb_0.4MgAl₁₁O₁₉ green phosphor particles. The characteristics of as-prepared particles such as photoluminescence, crystallinity, and morphology were compared with those of post-treated particles. The as-prepared particles at 1700 °C had higher crystallinity and photoluminescence properties compared with those of post-treated particles. The morphology of as-prepared particles obtained at low temperatures changed from spherical shape to plate-like shape after post-treatment at 1400 °C for 3 h. The particles directly prepared at 1700 °C had the mean size of 0.7 μm and non-aggregation characteristics. This study has demonstrated that without post-treatment processing/annealing, spherical phosphor particles having complex composition could be prepared by a one-step synthesis. Received: 20 December 1999 / Accepted: 25 May 2000 / Published online: 9 August 2000     

Double layer oxidation resistant coating for carbon fiber reinforced silicon carbide matrix composites

Double layer coatings, with celsian-Y₂SiO₅ as inner layer and Y₂Si₂O₇ as outer layer, were prepared by microwave sintering on the surface of carbon fiber reinforced silicon carbide matrix composite. Both celsian, Y₂SiO₅ and Y₂Si₂O₇ were synthesized by in situ method using BAS glass, Y₂O₃ and SiO₂ as staring materials. The sintering temperature was 1500 °C, and little damage was induced to the composite. The composition and micrograph of the fired coating were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The oxidation and thermal shock resistance of samples with doubled-layered coating were characterized at 1400 °C in air. After 150 min oxidation and thermal cycling between 1400 °C and room temperature for 15 times, the weight loss of double layer-coated sample was 1.22% and there were no cracks in the coating.     

Pulsed laser deposition of silicate phosphor thin films

Three types of silicate phosphor thin films, emitting in the red-green-blue (RGB) primary colors, were fabricated by pulsed laser deposition, including manganese and lead doped calcium silicate (CaSiO₃:MnPb) for red color, manganese doped zinc silicate (Zn₂SiO₄:Mn) for green color and cerium doped yttrium silicate (Y₂SiO₅:Ce) for blue color. A correlation was observed between photoluminescence intensity with film crystallinity and surface morphology. RGB phosphor thin films with excellent color saturation were obtained. Luminescence mechanisms for these phosphor thin films are discussed.     

Chemical and phase compositions of silicon oxide films with nanocrystals prepared by carbon ion implantation

The chemical and phase compositions of silicon oxide films with self-assembled nanoclusters prepared by ion implantation of carbon into SiO _x (x < 2) suboxide films with subsequent annealing in a nitrogen atmosphere have been investigated using X-ray photoelectron spectroscopy in combination with depth profiling by ion sputtering. It has been found that the relative concentration of oxygen in the maximum of the distribution of implanted carbon atoms is decreased, whereas the relative concentration of silicon remains almost identical over the depth in the layer containing the implanted carbon. The in-depth distributions of carbon and silicon in different chemical states have been determined. In the regions adjacent to the layer with a maximum carbon content, the annealing results in the formation of silicon oxide layers, which are close in composition to SiO₂ and contain silicon nanocrystals, whereas the implanted layer, in addition to the SiO₂ phase, contains silicon oxide species Si²⁺ and Si³⁺ with stoichiometric formulas SiO and Si₂O₃, respectively. The film contains carbon in the form of SiC and elemental carbon phases. The lower limit of the average size of silicon nanoclusters has been estimated as ∼2 nm. The photoluminescence spectra of the films have been interpreted using the obtained results.     

Preparation and characterizations of SiO2-coated nanoparticles of Mn0.4Zn0.6Fe2O4

Core/shell nanoparticles consisting of a magnetic core of zinc-substituted manganese ferrite (Mn_0.4Zn_0.6Fe₂O₄) and a shell of silica (SiO₂) are prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) as a precursor material for silica and salts of iron, manganese and zinc as the precursor of the ferrite. Three weight percentages of the shell materials of SiO₂ are used to prepare the coated nanoparticles. The X-ray diffractograms (XRD) of the coated and uncoated magnetic nanoparticles confirmed that the magnetic nanoparticles are in their mixed spinel phase in an amorphous matrix of silica. Particles sizes of the samples annealed at different temperatures are estimated from the width of the (3 1 1) line of the XRD pattern using the Debye-Sherrer equation. The information regarding the crystallographic structure together with the particles sizes extracted from the high-resolution transmission electron microscopy (HRTEM) of a few selected samples are in agreement with those obtained from the XRD. HRTEM observations revealed that particles are coated with silica. The calculated thickness is in agreement with that obtained from the HRTEM pictures. Hysteresis loops observed in the temperature range 300 down to 5 K and Mössbauer spectra at room temperature indicate superparamagnetic relaxation of the nanoparticles.     

Luminescence properties of Mn doped Zn2SiO4 phosphor films synthesized by combustion CVD

Zn₂SiO₄:Mn²⁺ phosphor films were successfully prepared by a novel combustion chemical vapor deposition (CCVD) method. In the CCVD process, a flammable solution, containing precursor materials, is atomized and sprayed through a specially designed nozzle and ignited to form a combustion flame. This enables crystallized films to be directly deposited onto a substrate in open-atmosphere with no post deposition heat treatment. SEM images indicated that the film deposited at 1200 °C consisted of densely packed particles with a fine grain size of several 100 nm. Strong Photoluminescence (PL) and cathodoluminescence (CL) intensities were observed with Zn₂SiO₄:Mn²⁺ samples deposited at a substrate temperature of 1200 °C exhibiting the best crystallinity and highest luminescence. The optimum doping level for films deposited using CCVD was found to be ∼4 mol% Mn²⁺ of starting concentration, with a maximum CL luminescence equivalent to 53% of the luminescence measured from a commercial powder phosphor. A relatively fast CL decay with life time about 0.6-0.7 ms was also observed from these films.     

Synthesis and characterization of spherical core-shell particles SiO2@AgEu(MoO4)2

Submicron spherical SiO₂ particles have been coated with AgEu(MoO₄)₂ phosphor layers by a sol-gel process, followed by surface reaction at high temperature, to get core/shell structured SiO₂@AgEu(MoO₄)₂ particles. X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the resulted core-shell phosphors. The luminescent properties of the core-shell structured phosphors have also been measured at room temperature, and their photoluminescence (PL) spectra are similar to the pure AgEu(MoO₄)₂ phosphor prepared by the same sol-gel method exhibiting red emission.     

Synthesis and characteristics of nano-size sandwich structure (Y,Gd)BO3: Eu3+ phosphors

The sandwich structure core–shell–shell nanospheres SiO₂@(Y,Gd)BO₃:Eu³⁺@SiO₂ (SiO₂@YGB@SiO₂) have been synthesized by depositing YGB nanoparticles on silica core surface through the precipitation method, followed by sol–gel processing of tetraethoxysilane (TEOS) to form smooth silica shell over the surface of YGB. The phosphors were characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), transmission electronic microscope (TEM) and photoluminescence spectra. The results showed that the phosphors with spherical morphology can be produced easily by assembling the core–shell or core–shell–shell structure, and the XRD patterns indicated that the crystallinity of YGB is weakened due to the core–shell structure, which resulting from the local site symmetry of Eu³⁺ was decreased. The photoluminescence properties of the product are compared with those of the pure YGB, the core–shell structure SiO₂@YGB and YGB@SiO₂. The emission intensity, relative luminous efficiency and Red/Orange values of phosphors are increased in the order SiO₂@YGB@SiO₂>SiO₂@YGB>YGB@SiO₂>YGB; and the chromaticity coordinates of the phosphors are shifted from orange of pure YGB to red of SiO₂@YGB@SiO₂.     

Synthesis and cathodoluminescent properties of Y2SiO5:Tb3+ phosphors prepared from uniform precursor

The luminescent properties of phosphors are sensitive to the size of phosphor particles. The commercial Y₂SiO₅:Tb³⁺ phosphors usually show relatively larger particle size (5–10 μm) due to the irregular morphology of rare earth oxide precursor and thus degrade the luminescent properties. In this paper, we report the Y₂SiO₅:Tb³⁺ phosphors synthesized from the uniform Tb-doped Y₂O₃ precursor by a homogeneous precipitation method. Compared with the commercial phosphors, the obtained Y₂SiO₅:Tb³⁺ phosphors manifest the uniform morphology with much smaller particles distributing from 0.8 μm to 1.9 μm. Consequently, the cathodoluminescent intensity under low excitation voltage (1–5 kV) was increased, demonstrating a strong green emission with a dominant wavelength of 545 nm. Our results indicate an effective way to develop the high-quality phosphors for field emission display.     

Luminescence and structure of nanosized inclusions formed in SiO2 layers under double implantation of silicon and carbon ions

Luminescent and structural characteristics of SiO₂ layers exposed to double implantation by Si⁺ and C⁺ ions in order to synthesize nanosized silicon carbide inclusions have been investigated by the photoluminescence, electron spin resonance, transmission electron microscopy, and electron spectroscopy methods. It is shown that the irradiation of SiO₂ layers containing preliminary synthesized silicon nanocrystals by carbon ions is accompanied by quenching the nanocrystal-related photoluminescence at 700–750 nm and by the enhancement of light emission from oxygen-deficient centers in oxide in the range of 350–700 nm. Subsequent annealing at 1000 or 1100°C results in the healing of defects and, correspondingly, in the weakening of the related photoluminescence peaks and also recovers in part the photoluminescence of silicon nanocrystals if the carbon dose is less than the silicon dose and results in the intensive white luminescence if the carbon and silicon doses are equal. This luminescence is characterized by three bands at ～400, ～500, and ～625 nm, which are related to the SiC, C, and Si phase inclusions, respectively. The presence of these phases has been confirmed by electron spectroscopy, the carbon precipitates have the sp ³ bond hybridization. The nanosized amorphous inclusions in the Si⁺ + C⁺ implanted and annealed SiO₂ layer have been revealed by high-resolution transmission electron microscopy.     

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.     

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.