Fine yellow α-SiAlON:Eu phosphors for white LEDs prepared by the gas-reduction–nitridation method

Yellow-emitting a-SiAlON:Eu²⁺ phosphors were synthesized by the gas reduction and nitridation of a homogeneous oxide precursor in a CaO–Al₂O₃–SiO₂–Eu₂O₃ system at 1400–1450 °C using an NH₃–CH₄ mixture gas as a reduction–nitridation agent. The precursor was prepared by a sol–gel process using a low-cost nitrate, tetraethyl orthosilicate and citric acid as the starting materials. The effects of reaction parameters such as heating rate, temperature, holding time and CH₄ content on the composition, microstructure and photoluminescence of the prepared powders were investigated. Nearly single-phase α-SiAlON was successfully synthesized by the one-step gas reduction and nitridation without the need for post-annealing at a higher temperature. The prepared powders consisted of relatively well-dispersed and uniform crystals with a hexagonal shape. The photoluminescence spectra of Eu-doped Ca-α-SiAlON phosphors excited by near-ultraviolet or blue light showed a broad, yellow emission band at 500–700 nm, which agrees well with that obtained from phosphors prepared by the conventional solid-state reaction.     

Fabrication and optical properties of NUV-emitting SiO2–SrB4O7:Eu glass–ceramic thin films

SiO₂–SrB₄O₇:Eu²⁺ glass–ceramic thin films were fabricated for possible application in near ultraviolet (NUV) emitting devices. Nano-sized SrB₄O₇:Eu²⁺ powders were prepared by a Pechini-type sol–gel method and a subsequent ball-milling treatment. The powders showed NUV emissions centered at 367 nm, upon irradiation with UV of shorter wavelengths, due to an allowed 4f⁶5d¹ → 4f⁷ electronic transition of Eu²⁺ ions. The glass–ceramic thin films were prepared by dip-coating of tetraethylorthosilicate (TEOS) solutions dispersed with the nano-sized SrB₄O₇:Eu²⁺ powders and a subsequent heat-treatment. It was found that the glass–ceramic thin films had relatively high thermal stability up to 800 °C in terms of the Eu²⁺ emissions. SiO₂ layers surrounding SrB₄O₇:Eu²⁺ appeared to be effective for the surface passivation of the phosphor particles.     

Characteristics of Eu-doped Ca-α-SiAlON phosphor powders prepared by spray pyrolysis process

Eu²⁺-doped Ca-α-SiAlON phosphor powders with fine size and regular morphology were prepared by combining spray pyrolysis and the carbothermal reduction and nitridation processes. The precursor powders were prepared by spray pyrolysis from the spray solution with ethylenediaminetetraacetic acid, citric acid, and sucrose; they had large sizes, were hollow, and had thin wall structures. The precursor powders containing a carbon component turned into Ca-α-SiAlON phosphor powders after firing at 1450 °C under a H₂/N₂ mixture gas. The mean size of the phosphor powders was 5.1 μm. The phosphor powders had a broad excitation spectra range of 250-500 nm; this consisted of two broadbands centered at 305 and 400 nm. When excited by a 455-nm blue light, the emission spectra of the phosphor powders displayed a broadband in the range of 500-700 nm, which resulted in a yellow emission. The wavelength of the emission spectrum showing the maximum intensity was 576 nm.     

Influence of calcination temperature on luminescent properties of Sr3Al2O6:Eu, Dy phosphors prepared by sol–gel-combustion processing

The detailed preparation process of Eu²⁺ and Dy³⁺ ion co-doped Sr₃Al₂O₆ phosphor powders with red long afterglow by sol–gel-combustion method in the reducing atmosphere is reported. X-ray diffraction, scanning electron microscopy and photoluminescence spectroscopy are used to investigate the effects of synthesis temperature on the crystal characteristics, morphology and luminescent properties of the as-synthesized Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors. The results reveal that Sr₃Al₂O₆ crystallizes completely when the combustion ash is sintered at 1200 °C. The excitation and the emission spectra indicate that the excitation broad-band lies chiefly in visible range and the phosphor powders emit strong light at 618 nm under the excitation of 472 nm. The light intensity and the light-lasting time of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors are increased when increasing the calcination temperatures from 1050 to 1200 °C. The afterglow of Sr₃Al₂O₆:Eu²⁺, Dy³⁺ phosphors sintered at 1200 °C lasts for over 600 s when the excited source is cut off. The red emission mechanism is discussed according to the effect of nephelauxetic and crystal field on the 4f⁶5d¹ → 4f⁷ transition of the Eu²⁺ ions.     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

Photoluminescence and thermal stability of yellow-emitting Sr-α-SiAlON:Eu<Superscript>2+</Superscript> phosphor

Novel α-SiAlON:Eu²⁺-based yellow oxynitride phosphors with the formula Sr_0.375−x Eu _x ²⁺Si_12−m−n Al _m+n O _n N_16−n (m = 0.75, n = x = 0.004–0.04) have been prepared by firing the powder mixture of SrSi₂, α-Si₃N₄, AlN, and Eu₂O₃ at 2,000 °C for 2 h under 1 MPa nitrogen atmosphere. The luminescence properties, the dependence of the activator concentration of Eu²⁺ and the thermal stability of Sr-α-SiAlON:Eu²⁺ phosphor have been investigated in comparison with Ca-α-SiAlON:Eu²⁺ phosphor. Similar to Ca-α-SiAlON:Eu²⁺ phosphor, Sr-α-SiAlON:Eu²⁺ phosphor has the excitation wavelength ranging from the ultraviolet region to 500 nm, and exhibit intense yellow light. The strongest luminescence was achieved at about x = 0.02 with the emission peak at 578 nm, slightly shorter than that of Ca-α-SiAlON:Eu²⁺ phosphor at 581 nm. Temperature-dependent emission intensity of Sr-α-SiAlON:Eu²⁺ phosphor is comparable to that of Ca-α-SiAlON:Eu²⁺ phosphor. The results suggest that the different position of the emission peak for Sr- and Ca-α-SiAlON:Eu²⁺ depends on the composition and the Stokes shift, and the thermal stability is nearly independent of Sr and Ca or fixed by the network of (Si, Al)–(O, N) in α-SiAlON at the same Eu²⁺ concentration.     

Study of (Bi4−x La x ) Ti3O12 Powders and Ceramics Prepared by Sol-Gel Method

La-modified (Bi_4–x La _x )Ti₃O₁₂ (abbreviated as BLT) powders were prepared by sol-gel processing methods. The powders were characterized by differential thermal analysis (DTA) and laser-diffraction particle-size analysis. The (Bi_4–x La _x )Ti₃O₁₂ ceramics were prepared from the powders and characterized by X-ray diffraction (XRD). The results indicate that the sol-gel method can be used to prepare nanometer powder for the new types of BLT ferroelectric ceramics. The solid reaction of BLT powders occurs at 730°C approximately resulting in the growth of BLT grain. The average grain size may be varied in the range 60–500 nm, depending on the calcination temperature of the powders. The (Bi_4–x La _x )Ti₃O₁₂ ceramics prepared from the powders were polycrystalline materials with completely monoclinic (Bi_4–x La _x )Ti₃O₁₂ phase.     

Synthesis,photoluminescence and mechanoluminescence properties of Eu<Superscript>3+</Superscript> ions activated Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> phosphors

A new series of Eu³⁺ ions-activated calcium gadolinium tungstate [Ca₂Gd₂W₃O₁₄] phosphors were synthesized by conventional solid-state reaction method. The X-ray diffraction patterns of the powder samples indicate that the Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors are of tetragonal structure. The prepared phosphors were well characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), and mechanoluminescence (ML) spectra. PL spectra of Eu³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ _exci = 392 nm (⁷F₀ → ⁵L₆). The energy transfer from tungstate groups to europium ions has also reported. Mechanoluminescence studies of Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors have also been explained systematically.     

Rapid densification and reaction sequences in self-reinforced Y-α-SiAlON ceramics with barium aluminosilicate as an additive

Y-α-SiAlON (Y_1/3Si₁₀Al₂ON₁₅) ceramics with 5 wt.%BaAl₂Si₂O₈ (BAS) as an additive were synthesized by spark plasma sintering (SPS). The kinetic of densification, phase transformation sequences and grain growth during sintering process were investigated. Full densification could be achieved by 1600 °C without holding and using a heating rate of 100 °C min⁻¹, but the transformation from α-Si₃N₄ to α-SiAlON is not completed simultaneously with the densification process. The equilibrium phase assemblage could be reached after SPS at 1800 °C for 5 min and the resultant material possesses self-reinforced microstructure with high hardness of 19.2 GPa and fracture toughness of 6.8 MPa m^1/2. The complete crystallization of BAS is beneficial to the high temperature mechanical properties. The obtained could maintain the room strength up to 1300 °C.     

Study of the effect of Li<Superscript>+</Superscript> concentration on the photoluminescence properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphors

Y₂O₃:Eu³⁺ phosphors were prepared by hydrothermal method. Effect of the doping concentration of Eu³⁺ on the photoluminescence properties of Y₂O₃:Eu³⁺ phosphor was studied in details. It was found that the strongest emission intensity is achieved as atomic ratio of Y³⁺ to Eu³⁺ is 8. As concentration of Eu³⁺ exceeds the critical concentration, the emission intensity decreases dramatically due to the concentration quenching of Eu³⁺. Also, the effect of Li⁺ on the photoluminescence performance of the Y₂O₃:Eu³⁺ phosphor is studied in this work. According to the results, the doping of Li⁺ may greatly improve the PL performance of the Y₂O₃:Eu³⁺ phosphors due to the flux effect and improved crystallinity caused by the doping of Li⁺.     

Sinterability of β-SiAlON powder prepared by carbothermal reduction and simultaneous nitridation of ultrafine powder in the Al2O3-SiO2 system

Three types of -SiAlON (Si_{6 – z} Al _z O _z N_{8 – z} ) powder were prepared by the carbothermal reduction and simultaneous nitridation of ultrafine powders in the Al₂O₃-SiO₂ system. The ultrafine starting oxide powders, prepared using the vapour-phase reaction technique, were mixed with carbon powder and heated at 1400 °C for 1 h under flowing nitrogen to form -SiAlON and followed by heating at 570 °C for 1 h in air to remove residual carbon. The resulting powders contained only -SiAlON with z values of 1.63, 2.05, and 2.99. The relative density (bulk density/true density) of -SiAlON compacts pressureless sintered at 1800 °C for 1 h under flowing nitrogen increased with z and reached 89.9% at z = 2.99. When the -SiAlON compact with z = 2.99 was hot pressed at 1800 °C for 1 h under flowing nitrogen, a maximum relative density of 93.6% was achieved. Although this hot pressed compact contained a small amount of 15R-SiAlON in addition to -SiAlON, it possessed a small average grain size (typically 0.5 m diameter) and high Vickers hardness (19.2 GPa).     

Engineering of luminescence from Gd2O3:Eu nanophosphors by pulsed laser deposition

Nanostructured Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The dependence of structural, morphological and optical properties of these films on photoluminescence was systematically studied by varying the annealing temperature, Eu³⁺ incorporation concentration and laser fluence. The intensity of the XRD peak from (2 2 2) crystal plane was found to increase with annealing temperature in the range 973–1173 K. Films annealed at 1173 K show a preferential growth along (2 2 2) crystal plane of the cubic Gd₂O₃ and enhanced photoluminescence at 612 nm. XRD and Micro-Raman spectra and lattice strain investigations suggest that Eu³⁺ incorporation introduce a strong lattice distortion in Gd₂O₃ matrix. Morphological investigations using atomic force microscopy indicate a strong influence of the annealing process on the surface roughness and particle size. This kind of transparent thin film phosphors may promise for applications in flat-panel displays and X-ray imaging systems.     

Synthesis and photoluminescence properties of LiEu(W,Mo)<Subscript>2</Subscript>O<Subscript>8</Subscript>:Bi<Superscript>3+</Superscript> red-emitting phosphor for white-LEDs

LiEu_1−x (W_2−y Mo _y )O₈:xBi³⁺ series red-emitting phosphors were synthesized by solid state reaction. The structure, morphology, and photoluminescent properties of phosphors were studied by X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectrum, respectively. X-ray powder diffraction analysis showed that the as-obtained phosphors belong to the scheelite structure. The average particle size of the investigated phosphor was about 8 μm. The excitation spectrum exhibits a charge-transfer broad band along with some sharp peaks from the typical 4f–4f transitions of Eu³⁺. Under excitation of UV, near-UV, or blue light, these phosphors showed strong red emission at 615 nm due to ⁵D₀–⁷F₂ transition of Eu³⁺. The incorporation of Mo⁶⁺ into LiEuW₂O₈:Bi³⁺ could induce red-shift of the charge-transfer broad band and a remarkable increase of photoluminescence. The highest red-emission intensity was observed with LiEu_0.80Mo₂O₈:0.20Bi³⁺. Compared with the commercial red-emitting phosphor, Y₂O₂S:Eu³⁺, the emission intensity of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor is much stronger than that of Y₂O₂S:Eu³⁺ and its chromaticity coordinates are closer to the standard values than that of the commercial phosphor. The optical properties of LiEu_0.80Mo₂O₈:0.20Bi³⁺ phosphor make it attractive for the application in white-light-emitting diodes (LEDs), in particular for near-UV InGaN-based white-LEDs.     

Thermal annealing effect on Y2O3:Eu phosphor films prepared by yttrium 2-methoxyethoxide sol–gel precursor

In this work, we demonstrate that yttrium 2-methoxyethoxide is a convenient sol–gel precursor to synthesize the Y₂O₃:Eu³⁺ phosphor films. The crystallization of Y₂O₃:Eu³⁺ phosphor films prepared from the yttrium 2-methoxyethoxide occurs at about 550 °C. We have also observed that our Y₂O₃:Eu³⁺ phosphor films undergo crystal structure change above annealing temperature of 750 °C which is not previously observed in the sol–gel fabrication method. The change of photoluminescent (PL) spectra is related to the evolution of Y₂O₃ crystal structure. It is shown in this investigation that the post-annealing treatment will help to produce phosphor films of improved brightness. The reasons assigned are the effective elimination of OH impurities and the grain growth of phosphor films.     

Greatly improved photoluminescence properties of the electrodeposited Y2O3:Eu thin film phosphors by the addition of Na and K ions

In this work, Y₂O₃:Eu³⁺ thin film phosphors were prepared by electro-deposition method. The effect of Na⁺ and K⁺ ions on the photoluminescence properties of Y₂O₃:Eu³⁺ thin film phosphor was studied in details. It was found that the addition of Na⁺ and K⁺ ions could improve the photoluminescence intensity by 3 to 4 times. The highly improved photoluminescence intensity may be caused by different factors. The improved crystallinity and the increased optical volume caused by the flux effect of Na⁺ and K⁺ ions could be the major reasons for the enhanced photoluminescence intensity. It was also found that the average lifetime of Y₂O₃:Eu³⁺ thin film phosphors could be adjusted by the molar amount of Na⁺ and K⁺ ions.     

Effect of dopant concentration and particle size on fluorescence properties of Y2O3:Eu3+ derived in presence of NIPAM/AAc copolymer

Y₂O₃:Eu³⁺ nano phosphors (about 65 nm in size) were prepared via co-precipitation method by using co-polymer NIPAM/AAc as a template with narrow size distribution. The aim of the paper is to indicate the co-polymer influence on size and luminescence characteristics of nano phosphors. In this respect, phase content and morphology were characterized by X-ray diffraction and transmission electron microscopy. All the powders were well crystallized and the particles were clearly spherical with good dispersibility. Luminescence measurements were used to investigate the role of precursor in powders and the utmost luminescence intensity was observed at 4 mol% of Eu³⁺ while the quenching concentration of Eu³⁺ ions has occurred at 5 mol%.     

Synthesis and photoluminescence properties of SrLu2O4:Eu superfine phosphor

Superfine powder SrLu₂O₄:Eu³⁺ was synthesized with a precursor prepared by an EDTA - sol-gel method at relatively low temperature using metal nitrate and EDTA as starting materials. The heat decomposition mechanism of the precursor, formation process of SrLu₂O₄:Eu³⁺and the properties of the particles were investigated by thermo-gravimetric (TG) - differential thermal analysis (DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) analyses. The results show that pure SrLu₂O₄:Eu³⁺ superfine powder has been produced after the precursor was calcinated at 900 °C for 2 h and has an elliptical shape and an average diameter of 80-100 nm. Upon excitation with 250 nm light, all the SrLu₂O₄:Eu³⁺ powders show red and orange emissions due to the 4f-4f transitions of Eu³⁺ ions. The highest photoluminescence intensity at 610 nm was found at a content of about 6 mol% Eu³⁺. Splitting of the ⁵D₀-⁷F₁ emission transition revealed that the Eu³⁺ ions occupied two nonequivalent sites in the crystallite by substituting Lu³⁺ ions.     

Effect of Ni-modified α-Al2O3 prepared by sol–gel and solvothermal methods on the characteristics and catalytic properties of Pd/α-Al2O3 catalysts

In the present study, Ni-modified α-Al₂O₃ with Ni/Al ratios of 0.3 and 0.5 were prepared by sol–gel and solvothermal method and then were impregnated with 0.3 wt.% Pd. Due to different crystallization mechanism of the two preparation methods used, addition of nickel during preparation of α-Al₂O₃ resulted in various species such as NiAl₂O₄, mixed phases between NiAl₂O₄ and α-Al₂O₃, and mixed phases between NiAl₂O₄ and NiO. As revealed by NH₃-temperature programmed desorption, formation of NiAl₂O₄ drastically reduced acidity of alumina, hence lower amounts of coke deposited during acetylene hydrogenation was found for the Ni-modified α-Al₂O₃ supported catalysts. For any given method, ethylene selectivity was improved in the order of Pd/Ni–Al₂O₃-0.5 > Pd/Ni–Al₂O₃-0.3 > Pd/Ni–Al₂O₃-0  Pd/α–Al₂O₃-commercial. When comparing the samples prepared by different techniques, the sol–gel-made samples showed better performances than the solvothermal-derived ones.     

Synthesis of Ca-α-SiAlON:Eux phosphor powder by carbothermal-reduction–nitridation process

Yellow-emitting Ca-α-SiAlON:Eu_x phosphor powders have been synthesized by the carbothermal-reduction–nitridation of a homogeneous Ca–Si–Al–Eu–C–O mixture at 1550 °C in flowing nitrogen. The resulting phosphor powder emits yellow luminescence with a peak wavelength at 575–590 nm under ultraviolet excitation at 370 nm. Compared with commercial Ce³⁺-doped yttrium aluminum garnet (YAG:Ce³⁺) phosphor powder, the synthesized Ca-α-SiAlON:Eu_x phosphor powder exhibits better thermal stability.     

Preparation and photoluminescence properties of γ-KCaPO4: Eu phosphors for near UV-based white LEDs

Novel whitish-blue phosphors based on a phosphate host matrix, γ-KCaPO₄: Eu²⁺, were prepared by a conventional solid-state reaction method using slightly phosphorus deficient conditions and their photoluminescence properties were investigated. The concentration quenching process, temperature dependence of the luminescence and decay curve were also investigated. The γ-KCaPO₄: Eu²⁺ phosphor was efficiently excited by UV-Visible light at wavelengths of 200-450 nm and exhibited a bright whitish-blue emission with a maximum peak wavelength of 473 nm. All of these characteristics suggest that the γ-KCaPO₄: Eu²⁺ phosphors combined with red phosphors could be applicable to near UV-based white LEDs, i.e., only two kinds of phosphor powders are needed for the formation of white light.