Synthesis,characterization and studies of radiative properties on Eu3+-doped ZnAl2O4

Eu³⁺-doped ZnAl₂O₄ phosphors were successfully synthesized in air atmosphere at 900 °C. The phosphors were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), thermally stimulated luminescence (TSL) and photoluminescence (PL) techniques. The average particle size of the system as determined from SEM was found to be 100–150 nm (for samples annealed at 900 °C). PL spectra of the doped phosphors showed emission peaks corresponding to Eu³⁺ ions. Lifetime studies revealed Eu³⁺ ions to be in two different sites. The asymmetric ratio (I₆₁₆/I₅₉₂) was observed to be about 3.75. This suggested that Eu³⁺ ion entered the host mainly substituting Al³⁺ site distorting the local environment and is partly located on surface of the phosphors. A prominent glow peak at 430 K was observed in the TSL of γ-irradiated Eu³⁺-doped ZnAl₂O₄ phosphors. Trap parameters for this peak have been determined and the probable mechanism for the glow peak is proposed. CIE chromaticity coordinates for the system were evaluated. It was observed that, the system could be employed as a potential red emitting phosphor. Commercial utility of the phosphor was investigated by comparing it with commercial red phosphor. The PL intensity of the as prepared phosphors was 63% of that of the commercial phosphor. Apart from this, various radiative properties such as the Judd–Ofelt intensity parameters, spontaneous emission probabilities, luminescence branching ratios, radiative lifetimes and quantum efficiency were evaluated for the system.     

Effect of doping concentration and annealing temperature on luminescence properties of Y2O3:Eu3+ nanophosphor prepared by colloidal precipitation method

Eu³⁺ doped Y₂O₃ nanophosphors have been synthesized using the simple colloidal precipitation method. Doping of Eu³⁺ ions in host yttria lattice has been achieved through slow re-crystallization process under wet-chemical conditions followed by annealing at high temperatures (300–1400 °C). The nanophosphors were characterized by using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), atomic force microscopy (AFM) and spectrofluorometer techniques. XRD analysis reveals formation of pure cubic phase of Y₂O₃ in samples annealed at 700 °C or above. Further, the XRD data was successfully used to retrieve the crystallite size and size distribution from powder samples using the FW((1/5)/(4/5))M method. Crystallite size (11–50 nm) extracted from XRD has been found to be consistent with AFM measurements. The PL emission spectra of nanophosphors show bright red emission at 612 nm due to hypersensitive electric dipole (ED) ⁵D₀–⁷F₂ transition of Eu³⁺ ions in Y₂O₃ lattice. Further, photoluminescence studies indicate that optimum value of the Eu³⁺ to get best luminescence properties is 12 at%. Surface conjugations of these nanophosphors with water soluble dextran biomolecules have also been performed. Surface conjugated rare earth nanophosphors have great potential for bio-applications.     

Luminescence enhancement by the reduction–oxidation synthesis in monoclinic RE2O3 (RE=Eu,Gd) phosphors containing Eu3+ activator

A novel synthesis was developed for enhanced luminescence in sesquioxide phosphors containing Eu³⁺ activator. It consisted of two annealing steps: reduction under vacuum with gaseous H₂ at 10 Torr and 1300 °C and re-oxidation at 300–1500 °C in air. The integrated luminescence intensity of the monoclinic Eu₂O₃ phosphor was enhanced ca. 21 times by this method compared with conventional processing. The photoluminescence (PL) intensity was maximized at re-oxidation temperatures of 500–1100 °C. The PL characteristics of monoclinic Eu₂O₃ and Gd₂O₃:0.06Eu samples were compared with a commercial cubic Y₂O₃:Eu phosphor. The evolution of physical characteristics during the two-step annealing was studied by Raman spectroscopy, XPS, XRD, PL decay analysis, and SEM. PL decay lifetime increased proportionally to the PL intensity over the range 0.5–100 μs. Additional vibrational modes appeared at 490, 497, and 512 cm^?1 after the two-step annealing. The increase in PL intensity was ascribed to the formation of excess oxygen vacancies and their redistribution during annealing. Resonance crossovers between the charge transfer state and the emitting ⁵D_J states are discussed in relation to reported luminescence saturation mechanisms for oxysulfides Ln₂O₂S:Eu³⁺ (Ln=Y, La).     

Synthesis and photoluminescent behavior of Eu3+-doped alkaline-earth tungstates

Eu³⁺-doped alkaline-earth tungstates MWO₄ (M=Ca²⁺, Sr²⁺, Ba²⁺) were prepared by a polymeric precursor method based on the Pechini process. The polymeric precursors were calcined at 700 °C for 2 h in order to obtain well-crystallized powders and then characterized by X-ray diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and photoluminescence spectroscopy (PL). All prepared samples showed a pure crystalline phase with scheelite-type structure confirmed by XRD. It was noted that the charge-transfer band shifted from 260 to 283 nm when calcium is replaced by strontium. However, this band was not observed for Eu³⁺-doped barium tungstate. Upon excitation at 260 nm, the emission spectra are dominated by the red ⁵D₀→⁷F₂ transition at 618 nm. By analyzing of the emission lines, it was inferred that Eu³⁺ ions occupy low symmetry sites in the host lattice. It was also found that Eu³⁺-doped SrWO₄ displays better chromaticity coordinates and greater luminescence intensity than the other samples.     

Blue emission in Eu2+ activated MgXAl10O17 (X = Sr,Ca) phosphors

Here we reported photoluminescence properties of Eu²⁺ activated in novel and existing MgXAl₁₀O₁₇ (X = Sr, Ca) phosphor which has been prepared by combustion synthesis at 550 °C under UV and near UV excitation wavelength. The PL emission properties of MgSrAl₁₀O₁₇:Eu²⁺ were monitored at 254 nm and 354 nm respectively keeping emission wavelength at 469 nm. Whereas novel MgCaAl₁₀O₁₇:Eu²⁺ exhibit emission band at 452 nm keeping excitation at 378 nm. These blue emission corresponds to 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions. Further phosphor was analyzed by XRD for the confirmation of desired phase and purity.     

New synthesis of high-quality storage phosphors

We present a single step synthesis method for the photostimulable X-ray storage phosphor BaFBr:Eu²⁺ which results in a highly sensitive powder with a relatively small average grain size of 5.4 μm. The starting chemical reagents are BaCO₃, NH₄F, NH₄Br and EuF₃. The reaction initiated by the decomposition of the ammonium materials leads to highly volatile hydrogen halide gases which react with the BaCO₃ to form BaFBr at temperatures up to 300 °C. Further heating results in the incorporation of Eu²⁺ and the formation of halide vacancies at temperatures in between 390 and 580 °C. The resulting photostimulated luminescence (PSL) efficiency is optimized after sintering at 800 °C. The reaction process is monitored by differential thermal analysis (DTA) and the reaction products are detected by mass-spectroscopy which confirms the proposed chemical reactions. Intermediate and final products are identified using X-ray diffraction. Photoluminescence (PL) and PSL spectra show the incorporation of Eu²⁺ into the lattice, as well as a PL peak at 470 nm which is not present in the PSL spectrum. This peak is shown to originate from O^2? in the lattice and directly affects the PSL sensitivity.     

Effects of heat treatment and TiO2 content on the optical properties of Eu3+ doped TiO2–SiO2 thin films

The photoluminescence properties of Eu³⁺-doped TiO₂–SiO₂ thin films were investigated. The films were deposited on silicon substrates by the sol–gel process using the dip-coating method. The molar ratio of TiO₂ content was varied from 25% to 100%, while Europium concentration was fixed to 1%. The obtained films were calcinated at various temperatures ranging from 400 °C to 1300 °C, which allowed determining the optimal conditions for the Eu³⁺ luminescence. Meanwhile, the structure of TiO₂–SiO₂ powders, prepared in the same conditions as the films, was also studied by Raman spectroscopy. It revealed the role of Europium and SiO₂ on the stabilization of the anatase phase and the importance of the silica matrix in the control of titania particle size.     

Development of zeolite-derived novel aluminosilicate phosphors

In this research, zeolite-derived aluminosilicate phosphors were synthesized through the ion exchange route. Red light-emitting property of Eu³⁺-doped aluminosilicate phosphors were discussed from a view point of the Eu content, heat-treatment condition and the oxidation state of Eu ions. The crystalline phase of the host aluminosilicates could be successfully controlled as designed based on the published NaAlO₂–SiO₂ binary phase diagram. Orange-red emission peaks derived from the ⁵D₀→⁷F_j (j=0, 1, 2, 3, 4) transition of Eu³⁺ were observed around 590–700 nm, and 4f⁶5d→4f⁷ transition of Eu²⁺ was observed at around 400–500 nm. The relative intensity I(⁵D₀→⁷F₂) of the dominant emission peak at 612 nm increased consistently with the Eu content. The results of the XANES spectroscopy analysis revealed that Eu²⁺ ion in the 1400 °C as heat-treated host aluminosilicate were successfully converted to Eu³⁺ by the additional annealing at 1100 °C. The Eu contents and heat-treatment conditions were determined to exhibit the best performance as a red phosphor, which were 10 wt% and 1500 °C, respectively     

Probing lattice defects in Sr2MgSi2O7:Eu2+,Dy3+

The Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ materials were prepared with a solid state reaction and their microscopic structure (at 295 K only) and luminescence were studied at selected temperatures between 150 and 295 K. Undisturbed Sr crystal planes were common in the TEM images of the undoped Sr₂MgSi₂O₇ material, whereas with Eu²⁺ doping more disturbed planes were observed even in the nanometer scale. With Dy³⁺ co-doping, a large number of small lattice domains created by the discontinuities in the crystal structure was observed. The domains with different orientations seem to be centered around point defects. The decay curves of Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ showed fast (ms scale) persistent luminescence. The intensity of persistent luminescence increased considerably between 200 and 250 K while remaining constant in the ranges of 150–200 and 250–295 K. The changes were used to study the depth of the traps. In general, Dy³⁺ co-doping was found to deepen the traps.     

Photoluminescence properties of Eu2+–Mn2+ codoped Ca-α-SiAlON phosphors

Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors, Ca_0.736?ySi_9.6Al_2.4O_0.8N_15.2:0.064 Eu²⁺, yMn²⁺, were firstly synthesized by the high temperature solid state reaction method. The effects of doped Eu²⁺ and Eu²⁺–Mn²⁺ concentrations on the photoluminescence properties of the as-prepared phosphors were investigated systematically. Powder X-ray diffraction shows that pure Ca-α-SiAlON phase is synthesized after sintering at 1700 °C for 2 h under 0.5 MPa N₂ atmosphere. The excitation spectra of Eu²⁺-doped Ca-α-SiAlON phosphors are characterized by two dominant bands centered at 286 nm and 395 nm, respectively. The photoluminescent spectrum of Eu²⁺-doped Ca-α-SiAlON phosphor exhibits an intense emission band centered at 580 nm due to the allowed 4f ⁶5d→4f ⁷ transition of Eu²⁺, showing that the phosphor is a good candidate for creating white light when coupled to a blue LED chip. The intensities of both excitation and emission spectra monotonously decrease with the increment of codoped Mn²⁺ content (i.e. y value), indicating that energy transfer between Eu²⁺ and Mn²⁺ is inefficient in the case of Eu²⁺–Mn²⁺ codoped Ca-α-SiAlON phosphors.     

Spectroscopic properties of Co2+: ZnAl2O4 nanocrystals in sol–gel derived glass–ceramics

Transparent glass–ceramics containing zinc–aluminum spinel (ZnAl₂O₄) nanocrystals doped with tetrahedrally coordinated Co²⁺ ions were obtained by the sol–gel method for the first time. The gels of composition SiO₂–Al₂O₃–ZnO–CoO were prepared at room temperature and heat-treated at temperature ranging 800–950 °C. When the gel samples were heated up to 900 °C, ZnAl₂O₄ nanocrystals were precipitated. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. X-ray diffraction analysis shows that the crystallite sizes of ZnAl₂O₄ crystal become large with the heat-treatment temperature and time, and the crystallite diameter is in the range of 10–15 nm. The dependence of the absorption and emission spectra of the samples on heat-treatment temperature were presented. The difference in the luminescence between Co²⁺ doped glass–ceramic and Co²⁺ doped bulk crystal was analysed. The crystal field parameter D_q of 423 cm⁻¹ and the Racah parameters B of 773 cm⁻¹ and C of 3478.5 cm⁻¹ were calculated for tetrahedral Co²⁺ ions.     

The influence of Eu3+ doping on photoluminescent properties of red emitting phosphor YInGe2O7:Eu3+ by microwave assisted and conventional sintering method

This paper describes an investigation of the crystalline morphology and photoluminescent properties of YInGe₂O₇ powders doped with different Eu³⁺ concentrations using microwave assisted sintering and conventional sintering. X-ray powder diffraction analysis confirmed the formation of monoclinic YInGe₂O₇ structure as YInGe₂O₇:Eu³⁺ powders were sintered at 1200 °C in microwave furnace for 1 h, and the raw material phase of Y₂O₃ was observed when Eu³⁺ concentration was below 30 mol%. Scanning electron microscopy showed microwave assisted sintering results in smaller particle size and more uniform grain size distribution. In the photoluminescent (PL) studies, the concentration quenching effect was observed under the excitation at 393 nm, but not under the excitation at CTS band. The ⁵D₀→⁷F₂ transition (620 nm), exhibits a non-exponential decay behavior as YInGe₂O₇:Eu³⁺ powders were sintered by microwave with the Eu³⁺ concentration higher than 50 mol%.     

White-light generation through Ce3+/Mn2+-codoped and Eu2+-doped Ba1.2Ca0.8SiO4 T-phase phosphors

Hexagonal Ba_1.20Ca_0.8?2x?ySiO₄:xCe³⁺,xLi⁺,yMn²⁺ phosphors exhibit two emission bands peaking near 400 and 600 nm from the allowed f–d transition of Ce³⁺ ions and the forbidden ⁴T₁–⁶A₁ transition of Mn²⁺ ions, respectively. The strong interaction between Ce³⁺/Mn²⁺ ions is investigated in terms of energy transfer, crystal field effect, and microstructure by varying their concentrations. They show a higher quenching temperature of 250 °C than that of a commercially used (Ba,Sr)₂SiO₄:Eu²⁺ phosphor (150 °C). Finally, mixtures of these phosphors with green-emissive Ba_1.20Ca_0.70SiO₄:0.10Eu²⁺ are tested and yielded correlated color temperatures from 3500 to 7000 K, and color rendering indices up to 95%.     

100 MeV Si8+ ion induced luminescence and thermoluminescence of nanocrystalline Mg2SiO4:Eu3+

Nanoparticles of Mg₂SiO₄:Eu³⁺ have been prepared by the solution combustion technique and the grain size estimated by PXRD is found to be in the range 40–50 nm. Ionoluminescence (IL) studies of Mg₂SiO₄:Eu³⁺ pellets bombarded with 100 MeV Si⁸⁺ ions with fluences in the range 1.124–22.48×10¹² ions cm^?2 are carried out at IUAC, New Delhi, India. Five prominent IL bands with peaks at 580 nm, 590 nm, 612 nm, 655 nm and 705 nm are recorded. These characteristic emissions are attributed to the luminescence centers activated by Eu³⁺ cations. It is found that IL intensity decreases rapidly in the beginning. Later on, the intensity decreases slowly with further increase of ion fluence. The reduction in the ionoluminescence intensity with increase of ion fluence might be attributed to degradation of Si–O (ν₃) and Si–O (2ν₃) bonds present on the surface of the sample. The red emission with peak at 612 nm is due to characteristic emission of ⁵D₀→⁷F₂ of the Eu³⁺ cations. Thermoluminescence (TL) studies of Mg₂SiO₄:Eu³⁺ pellets bombarded with 100 MeV Si⁸⁺ cations with fluences in the range 5×10¹¹ ions cm^?2 to 5×10¹³ ions cm^?2 are made at RT. Two prominent and well resolved TL glows with peaks at ～220 °C and ～370 °C are observed. It is observed that TL intensity increases with increase of ion fluence. This might be due to creation of new traps during swift heavy ion irradiation.     

Formation and its mechanism of copper metal layers at surface by annealing in reduced atmosphere in CuO–Li2O–Nb2O5–SiO2 glass

A trace amount (0.5 mol%) of CuO-doped 40Li₂O–32Nb₂O₅–28SiO₂ glass (mol%) exhibits the formation of copper metal layers at the glass surface by annealing at temperatures (530 °C) below the glass transition temperature (544 °C) in the reduced atmosphere of 7% H₂–93%Ar. The coordination state of copper ions is examined from optical absorption and Fourier transform infrared (FT-IR) spectrum measurements, indicating the formation of Si–OH and Si–H bonds due to the diffusion of hydrogen into the inside of the glass and the reduction of Cu⁺ and Cu²⁺ ions. The mechanism of the formation of copper metals at the surface is proposed, in which the key points are the reduction of Cu²⁺ to Cu⁺ ions due to the hydrogen and the migration of Cu⁺ ions in the interior of the glass to the surface. The first finding on copper metal layers at the glass surface might have a potential for practical applications such as electrodes in glass.     

The influence of some processing conditions on host crystal structure and phosphorescence properties of SrAl2O4:Eu2+, Dy3+ nanoparticle pigments synthesized by combustion technique

The spectroscopic and host phase properties of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors with a series of different initiating combustion temperature, urea concentration as a fuel and critical pH of precursor solution are investigated. The SrAl₂O₄:Eu²⁺, Dy³⁺ nanoparticle pigments were obtained by exothermic combustion process within less than 5 min. The sample that ignited at initiating combustion temperature of 600 °C exhibits highest intensity emission peak at 517 nm in which the SrAl₂O₄ host phase has the maximum fraction of monoclinic SrAl₂O₄ phase. The excitation spectra consist of 240 and 254 nm broad peaks. The experimental results show that the optimum ratio of urea is 2.5 times higher than theoretical quantities for best emission condition of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphor particles. The critical pH was obtained about 5.2. The crystallite size of these pigments is about 40 nm before thermal treatment and 62 nm after thermal treatment, respectively.     

Synthesis and luminescence of La2BaZnO5 phosphors

A modified synthesis of La₂BaZnO₅ phosphors activated with rare earths Eu³⁺, Tb³⁺, Pr³⁺ and Sm³⁺, and ns² ion Bi³⁺ is reported. RE₂BaZnO₅ compounds are conventionally prepared by two step solid state reaction. In the first step, carbonates or similar precursors are intimately mixed and heated at 900 °C to decompose the precursors to oxides. To eliminate the unwanted phases like BaRE₂O₄, the resulting powders are reheated at 1100 °C for long time. We prepared La₂BaZnO₅ phosphors activated with various activators by replacing the first step by combustion synthesis. Results on photoluminescence are presented. PL results on Eu³⁺ and Tb³⁺ are in good agreement with the literature reports. PL emission from Sm³⁺, Pr³⁺ and Bi³⁺ had not been reported earlier. Excitation spectrum of Eu³⁺ is dominated by a charge transfer band around 318 nm, while for the other rare earths a band at 240 nm is always present. This is attributed to the host absorption.     

X-ray excited luminescence and photoluminescence of Bi4(GeO4)3 glass-ceramics

Bi₄(GeO₄)₃ glass materials have been characterized by X-ray excited luminescence, photoluminescence and cathodo-luminescence measurements. The materials were obtained by crystallization at different temperatures and their spectroscopic parameters were compared before and after crystallization. Thermoluminescence curves recorded after electron irradiation of BGO glass behave similarly to BGO crystals, showing several peaks between 408 K (135 °C) and 610 K (337 °C). The differences between the Bi₄(GeO₄)₃ crystals and glass materials are believed to result from the random distribution of GeO₄ tetrahedra around Bi³⁺ ions which influences the photoluminescence and TL parameters. The CL images of glass-ceramic samples obtained by partial crystallization at 600 °C show luminescent crystalline structures, which are probably responsible for the increase in scintillation efficiency.     

5D0→7F1 and 5D0→7F2 transition in europium doped halosulphates for mercury-free lamps

Polycrystalline Na₃SO₄F:Eu and NaMgSO₄F:Eu halosulphate phosphors prepared by a wet chemical method have been studied for its photoluminescence (PL) and thermoluminescence (TL) characteristics. Two well resolved peaks are observed at 593 nm and 614 nm, which are assigned to due to ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions of Eu³⁺ ions. TL is observed at temperatures between 100 °C and 300 °C. In this paper, we report PL emission spectra of Eu³⁺ and TL glow curves, which are more sensitive than the standard TLD-CaSO₄:Dy. The presented phosphors are applicable for the mercury free lamps and solid state lighting devices.     

Preparation and photoluminescence properties of the Sr1.56Ba0.4SiO4:0.04Eu2+ phosphor

The Sr_1.56Ba_0.4SiO₄:0.04Eu²⁺ phosphors were prepared via a combustion reaction and following the calcination method at low temperature. The influences of the amount of the uncommonly used SrCl₂ flux, different calcination temperatures and time on the structure and the photoluminescence (PL) properties of the phosphors were investigated. Under the excitation of 450 nm blue light, the phosphor shows the intense broad emission band from 490 nm to 650 nm, and the emission peak is centered at 553 nm. The luminescence intensity of Sr_1.56Ba_0.4SiO₄:0.04Eu²⁺ was very sensitive to the crystallinity and morphology characteristics of the phosphor. The phosphor calcined at 950 °C for 3 h in 20%H₂/80%Ar atmosphere exhibits improved PL properties due to its high crystallinity and excellent morphology characteristics. The use of the SrCl₂ flux provides a novel way to improve the crystallinity of the silicates phosphors at low preparation temperature.