Eu-doped glass materials for red luminescence

Red luminescence (at wavelength about 622 nm) from Eu³⁺ ions embedded in PbO–Bi₂O₃–Ga₂O₃–BaO glass hosts is reported for room and liquid helium temperatures. The substantial influence of energy transfer processes between the host and Eu³⁺ ions is shown experimentally through the dependences of photoluminescence on light polarization and excitation wavelength. Only polarized, excited pulsed XeII laser light (λ=714 nm) gives substantial luminescence with efficiency up to 14.3%. The role of phonon-relaxation subsystem in the observed luminescence is discussed.     

57Fe Mössbauer study of Eu1−x Sr x FeO3−y

The samples of Eu_1–x Sr _x FeO_3–y (x=0.0–1.0) were prepared by the solid state reaction method. Their X-ray diffraction patterns and⁵⁷Fe Mössbauer spectra at room temperature were measured. It is found that Sr ions incorporate in the lattice of EuFeO₃, the change of crystal structure is related to the dopant.⁵⁷Fe Mössbauer spectra consist of one magnetic, one doublet and one single paramagnetic components. The Fe ions in the cubic phase are in intermediate valence state between Fe(III) and Fe(IV) and may participate in electron hopping.     

Extraordinary Magnetic Properties of Ca1–xEuxS and Sr1–xEuxS Solid Solutions

The electron paramagnetic resonance (EPR) spectra and the stationary magnetic susceptibility are investigated for Ca_1–x Eu _x S and Sr_1–x Eu _x S solid solutions (0.00005 < x < 0.0032). The EPR spectrum of Eu²⁺ in both matrices contains a wide structureless line in addition to the narrow lines of the superfine structure characteristic of ions with high local symmetry. Because of the extraordinary temperature dependence of this line in CaS:Eu, it is associated with strongly interacting magnetic centers, namely, exchange-coupling pairs and chains or more complex clusters of magnetic ions. At the same time, the dependence of the stationary magnetic susceptibility in the temperature range 4.2–50 K has no peculiarities for CaS:Eu and SrS:Eu and obeys the Curie law.     

Synthesis, luminescence and crystallographic structure of Eu-doped garnet-type yafsoanite Ca3Te2(ZnO4)3

A red-emitting phosphor of Eu³⁺-doped calcium–tellurium–zinc oxide, Ca₃Te₂(ZnO₄)₃, with a garnet-type structure was synthesized by high temperature solid-state reactions. This phosphor exhibited a strong red emission. The photoluminescence excitation spectrum showed that Ca₃Te₂(ZnO₄)₃:Eu³⁺ can be effectively excited by UV–visible light. The property of long-wavelength excitation for this material has a benefit as a red phosphor in application of white light-emitting diodes. The colour coordinates were calculated. The excitation and emission spectra and luminescence decay curves were obtained using a pulsed, tunable, narrowband dye laser. Crystallographic sites and charge compensation mechanism of Eu³⁺ ions were discussed. The emission line from Eu³⁺ in intrinsic crystallographic site in the lattice was located at 579.56 nm. The emission line from Eu³⁺ in another disturbed site, which is created by the defects created by the charge-compensation, was located at 580.88 nm. The disordered crystallographic sites of Eu³⁺ are benefit for their strong red luminescence corresponding to the ⁵D₀→⁷F₂ transition.     

Effects of x and R3+ on the luminescent properties of Eu3+ in nanocrystalline YVxP1-xO4:Eu3+ and RVO4:Eu3+ thin-film phosphors

Using inorganic oxides and salts instead of alkoxides as the main starting materials, we prepared nanocrystalline YV_xP_1-xO₄:Eu³⁺ and RVO₄:Eu³⁺ (0x1; R=Y,La,Gd) thin-film phosphors by the Pechini sol–gel dip-coating process. The resulting films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra as well as luminescence decay. The results of XRD showed that a solid solution formed in the YV_xP_1-xO₄:Eu³⁺ film series from x=0 to x=1 with zircon structure. The same structure also held for the GdVO₄:Eu³⁺ film, but the LaVO₄:Eu³⁺ film crystallized with a different structure, monazite. AFM and SEM studies revealed that the phosphor films consisted of spherical particles ranging from 90 to 400 nm depending on the film compositions. With the increase of x values in YV_xP_1-xO₄:Eu³⁺ films, the integrated emission intensity and the red (⁵D₀–⁷F₂)-to-orange (⁵D₀–⁷F₁) intensity ratio of Eu³⁺ increase due to the increased energy-transfer probability from VO₄^3- to Eu³⁺ and the increased polarizability of the surrounding oxygen ions, respectively. The x values also have an influence on the decay behavior of Eu³⁺. The YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films showed very similar luminescence properties due to their same crystal structures. However, the LaVO₄:Eu³⁺ film exhibited a much different emission property from those of the YVO₄:Eu³⁺ and GdVO₄:Eu³⁺ films due to the structural effects. PACS 73.63.Bd; 78.55.Hx; 78.66.Nk; 81.15.Lm; 81.20.Fw     

Electron spin resonance and luminescence in Ga2−xEuxS3 single crystals

In present work electron spin resonance (ESR) and luminescence have been studied in Ga_2−xEu_xS₃ single crystals. The ESR and photoluminescence (PL) spectra of Ga_2−xEu_xS₃ were observed and the intensity of these spectra has increased linearly with the Eu concentrations in the samples. At the low temperature of 3.8 K in Ga_2−xEu_xS₃ single crystals, when the magnetic field has been applied as the perpendicular to the direction of [110], the hyperfine structure of ESR spectra has been observed. The exchange interaction of Eu²⁺ atoms in Ga_2−xEu_xS₃ single crystals have been determined as, g=4.2. The PL spectrum of pure Ga₂S₃ single crystals was recorded at 4.2 K and consisted of a narrow high-energy band at 2.53–2.38 eV and a low-energy band at 2.14–1.59 eV. Ga_2−xEu_xS₃ resulted in complete quenching of the impurity luminescence bands gave rise to a green europium band (2.38–2.14 eV) in the luminescence spectrum. Crystals of Ga_2−xEu_xS₃ emitted bright green electroluminescence (EL) spectrum when they excited with static and alternating electric fields at 77 K. We have also determined the field and frequency dependences of the EL.     

Synthesis and optical properties of red emitting Eu doped CaZrO3 phosphor

Eu³⁺ activated Ca_1−xEu_xZrO₃ (x = 0.01–0.05) phosphor with perovskite structure has been synthesized by sol–gel combustion method. The structure, morphology and optical properties of materials were characterized by X-ray diffraction, scanning electron microscopy and fluorescence spectrometry. The XRD results indicate that crystals of CaZrO₃:Eu³⁺ belongs to orthorhombic perovskite structure. The phosphors can be effectively excited by UV light and the emission spectra results indicate that red luminescence of CaZrO₃:Eu³⁺ due to electric dipole transition ⁵D₀ → ⁷F₂ at 616 nm is dominant. Thus, these prepared phosphors show remarkable luminescent properties which find applications in display devices.     

Spectral-luminescent properties of AgLa<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Eu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> solid solutions

The luminescent properties of AgLa_{1 − x} Eu _x (MoO₄)₂ (x = 0.1, 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0) under laser excitation (λ = 337.1 nm) are studied. It is shown that, upon substitution of Eu³⁺ for La³⁺, the symmetry of luminescence centers does not vary. According to the X-ray diffraction data, all samples have scheelite-like structure; the pattern of variation in volumes of their unit cells counts in favor of the presence of a continuous series of solid solutions. It is found that an increase in the europium concentration in AgLa_{1 − x} Eu _x (MoO₄)₂ leads to an increase in the luminescence intensity with a maximum at x = 0.9.     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

Effect of halide ion concentration and irradiation dose dependent photostimulated luminescence investigation in the image screen phosphor CsBr1-xClx:Euy 2+

Photoluminescence(PL) characterization is carried out on CsBr_1-xCl_x:Eu_y²⁺ (x = 0.05, 0.1, 0.2, 0.3 y = 100 ppm, 200 ppm) crystals grown in vacuum with the Bridgman technique. PL studies show an increase in luminescence intensity with a decrease in bromide ion content. F(Br^–) and F(Cl^–) centers are formed due to -ray irradiation at room temperature. Photostimulated luminescence (PSL) emission is found to increase with an increase in irradiation dose from 7.5 Gy to 30 Gy at room temperature. From the results it is demonstrated that out of the different compositions studied, CsBr_0.9Cl_0.1:Eu²⁺ (200 ppm) phosphor has a linear PSL response with respect to irradiation dose.     

Elaboration of nanostructured Eu3+-doped Gd2O3 phosphor fine spherical powders using polyol-mediated synthesis

Red-emitting Eu³⁺-doped Gd₂O₃ spherical powders were directly precipitated using a polyol method. The as-synthesized powders consist of agglomerates with a spherical shape and a size ranging between 0.4 and 0.6 μm. Each agglomerate is nanostructured and consists of a packing of nanocrystallites (3–5 nm) of a bcc oxide phase whose luminescence presents original features in comparison with bulk materials. The powders were further calcinated and the size of both crystallites and agglomerates, the crystalline structure and the luminescence were studied as a function of the annealing temperature. For temperatures lower than 900 °C, the samples obtained are highly crystalline and possess the classical Eu³⁺ red luminescence. For optimized temperature, the morphology of the particles can be preserved leading to spherical, dense, luminescent and almost monodisperse oxide powders, 0.5 μm in size. PACS 81.07.Bc; 81.07.Wx; 81.16.Be; 75.50.-y; 42.70.-a     

Enhanced electroluminescence of Eu by Tb in complexes Tb1−xEux(TTA)3Dipy

A series of rare earth ternary compounds of Tb_1−xEu_x(TTA)₃Dipy (HTTA=thenoyltrifluoroacetone, Dipy=2,2′-dipyridyl) have been synthesized, and the characteristics of the compounds have been performed by DTA-TG, IR, UV and fluorescence spectroscopy. Photoluminescence measurements indicated that the complexes of Eu(III) emit strong red luminescence under UV radiation. IR spectra suggest that complexes have been successfully synthesized, and TG curves indicate that the complexes are stable up to a temperature of about 220 °C. The Eu complex was blended with poly(N-vinylcarbazole) (PVK) and spin coated into films, and electroluminescence devices with the structure of Indium Tin Oxide (ITO)/PVK:Tb_1−xEu_x(TTA)₃Dipy/BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)/aluminum quinoline (AlQ)/Al were fabricated, the luminescence of Eu³⁺ complexes enhances after doping with Tb³⁺. Therefore, it may be an effective method to improve the EL intensity of the lanthanide complex.     

Effect of Mg and Ti doping on the luminescence of Y2O3:Eu

The Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV materials (x_Eu: 0.02, x_Mg: 0.08, x_Ti: 0.04) were prepared by solid state reaction. The purity and crystal structure of the material was studied with the X-ray powder diffraction. Luminescence properties were studied in the UV-VUV range with the aid of synchrotron radiation. The emission of Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV had a maximum at 612 nm (λ_exc: 250 nm) due to the ⁵D₀→⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em: 612 nm) showed a broad band at 233 nm, due to the charge transfer transition between O²⁻ and Eu³⁺, and at 297 nm due to the Ti→Eu³⁺ energy transfer. Only very weak persistent luminescence was discovered. In the room and 10 K temperature excitation spectra, the line at 208 nm is due to the formation of a free exciton (FE) and a broad band at 199 nm was related to the valence-to-conduction band absorption of the Y₂O₃ host lattice. The absorption edge was ca. 205 nm giving 6.1 eV as the energy gap of Y₂O₃.     

Effect of Na+ co-dopant and activator concentration on luminescent properties of CaGa4O7:Eu3+

Two series of calcium gallate phosphors: Ca_1?xEu_xGa₄O₇ and Ca_1?2xEu_xNa_xGa₄O₇ (x=0, 0.002, 0.01, 0.02, 0.03, 0.05) were synthesized by a modified Pechini method and their optical properties at 298 and 77 K were investigated. In undoped CaGa₄O₇ upon 255 nm excitation a bluish white emission (λ_max=500 nm) followed by an afterglow of the same color lasting for 10–20 s was observed. Eu³⁺-doping quenched the host-related luminescence and the characteristic red emission of the dopant with maximum at 613 nm appeared. Its excitation spectrum consisted of a broad band assigned to ligand to metal, O^2?→Eu³⁺, charge transfer absorption and narrow lines arising from intraconfigurational transitions within the 4f⁶ states of Eu³⁺ ion. The effects of Eu³⁺ concentration and Na⁺ co-doping on the luminescence properties and decay kinetics were studied. Low temperature emission spectra showed that Eu³⁺ ions are positioned in environments of different symmetries. Their relative populations changed with the activator content. Co-doping with Na⁺ ions led to a remarkable reduction of the number of Eu³⁺ sites as well as to noticeable improvement of the luminescence brightness though it did not affect the decay time of the emission. The quantum efficiencies of singly doped CaGa₄O₇:Eu³⁺ were very low (in the range of 1–3.7%). Na⁺ co-doping improved this parameter leading to the highest efficiency of 11% for CaGa₄O₇:3%Eu³⁺,3%Na⁺.     

Probing of inversion symmetry site in Eu-doped GdPO4 by luminescence study: Concentration and annealing effect

Eu³⁺-doped gadolinium orthophosphate (GdPO₄) (Eu³⁺ at%=0, 2, 5, 7, 10, 15, 20 and 30) nanoparticles have been prepared by ethylene glycol route and subsequently heated at 500 and 900 °C. The crystallite size increases with increasing heat-treatment temperature. Luminescence study shows that magnetic dipole transition (⁵D₀→⁷F₁) is prominent over the electric dipole transition (⁵D₀→⁷F₂), which has been attributed to occupancy of inversion symmetry site by more Eu³⁺ ions in Eu³⁺-doped GdPO₄. The luminescence intensity is enhanced as heat-treatment temperature increases from 500 to 900 °C due to the improved crystallinity. Optimum luminescence is observed for 5–7 at% Eu³⁺ in GdPO₄ nanoparticles. Above this concentration, luminescence intensity decreases due to concentration quenching effect. This is supported by lifetime study.     

Luminescence of aggregate centers in CsBr:Eu2+ single crystals

We have used the Bridgman method to grow CsBr:Eu²⁺ single crystals, adding an activator to the mix in the form of Eu₂O₃ in amounts of 0.0125, 0.0250, and 0.0500 mole %. At T = 300 K, we studied the absorption spectra, the photoluminescence (PL) spectra, and the photostimulated luminescence (PSL) spectra of the grown crystals. We have established that the structure of the photoluminescence and photostimulated luminescence centers in crystals grown from the CsBr:Eu₂O₃ mix includes isolated dipole centers Eu²⁺-V_Cs, emitting in bands with maxima at 432 nm and 455 nm respectively, and in crystals grown at activator concentrations of 0.025 and 0.050 mole % they also include aggregate centers (AC) based on CsEuBr₃ nanocrystals with emission bands at 515 m and 523 nm. We have shown that the maximum concentration of aggregate centers of the CsEuBr₃ nanocrystal type in CsBr:Eu²⁺ crystals is achieved for an activator content in the mix within the range 0.01–0.05 mole %. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 359–362, May–June, 2006.     

A potential red-emitting phosphor CaSrAl2SiO7:Eu for near-ultraviolet light-emitting diodes

A novel red-emitting phosphor CaSrAl₂SiO₇:Eu³⁺ was firstly synthesized through the high temperature solid state reaction at 1300 °C. The structure, diffuse reflection spectra, photoluminescence spectra, color-coordinate parameters and quantum efficiencies (QE) of phosphors were investigated. The obtained CaSrAl₂SiO₇:Eu³⁺ phosphors have the same structure with that of the Ca₂Al₂SiO₇ and Sr₂Al₂SiO₇ phosphor, which have the melilite structure. Optical properties were studied as a function of Eu³⁺ concentration x, when x>0.14, the intensity of absorption of the f–f transitions of Eu³⁺ at 393 nm is stronger than that of the broad charge transfer transition band (CTB) around 254 nm, and which matches well with the output lights of NUV–LEDs, whereas, the concentration of Eu³⁺x≤0.14, the absorption of 393 nm is weaker than that of CTB. The underlying reason of Eu³⁺ concentration on their luminescent properties was investigated and discussed in detail. As a result, comparing with the commercial red phosphor Y₂O₂S:Eu³⁺, the CaSrAl₂SiO₇:xEu³⁺ (x>0.14) phosphor exhibited excellent color purity and much higher brightness and could be considered as promising red phosphors for NUV–LEDs.     

Synthesis and luminescence properties of europium doped YBa3B9O18

Europium (Eu³⁺) doped YBa₃B₉O₁₈ were synthesized by conventional solid state solidification methods. (Y_1−xEu_x)Ba₃B₉O₁₈ formed solid solutions in the range of x=0–1.0. The luminescence property measurements upon excitation in ultraviolet–visible range show well-known Eu³⁺ excitation and emission. The charge transfer excitation band of Eu³⁺ dominates the excitation spectra. The emission spectrum of Eu³⁺ ions consists mainly of several groups of lines in the 550–720 nm region, due to the transitions from the ⁵D₀ level to the levels ⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions. The dependence of luminescence intensity on Eu³⁺ concentration shows no concentration quenching for fully concentrated EuBa₃B₉O₁₈. Eu³⁺ doped YBa₃B₉O₁₈ are promising phosphors for applications in displays and optical devices.     

Luminescent spectral characteristics of EuxLa1 - xTa7O19 polycrystals

Eu_xLa_{1 - x}Ta₇O₁₉ geptatantalates have been synthesized (x = 0.005-10). The luminescence and excitation spectra of these geptatantalates have been investigated at 77 and 300 K. It is supposed that the Eu³⁺ luminescence spectrum for all x may be interpreted within one type optical center with D_2d symmetry. The energy level diagram of the luminescence center has been worked out. It has been found that there is concentration dependence quenching of an europium luminescence. The reasons for this are discussed.     

Stabilization of Eu2+ in KLuS2 crystalline host: an EPR and optical study

Electron paramagnetic resonance and luminescence spectroscopies were applied to study the incorporation and charge stability of Eu²⁺ luminescent ions in single crystals of KLuS₂:Eu found in an earlier optical study [Jary et al., Chem. Phys. Lett. 574 , 61 (2013)]. The location of Eu²⁺ in the structure was unambiguously determined and three different centers were identified and described. Two of these centers correspond to substitution of Eu²⁺ for K⁺ and Lu³⁺ ions providing thus effective mechanism for Eu²⁺ incorporation due to the charge self‐compensation in the lattice. The observed luminescence spectra are consistent with the results of electron paramagnetic resonance experiment and can be decomposed accordingly. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)