Luminescence properties of Eu ions doped in Y2−xGdxO3 thin films grown by pulsed laser deposition method

Luminescence properties of Y_2−xGd_xO₃:Eu³⁺ (x = 0 to 2.0) thin films are investigated by site-selective laser excitation spectroscopy. The films were grown by pulsed laser deposition method on SiO₂ (100) substrates. Cubic phase Y₂O₃ and Gd₂O₃ and monoclinic phase Gd₂O₃ are identified in the excitation spectrum of the ⁷F₀ → ⁵D₀ transition of Eu³⁺. The emission spectra of the ⁵D₀ → ⁷F_J (J = 1 and 2) transition from individual Eu³⁺ centers were obtained by tuning the laser to resonance with each excitation line. The excitation line at around 580.60 nm corresponds to the line from Eu³⁺ with C₂ site symmetry of cubic phase. New lines at 578.65 and 582.02 nm for the C_S sites of Gd₂O₃ with monoclinic phase are observed by the incorporation of Gd in Y₂O₃ lattice. Energy transfer occurs between Eu³⁺ ions at the C_S sites and from Eu³⁺ ions at the C_S sites to those at the C₂ site in Y_2−xGd_xO₃.     

Structural and electrical properties of La2−xBaxMo2O9−x/2 (x = 0-0.18)

La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) have been prepared by solid state reaction method. The lattice parameter of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) determined by XRD data refinement shows a linear dependence on the dopant Ba content x. For the specimen with a La/Ba molar ratio of 0.18-0.2, additional reflection of secondary phase exists in the XRD pattern, so the value of solubility limit for Ba in La₂Mo₂O₉ is defined in range of 0.18 < x < 0.2. As the replacement degree of La³⁺ by Ba²⁺ increases, the bulk conductivity of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) decreases initially and then increases, a minimum value at La_1.9Ba_0.1Mo₂O_8.95 exists. Hebb-Wagner studies in argon atmosphere, which use an oxide-ion blocking electrode, show that La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) are predominantly oxide-ion conducting in the temperature ranging from 773 to 1173 K. The average thermal expansion coefficient of La_1.84Ba_0.16Mo₂O_8.92 determined by high-temperature XRD was deduced as great as 17.5 × 10⁻⁶ K⁻¹ between 298 and 1173 K.     

Structural and optical properties of Er-doped Y2Ti2O7 thin films by sol-gel method

Er³⁺-doped Y₂Ti₂O₇ and Er₂Ti₂O₇ thin films were fabricated by sol-gel spin-coating method. A well-defined pyrochlore phase Er_xY_2-xTi₂O₇ was observed while the annealing temperature exceeded 800 °C. The average transmittance of the Er_xY_2-xTi₂O₇ thin films annealed at 400 to 900 °C reduces from ∼ 87 to ∼ 77%. The refractive indices and optical band gaps of Er_xY_2-xTi₂O₇ (x = 0-2) annealed at 800 °C/1 h vary from 2.20 to 2.09 and 4.11 to 4.07 eV, respectively. The ∼ 1.53 μm photoluminescence spectrum of Er³⁺ (5 mol%)-doped Y₂Ti₂O₇ thin films annealed at 700 °C/1 h exhibits the maximum intensity and full-width at half maximum (∼ 60 nm).     

Synthesis and optical properties of (Gd1−x,Eux)2O2SO4 nano-phosphors by a novel co-precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphors were synthesized by a novel co-precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and NaOH starting materials. Composition of the precursor is greatly influenced by the molar ratio of NaOH to (Gd_1−x,Eu_x)₂(SO₄)₃ (the m value), and the optimal m value was found to be 4. Fourier transform infrared spectrum (FT-IR) and thermal analysis show that the precursor (m = 4) can be transformed into pure (Gd_1−x,Eu_x)₂O₂SO₄ nano-phosphor by calcining at 900 °C for 2 h in air. Transmission electron microscope (TEM) observation shows that the Gd₂O₂SO₄ phosphor particles (m = 4) are quasi-spherical in shape and well dispersed, with a mean particle size of about 30-50 nm. Photoluminescence (PL) spectroscopy reveals that the strongest emission peak is located at 617 nm under 271 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 10 mol% and the concentration quenching mechanism is exchange interaction among the Eu³⁺ ions. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions has a single exponential decay behavior.     

Upconversion and infrared luminescences in Er/Yb codoped Y2O3 and (Y0.9La0.1)2O3 transparent ceramics

Er³⁺ and Yb³⁺ codoped Y₂O₃ and (Y_0.9La_0.1)₂O₃ transparent ceramics were fabricated by the conventional ceramics processing with nanopowders. Compared to Er/Yb:Y₂O₃, Er/Yb:(Y_0.9La_0.1)₂O₃ ceramics had higher transmittance. Intense upconversion (UC) and infrared emission (1543 nm) were observed under excitation of 980 nm. According to three intensity parameters Ω₂, Ω₄, and Ω₆ fitted by the Judd-Ofelt theory, the spectroscopic quality parameters (X), radiative lifetimes (τ_rad), and emission cross-sections (α_em) were determined. Er/Yb:(Y_0.9La_0.1)₂O₃ ceramics owned broader peaks and longer lifetime (12.3 ms) at 1548 nm due to the glass-like structure of (Y_0.9La_0.1)₂O₃ ceramics. The results showed Y₂O₃ and Y_1.8La_0.2O₃ transparent ceramics are promising gain media for developing the solid-state 1.5 μm optical amplifiers and tunable UC lasers.     

Preparation, characterization and luminescence of La2TeO6 phosphor doped with Eu

Phosphors of La₂TeO₆ doped with Eu³⁺ ions have been synthesized by the oxidation of the corresponding rare-earths oxytellurides of formula La_2−xEu_xO₂Te (x = 0.02, 0.06, and 0.1) at 1050 K. Powder X-ray diffraction confirms that the as prepared materials consist of the orthorhombic La₂TeO₆ as main phase. The photoluminescence (PL) of red-emitting La_2−xEu_xTeO₆ powder phosphors is reported. The emission spectrum, exhibits an intense emission peak due to ⁵D₀ → ⁷F₂ transition at 616 nm, which indicates that the Eu³⁺ ion occupies a non-centrosymmetric site in the host lattice. These materials could find application for use as lamp phosphors in the red region.     

Synthesis and luminescence properties of color-tunable Ba1−ySryLa4−xTbx(WO4)7 (x = 0.02-1.2, y = 0-0.4) phosphors

Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ (x = 0.02-1.2, y = 0-0.4) phosphors were prepared via a solid-state reaction and their photoluminescence properties were investigated. An analysis of the decay behavior indicates that the energy migration between Tb³⁺ ions is conspicuous in the ⁵D₃ → ⁷F₄ transition due to the cross-relaxation in BaLa₄(WO₄)₇. A partial substitution of Ba²⁺ by Sr²⁺ can not only enhance the emission intensity but also increase the solid solubility of Tb³⁺ in Ba_1−ySr_yLa_4−xTb_x(WO₄)₇. The emission intensity of the ⁵D₄ → ⁷F_J (J = 4, 5, 6) transitions can be enhanced by increasing Sr²⁺ and Tb³⁺ concentrations, with the optimal conditions being x = 1.2, y = 0.4 (Ba_0.6Sr_0.4La_2.8Tb_1.2(WO₄)₇). Under near-UV excitation at 379 nm, the CIE color coordinates of Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ vary from blue (0.212, 0.181) at x = 0.04, y = 0, to green (0.245, 0.607) at x = 1.2, y = 0.4.     

Synthesis,characterization and photoluminescence properties of (Gd1−x,Eux)2O2SO4 sub-microphosphors by homogeneous precipitation method

(Gd_1−x,Eu_x)₂O₂SO₄ sub-microphosphors were synthesized by homogeneous precipitation method from commercially available Gd₂O₃, Eu₂O₃, H₂SO₄ and (NH₂)₂CO (urea) starting materials. Fourier transform infrared spectra show that the precursors with different molar ratios of (NH₂)₂CO to Gd₂(SO₄)₃ (the m value) are mostly composed of gadolinium hydroxyl, carbonate and sulfate groups with some crystal water. X-ray diffraction indicated that the precursor (m = 5) can be transformed into pure Gd₂O₂SO₄ phase after heat treated at 900 °C for 2 h in air. Field emission scanning electron microscope micrographs illustrate that the Gd₂O₂SO₄ phosphor particles (m = 5) are quasi-spherical in shape and well dispersed, with a mean particle size of about 300–500 nm. Photoluminescence spectroscopy reveals that the strongest emission peak for (Gd_1−x,Eu_x)₂O₂SO₄ sub-microphosphors is located at 618 nm under 270 nm light excitation, which corresponds to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The quenching concentration of Eu³⁺ ions is 5 mol% and the concentration quenching mechanism is due to the electric dipole–dipole interaction. Decay study reveals that the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions fits with a mono exponential function.     

Effects of La substitution for Nd in (Nd2−xLax)BaZnO5 solid solutions on microwave dielectric properties and crystal structure

The synthesis and microwave dielectric characterization of (Nd_2−xLa_x)BaZnO₅ solid solutions were studied. The samples obtained were single phase over the whole composition range and the lattice parameters of solid solutions were linearly increased with increasing the composition. Moreover, the expansion of the volume in the RO₈ (R=Nd and La) and BaO₁₀ polyhedra and ZnO₄ tetrahedron were recognized when Nd ions were substituted by La. These variations in the lattice parameters and volumes of the polyhedra are basically attributed to the differences in ionic radii between Nd³⁺ and La³⁺ ions. From the evaluation of microwave dielectric properties, it was shown that the appropriate τ_f values ranging from 4.6 to −5.0 ppm/°C are obtained by La substitution for Nd ion, and the highest Q · f value was 17,832 GHz at x=2.     

Conductivity of reduced La2Mo2O9 based oxides: The effect of tungsten substitution

The electrical properties of reduced LAMOX-type oxides (La_1.9Y_0.1Mo_2−yW_yO_9−δ with y = 0, y = 0.5, y = 1.0) were investigated by complex impedance spectroscopy.When reduced at 605 °C in hydrogen, La_1.9Y_0.1Mo₂O_9−δ is 10 times and 3 × 10⁵ times more conductive at 605 and 180 °C, respectively, than in air at the same temperatures. The conductivity curve presents a low slope (0.37 eV versus 1.2 eV in air).Besides, the stabilising effect of tungsten against reduction is evidenced, in good agreement with previous reports.In low oxygen partial pressures however (PO₂ < 10⁻¹⁸ Pa), the decomposition of the materials is detected, whatever the tungsten content (0 ≤ y ≤ 1 in La_1.9Y_0.1Mo_2−yW_yO_9−δ). This observation points out the efficiency limit of Mo⁶⁺/W⁶⁺ substitution to stabilise the structure against reduction, and the limit for an application as IT-SOFC electrolyte.However, given the high electronic conductivity upon reduction, the application of these materials in IT-SOFC electrodes could be considered.     

Low loss Sr1−xCaxLa4Ti5O17 microwave dielectric ceramics

Microwave dielectric ceramics in the Sr_1−xCa_xLa₄Ti₅O₁₇ (0 ≤ x ≤ 1) composition series were prepared through a solid state mixed oxide route. All the compositions formed single phase ceramics within the detection limit of in-house X-ray diffraction when sintered in the temperature range 1450-1580 °C. Theoretical density and molar volume decreased due to the substitution of Ca²⁺ for Sr²⁺ which was associated with a decrease in the dielectric constant (?_r) and temperature coefficient of resonant frequency (τ_f) but an increase in quality factor, Qf_o. Optimum properties were achieved for Sr_0.4Ca_0.6La₄Ti₅O₁₇ which exhibited, ?_r ∼ 53.7, Qf_o ∼ 11,532 GHz and τ_f ∼ −1.4 ppm/°C.     

Electrical and spectroscopic properties of Ti0.2 Sn0.8O2 solid solution for gas sensing

In this work we report the synthesis, microstructure, electric and spectroscopic properties, and sensing performances of Ti_xSn_1 − xO₂ (x = 0.1, 0.2, 0.3, 0.5, 0.7, 0.9) nano-powders and of SnO₂ and TiO₂ reference samples, prepared via sol-gel route starting from metal-organic precursors working in hydro-alcoholic media. Actually, the attention is particularly focused on properties of the sample with x = 0.2, in comparison with ones of the other solid solutions and of the single oxides. Indeed, this solid solution showed a borderline behaviour between that of the solid solution with x = 0.1 and that of the other solid solutions with x ≥ 0.3. An abrupt change in the structural, electrical and spectroscopic properties has been observed, passing from sample with x = 0.1, showing a behaviour very similar to that of SnO₂, to one x = 0.3 showing a behaviour very similar to that of TiO₂. The borderline properties of the mixed oxide with x = 0.2 represent the expected continuous transition among the two behaviours.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

All-solid-state cells based on solid electrolyte systems Cu1−xAgxI-Ag2O-Y, where x = 0.05-0.25; Y = MoO3, B2O3, SeO2, V2O5 and CrO3

All-solid-state cells of the configuration (−)Ag + SE//SE//I₂-phenothiazine + C(+) using the best conducting compositions of the solid electrolyte systems, namely, Cu_1−xAg_xI-Ag₂O-Y where x = 0.05, 0.1, 0.15, 0.2 and 0.25, Y = MoO₃, B₂O₃, SeO₂, V₂O₅ and CrO₃, as the electrolytes were fabricated. Discharge, polarization and power characteristics of these cells were also evaluated. The open circuit voltage values of these cells were in the range 620-635 mV. The stability of these cells has been indicated by the constancy of their OCV over a period of 6 months. The polarization and discharge studies on these cells have shown that typical cells based on the electrolytes with Y = B₂O₃, SeO₂ and V₂O₅ would possess discharge capacities of 12.84, 3.76 and 5.05 mA h and specific energy of 6.55, 1.81 and 2.77 W h kg⁻¹, respectively. The solid electrolytes have good electrochemical stability and compatibility with the Ag/Phenothiazine-I₂ electrode couple thus offering their suitability of application in microwatt power sources.     

Preparation of La1−xSrxMnO3 nanoparticles by sonication-assisted coprecipitation

La_1−xSr_xMnO₃ (x=0.3) (LSM) nanoparticles were prepared by a sonication-assisted coprecipitation method. The coprecipitation reaction is carried out with ultrasound radiation. Lower sintering temperatures are required for the sonication-assisted product. Fully crystallized LSM with an average particle size 24 nm is obtained after the as-prepared mixture is annealed at 900 °C for 2 h. Magnetic properties indicate that the transition temperature from the paramagnetic to ferromagnetic state of the sample is quite sharp and occurs at 366 K for samples annealed for 2 h at 900 and 1100 °C.     

Structural and dielectric properties of ferroelectric Sr1−xBaxBi2(Nb0.5Ta0.5)2O9 and Sr0.5Ba0.5Bi2(Nb1−yTay)2O9 ceramics

Ferroelectric Sr_1−xBa_xBi₂(Nb_0.5Ta_0.5)₂O₉ and Sr_0.5Ba_0.5Bi₂(Nb_1−yTa_y)₂O₉ were synthesized by solid state reaction route. X-ray diffraction studies confirm the formation of single phase layered perovskite solid solutions over a wide range of compositions (x=y=0.0, 0.25, 0.50, 0.75 and 1). The lattice parameters and the Curie temperature (T_c) have been found to have linear dependence on x and y. Transmission electron microscopy (TEM) suggest the lowering of orthorhombic distortion with increasing Ba²⁺ substitution. Variations in microstructural features as a function of x and y were monitored by scanning electron microscopy (SEM). The dielectric constant at room temperature increases with increase in both x and y. Interestingly Ba²⁺ substitution on Sr²⁺ site induces diffused phase transition and diffuseness increases with increasing Ba²⁺ concentration.     

Synthesis and electrochemical behavior of nanosized LiNi1−xCaxO2 cathode materials for high voltage secondary lithium-ion cells

A new class of LiNi_1−xCa_xO₂ (x = 0.0, 0.1, 0.2, 0.3 and 0.5) layered oxide materials has been synthesized by a simple low temperature solid-state route with mixed nitrates/urea with glycerol as the starting materials. First we have taken TG/DTA for observing the phase transformations of LiNi_0.9Ca_0.1O₂. The structure of the synthesized oxides was analyzed using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) to identify the crystal structure and cation environment, respectively. The synthesized ceramic oxide battery materials were examined by using transmission electron microscope (TEM), scanning electron microscope (SEM) analysis to determine the particle size, nature and morphological structure. SEM with energy dispersive X-ray spectroscopic analysis (EDAX) analysis was carried out to explore the composition of the prepared materials. The electrochemical performance of LiNi_1−xCa_xO₂ electrodes was analyzed using cyclic voltammetry (CV) and galvanostatic charge-discharge cycling studies in the voltage range 3.0-4.5 V. Electrode made with cathode active material, acetylene black and poly(vinylidene difluoride) yield a discharge capacity of 178.1 mAh g⁻¹ (x = 0.2) with good specific capacity over several charge-discharge cycles. These results have been also supported by cyclic voltammograms.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Low temperature step magnetization and magnetodielectric study in Bi0.95La0.05Fe1−xZrxO3 ceramics

Single-phase, co-doped (La³⁺, Zr⁴⁺) in polycrystalline Bi_0.95La_0.05Fe_1−xZr_xO₃ (with x = 0, 0.02, 0.04 and 0.06) ceramics (particle size ∼650 nm; tolerance factor ∼0.883) were prepared by solid state reaction of oxides, followed by rapid quenching of samples. Enhanced magnetization was observed in co-doped (La³⁺, Zr⁴⁺) BiFeO₃ which may be ascribed to the collapse of the spiral spin structure. Step magnetization was observed in zero field cooled (ZFC) and field cooled (FC) curves. The coexistence of ferromagnetism and ferroelectricity has been confirmed in the co-doped (La³⁺, Zr⁴⁺) in BiFeO₃ ceramics by means of (M–H) and (P–E) loops measurements. Magnetodielectric properties have been observed at room temperature.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.