Properties of Gd2O3:Eu, Tb nanopowders obtained by sol-gel process

A significant practical application for nanostructured materials is X-ray medical imagery, because it is necessary to use dense materials in order to enable absorption of high energy photons. An important requirement of these materials is UV-vis range emission produced by X-ray excitation, which can be influenced by the particle size. Europium doped gadolinium oxide is a well known red phosphor. Moreover, nanophosphors of Gd₂O₃ codoped with Tb³⁺, Eu³⁺ increase their light yield by energy transfer between Tb³⁺ and Eu³⁺. In this study, Gd₂O₃ nanopowders codoped with Eu³⁺ and Tb³⁺ (2.5 at.% Eu³⁺, and 0.005 and 0.01 at.% Tb³⁺) were obtained via a sol-gel process using gadolinium pentanedionate as precursor and europium and terbium nitrates as doping sources. In this paper, we report the influence of annealing temperature on the structure, morphology and luminescent properties of Gd₂O₃:Eu³⁺, Tb³⁺ by means of TGA, XRD, TEM and X-ray emission measurements.     

Preparation of Y2O3:Ce phosphors by homogeneous precipitation inside bicontinuous cubic phase

Yttrium oxide doped with cerium (Y₂O₃:Ce³⁺) blue emitting phosphors was prepared by a new method called the bicontinuous cubic phase (BCP) method. The experimental results showed that the prepared precursors were amorphous yttrium hydroxide with a spherical shape and primary size 30-50 nm. After heat treatment, high crystallinity and luminescence efficiency phosphors were obtained. The obtained Y₂O₃:Ce³⁺ phosphors had a strong blue emitting at 400 nm. The optimum Ce³⁺ concentration was 1 mol% to obtain the highest PL intensity. This study indicated that the calcining temperature of 700 °C needed for high luminescence efficiency in this work is much lower than 1000 °C or above needed for the conventional solid-state method.     

Ultraviolet emitting (Y1−xGdx)2O3−δ thin films deposited by radio frequency magnetron sputtering: Combinatorial modeling, synthesis, and rapid characterization

Gadolinium-doped, yttrium oxide thin films have been deposited on silicon (001) substrates by radio-frequency (RF) magnetron reactive sputtering that exhibit cathodoluminescence (CL) at ultraviolet frequencies. The maximum CL brightness occurred at λ314–315 nm characteristic of the ⁶P_3 / 2 → ⁸S (λ = 314 nm) transition observed in Gd-doped, yttrium oxide powders. The radiative recombination takes place at the rare earth activator Gd³⁺ site embedded in the Y₂O_3−δ host; the optical transition resides within the band gap of the Y₂O_3−δ host and the transition observed is characteristic of atomic gadolinium. A combinatorial approach to sputtering was used to deposit a film of variable composition from 1 to 23 at.% Gd in Y₂O_3−δ in order to rapidly discern the composition node of optimal CL brightness. A simulation was created for the purpose of predicting the film combinatorial composition for binary and ternary alloys prior to sputtering experiments in order to facilitate our combinatorial thin film synthesis technique. The model prediction varied from the real experimental composition profile by only 2.2 at.% Gd ± 1.6 at.% proving the predictor as a useful aide to complement combinatorial thin film experiments. A film of composition Y_1.56Gd_0.44O_3.25 (8.3 at.% Gd) yielded the maximum CL brightness. CL brightness increased continuously up to the 8.3 at.% Gd composition due to the increased number of activators present in the host. Beyond this composition the brightness drastically decreased. The oxygen composition in the combinatorial film was strongly dependent on the Gd composition; films were sub-stoichiometric δ > 0 below 6 at.% Gd and was over-stoichiometric δ < 0 beyond this composition.     

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).     

Hydrothermal synthesis and luminescent properties of Y2O3:Tb and Gd2O3:Tb microrods

One-dimensional (1D) Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods have been successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent calcination process in N₂/H₂ mixed atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectra (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-formed products via the hydrothermal process could transform to cubic Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ with the same morphology and slight shrinking in size after a postannealing process. Both Y₂O₃:Tb³⁺ and Gd₂O₃:Tb³⁺ microrods exhibit strong green emission corresponding to ⁵D₄ → ⁷F₅ transition (542 nm) of Tb³⁺ under UV light excitation (307 and 258 nm, respectively), and low-voltage electron beam excitation (1.5 → 3.5 kV), which have potential applications in fluorescent lamps and field emission displays.     

Color emission and dielectric properties of Eu-doped Gd2O3 gate oxide thin films

High-k Gd₂O₃ used for thin film transistor (TFT) gate insulators has been synthesized via a simple solution process. Phase analysis and capacitive performance reveal that a high dielectric constant of ~ 20 and a low leakage current level of < 10⁻⁸ A/cm² at 1 MV/cm with a good transparency under the visible wavelength region are readily produced by the sol-gel method. Eu³⁺ doping leads to an increased dielectric constant induced by the additional electric dipole transition, which is evidently visualized by the photoluminescence behavior and/or by the defect-controlled thin film microstructures. Thus, the solution-processed (Gd,Eu)₂O₃ film is a viable gate insulator to be considered for the proposed “color emissive” switching devices as well as for the low power-driven TFT devices.     

The photoluminescence properties of Y2O3:Eu prepared by surfactant assisted co-precipitation-molten salt synthesis

Y₂O₃:Eu³⁺ red phosphors were prepared by surfactant assisted co-precipitation-molten salt synthesis method. The effects of surfactant content and annealing temperature on the structure and luminescence were investigated by X-ray diffraction and fluorescence spectrophotometer. The use of surfactant reduces the impurities on the surface of particles and promotes the reaction. The color purity of as-prepared Y₂O₃:Eu³⁺ red phosphors is improved with the presence of surfactant. In the excitation spectra, two strong bands at 394 and 466 nm are attributed to ⁷F_0,1-⁵L₆, ⁷F_0,1-⁵D₂ transitions of Eu³⁺ ions respectively. With the excitation of 394 or 466 nm, the as-fabricated samples reveal excellent red emission as high as that of samples monitored by 254 nm. Thus, the Y₂O₃:Eu³⁺ is a promising red phosphor for ultraviolet-visible light-emitting diodes.     

The erosion behaviors of Y2O3 and YF3 coatings under fluorocarbon plasma

We deposited Y₂O₃ and YF₃ coatings using the electron beam evaporation method and investigated their erosion behavior under fluorocarbon plasma at various bias voltages. TEM analysis revealed that the Y₂O₃ coating was strongly fluorinated under the plasma, and the thickness of the fluorinated layer was increased up to a few hundred nm with bias voltage. XPS analysis also confirmed a significant Y-F bonding on the surface and showed fluorine content at a maximum on the surface, decreasing with the depth from the surface. The etch rate increased with bias voltage and it was slightly higher in YF₃ coating, implying that the etch rate depends on the surface fluorination and its removal by incident ions. Without applying bias voltage, the chemical reaction with the fluorocarbon plasma dominated, resulting in the formation of fine fluoride particles on the Y₂O₃ surface, but the YF₃ coating was intact and clean for the same condition. These results indicate that the YF₃ coating may be a new plasma-facing material that produces fewer contamination particles.     

Photoluminescence of TiO2 films co-doped with Tb/ Gdand energy transfer from TiO2/Gd to Tb ions

Nanometer TiO₂ thin films doped with different concentration of Tb were prepared by sol-gel method and characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. XRD results show preferentially oriented (101) anatase films. TEM image indicates that the TiO₂ films consist of TiO₂ grains with diameter about 15 nm. Under room temperature, strong visible luminescence of Tb³⁺ ions due to intra-4f shell transitions are obtained and the PL intensity is found to have a well matching relation with the doping concentration of Tb³⁺ ions. Concentration quenching of PL occurs when Tb³⁺ concentration exceeds a certain value (9.2 mol%). Furthermore, the luminescence intensity is improved obviously after co-doping with Gd³⁺ ions because of the sensitization effects of Gd³⁺ ions to Tb³⁺ ions in TiO₂ system. The energy transfer mechanism from TiO₂ and Gd³⁺ ions to Tb³⁺ ions was proposed.     

Luminescent properties of Gd2Ti2O7: Eu phosphor films prepared by sol-gel process

Gd₂Ti₂O₇: Eu³⁺ thin film phosphors were fabricated by a sol-gel process. X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800 °C and the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free phosphor films were obtained, which mainly consisted of grains with an average size of 70 nm. The doped Eu³⁺ showed orange-red emission in crystalline Gd₂Ti₂O₇ phosphor films due to an energy transfer from Gd₂Ti₂O₇ host to them. Both the lifetimes and PL intensity of the Eu³⁺ increased with increasing the annealing temperature from 800 to 1000 °C, and the optimum concentrations for Eu³⁺ were determined to be 9 at.%. of Gd³⁺ in Gd₂Ti₂O₇ film host.     

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.     

Upconversion in Er-doped Gd2O3 nanocrystals prepared by propellant synthesis and flame spray pyrolysis

In this study, monoclinic luminescent Gd₂O₃ nanocrystals doped with different concentrations of Er³⁺ (0.1, 1, and 10 mol%) were produced by propellant synthesis and flame spray pyrolysis (FSP). A comparison of their optical and morphological properties is reported. Following 980 nm excitation, an increase of the emission intensity from the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions was observed with increasing Er³⁺ concentration in the Gd₂O₃ nanocrystalline samples prepared via both techniques. However, the overall upconversion emission intensity was greater for the samples obtained by FSP. Furthermore, as the Er³⁺ concentration was increased, the intensity of the red (⁴F_9/2 → ⁴I_15/2) emission was observed to increase more rapidly in comparison to the green (²H_11/2, ⁴S_3/2 → ⁴I_15/2) emission resulting in an overall enhancement of the red component in the upconversion emission. Although both synthetic routes yield average crystallite sizes in the nanoscale, the TEM and SEM images confirm a more homogeneous morphology and lower particle aggregation for the nanocrystals produced by FSP.     

Luminescence enhancement of Y2O3:Eu and Y2SiO5:Ce,Tb core particles with SiO2 shells

This paper reports on the luminescence and microstructural features of oxide nano-crystalline (Y₂O₃:Eu³⁺) and submicron-sized (Y₂SiO₅:Ce³⁺,Tb³⁺) phosphor cores, produced by two different synthesis techniques, and subsequently coated by an inert shell of SiO₂ using a sol-gel process. The shells mitigate the detrimental effect of the phosphor particle surfaces on the photoluminescence emission properties, thereby increasing luminous output by 20-90%, depending on the core composition and shell thickness. For Y₂O₃:Eu³⁺, uniformly shaped, narrow particle size distribution core/shell particles were successfully fabricated. The photoluminescence emission intensity of core nanoparticles increased with increasing Eu³⁺ activator concentration and the luminescence emission intensity of the core/shell particles was 20-50% higher than that of the core particles alone. For Y₂SiO₅:Ce³⁺,Tb³⁺, the core/shell particles showed enhancement of the luminescence emission intensity of 35-90% that of the core particles, depending on the SiO₂ shell thickness.     

Novel blue-emitting Sr3Ga2O5Cl2:Eu phosphor for UV-pumped white LEDs

A novel blue-emitting Sr₃Ga₂O₅Cl₂:Eu²⁺ phosphor has been synthesized by a two-step solid-state reaction. The luminescence properties have been investigated by photoluminescence (PL) spectra, and temperature-dependent PL spectra. It shows an efficient broad absorption band around 400 nm, which matches well with the commercial near-ultraviolet light-emitting chips, and an efficient blue emission. It shows a higher thermal quenching temperature than that of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor. Sr₃Ga₂O₅Cl₂:Eu²⁺ phosphor is a promising blue-emitting component for UV chip excited white light-emitting-diodes.     

High mobility, transparent, conducting Gd-doped In2O3 thin films by pulsed laser deposition

Highly transparent and conducting thin films of gadolinium doped indium oxide, which have high electron mobility, were deposited on quartz substrate to study the effect of growth temperature and oxygen pressure on their structural, optical, and electrical properties. X-ray diffraction study reveals that these films are randomly oriented on the quartz surface. The average particle size of the films grown at 600 °C was calculated to be ∼ 23 nm. The optical transparency of the films increases with an increase in the growth temperature. The film transparency is also found to increase with increased oxygen pressure during deposition. The electrical properties of these films strongly depend on both the growth temperature and the oxygen pressure. Analysis of the electrical data shows that the mobility of the films increases with increase in the growth temperature.     

Preparation and characterization of sol-gel derived Er-Yb codoped SiO2/TiO2 core-shell nanoparticles

The Er³⁺-Yb³⁺ codoped silica/titania core-shell nanoparticles were prepared by hydrolysis of titanium alkoxide precursors in the presence of lanthanide ions via sol-gel method. The structure of the particles was characterized by field emission scanning electron microscopy and transmission electron microscopy. The diameter of the silica core is about 50 nm. The thickness of the titania shell is about 4 nm. A typical doping density of Er³⁺ in the titania shell is 4.51 at.%, and the one of Yb³⁺ is 12.20 at.%. The UV-vis-NIR absorption spectra and the photoluminescence spectra were also investigated.     

Influence of additional Eu coactivator on the luminescence properties of Tb3Al5O12:Ce, Eu

The luminescence properties of doubly activated terbium aluminium garnet samples were investigated in the present study. Commercial Tb₃Al₅O₁₂:Ce³⁺ (TAG:Ce) shows the typical Ce³⁺ ion luminescence of the allowed Ce³⁺ d–f transition. Eu³⁺ co-doping, however, reveals interesting results. In TAG:Ce, Eu, both Ce³⁺ and Eu³⁺ luminescence was measured at different Ce and Eu activator concentrations. The Ce³⁺ ion can be used as a sensitizer in the TAG lattice that transfers its energy directly or via the Tb sublattice to the activator Eu³⁺. The energy-level diagram was proposed to explain the luminescence mechanism. Application of TAG:Ce, Eu with improved chromaticity coordinates CIE (Commission Internationale de l’Eclairage) and color rendering index (CRI) in light emitting diodes (LEDs) is demonstrated.     

Investigation of Na3GdP2O8:Tb as a potential green-emitting phosphor for plasma display panels

The photoluminescent properties of a series of Tb³⁺-doped Na₃GdP₂O₈ phosphors excitable by vacuum ultraviolet and ultraviolet light are reported. The host related absorption, f-f and f-d transitions of Gd³⁺ and Tb³⁺, and charge transfer of O²⁻ → Gd³⁺ and O²⁻ → Tb³⁺ are assigned. Under 147 nm light excitation, Na₃GdP₂O₈:Tb³⁺ phosphors show efficient green emissions with a dominant peak at 545 nm. The optimal sample Na₃Gd_0.4Tb_0.6P₂O₈ shows a shorter decay time and a comparable brightness when compared with the commercial Zn₂SiO₄:Mn²⁺ green phosphor. These results demonstrate that it is a potential candidate for plasma display panels application.     

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.     

Y2O3与Gd2O3共掺杂SrZrO3热障涂层材料的热物理性能

采用固相反应法合成了5mol%Y2O3与5mol%Gd2O3共掺杂SrZrO3(Sr(Zr0.9Y0.05Gd0.05)O2.95,SZYG)粉末.采用X射线衍射(XRD)和差示扫描量热仪(DSC)分别研究了SZYG粉末在1450℃长期热处理后以及200~1400℃范围内的相稳定性.采用高温热膨胀仪测量了SZYG块材的热膨胀系数,结果表明:通过Y2O3与Gd2O3共掺杂改性可以明显抑制SrZrO3的相转变.在1000℃下SZYG块材的热导率是～1.36 W/(m.K),与SrZrO3和8YSZ块材相比降低~35%SZYG分别与8YSZ和Al2O3在1250℃热处理24 h表现出很好的化学相容性.