Effect of heat treatment on photoluminescence behavior of BaMgAl10O17:Eu phosphors

The blue phosphor of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) powders were prepared by solid-state reaction. The thermal degradation of BAM phosphor significantly reduces the intensity of the blue emission. BAM is reduced by an amount of 50% after heating at around 800 °C for 1 h. Photoluminescence (PL) excitation and emission spectra showed that the blue emission of 450 nm peak decreased with increasing annealing temperature. The ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ were observed at 590 and 615 nm emission lines over 1100 °C. Electron paramagnetic resonance (EPR) spectrum also detected two signals of Eu²⁺, corresponding to g=3.7156(9) for 88 mT, and g=2.9507(9) for 133 mT. X-ray absorption near edge structure (XANES) spectrum decreased the intensity of Eu²⁺ for 6977 eV with increasing annealing temperature, while high-energy peak of Eu³⁺ for 6984 eV was increased. The combined use of X-ray and neutron data by the Rietveld refinement appears to support that the secondary phase of EuMgAl₁₁O₁₉ magnetoplumbite structure in BAM may be formed by heat treatment.     

Long lasting phosphorescence of Sr4Al14O25:Eu,Dy thin films by magnetron sputtering

This paper reports the preparation process and the long lasting phosphorescence of the Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ thin films obtained by magnetron sputtering. Phosphorescence was achieved by annealing the films in reducing atmosphere. Sr₄Al₁₄O₂₅ thin film was obtained when the films were treated at 1200 °C, while SrAl₂O₄ was generated as the intermediate phase during the annealing process. Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ film generated an emission at 485 nm, and SrAl₂O₄:Eu²⁺,Dy³⁺ film showed an emission peaking at 515 nm. Afterglow characteristics were observed for both films, and Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺ film showed a better afterglow property than the SrAl₂O₄:Eu²⁺,Dy³⁺ film due to a deeper trap level and a higher trap concentration formed in the thin films.     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Highly enhanced luminescence of SrB4O7:Eu phosphor prepared by the combustion method using glycine as fuel

Eu²⁺ ion doped into SrB₄O₇ matrix was prepared by combustion method heated at 900 °C in air, using urea (U) or glycine (G) as fuels in different ratios (U100, A10, A25, G10, G25, G75, and G100). In some compositions, ammonium acetate (AA) was used to reduce the exothermicity of combustion reaction. X-ray diffraction and luminescence spectroscopy were used to characterize the material. The high intense emission band at 367 nm is assigned to 4f⁶5d → 4f⁷(⁸S_7/2) transition arisen from divalent europium ion. It is observed that the interconfigurational transition is dependent on the molar ratio of glycine:urea fuels. Glycine fuel favors Eu²⁺ formation in SrB₄O₇ host lattice prepared by combustion method.     

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4:Eu

It has been found that charge compensated CaMoO₄:Eu³⁺ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO₄:Eu³⁺ without charge compensation. Two approaches to charge compensation, (a) 2Ca²⁺ → Eu³⁺ + M⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ and K⁺ acting as a charge compensator; (b) 3Ca²⁺ → 2Eu³⁺ + vacancy, are investigated. The influence of sintering temperature and Eu³⁺ concentration on the luminescent property of phosphor samples is also discussed.     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Preparation, patterning and luminescent properties of nanocrystalline Gd2O3:A (A=Eu, Dy, Sm, Er) phosphor films via Pechini sol–gel soft lithography

Nanocrystalline Gd₂O₃:A (A=Eu³⁺, Dy³⁺, Sm³⁺, Er³⁺) phosphor films and their patterning were fabricated by a Pechini sol–gel process combined with a soft lithography. X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and optical microscopy, UV/vis transmission 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 500 °C and that the crystallinity increased with the elevation of annealing temperatures. Uniform and crack free non-patterned phosphor films were obtained by optimizing the composition of the coating sol, which mainly consisted of grains with an average size of 70 nm and a thickness of 550 nm. Using micro-molding in capillaries technique, we obtained homogeneous and defects-free patterned gel and crystalline phosphor films with different stripe widths (5, 10, 20 and 50 μm). Significant shrinkage (50%) was observed in the patterned films during the heat treatment process. The doped rare earth ions (A) showed their characteristic emission in crystalline Gd₂O₃ phosphor films due to an efficient energy transfer from Gd₂O₃ host to them. Both the lifetimes and PL intensity of the rare earth ions increased with increasing the annealing temperature from 500 to 900 °C, and the optimum concentrations for Eu³⁺, Dy³⁺, Sm³⁺, Er³⁺ were determined to be 5, 0.25, 1 and 1.5 mol% of Gd³⁺ in Gd₂O₃ films, respectively.     

In:Ga2O3氧化物半导体晶体的生长与性能研究

β-Ga₂O₃晶体是一种新型宽禁带氧化物半导体材料, 本征导电性差。为了在调控导电性能的同时兼顾高的透过率和结晶性能, 离子掺杂是一种有效的途径。采用光学浮区法生长出ϕ8 mm×50 mm蓝色透明In:Ga₂O₃晶体, 晶体具有较高的结晶完整性。In³⁺离子掺杂后, β-Ga₂O₃晶体在红外波段出现明显的自由载流子吸收, 热导率稍有减小。室温下, In:Ga₂O₃晶体的电导率和载流子浓度分别为4.94×10^-4 S/cm和1.005×10¹⁶ cm^-3, 其值高于β-Ga₂O₃晶体约1个数量级。In:Ga₂O₃晶体电学性能对热处理敏感, 1200℃空气气氛和氩气气氛退火后电导率降低。结果表明, In³⁺离子掺杂能够调控β-Ga₂O₃晶体的导电性能。     

Valency states of Yb, Eu, Dy and Ti ions in Li2B4O7 glasses

Absorption and emission spectra of Eu and Dy, Yb and Ti ions in Li₂B₄O₇ glasses grown in oxygen and hydrogen gas atmospheres were measured for valency states and lattice-sites analysis. For the Li₂B₄O₇ glass doped with Eu²⁺, Eu³⁺ and Dy³⁺ ions which were grown in oxidizing and reducing atmospheres, absorption and emission bands due to these ions were investigated before and after γ-irradiation. For the Yb³⁺-doped Li₂B₄O₇ glass, a weak, broad band was observed near the sharp 976.3 nm absorption band. The origin of this band is discussed in comparison with other glasses. Moreover, irradiation experiments using γ-rays were also performed in order to investigate the possibility of valency change of Yb ions. It was found that Ti⁴⁺ ions, which are produced under oxidizing atmosphere, change to Ti³⁺ ions after γ-irradiation with a dose of 10⁵ Gy. An additional absorption band observed at about 500 nm is due to the Ti³⁺ ions accompanied by charge-compensating vacancy and does not give any emission.     

Nanosized strontium aluminate phosphors prepared via a reverse microemulsion route

Nanosized strontium aluminate phosphors co-activated by Eu²⁺ and Dy³⁺ were prepared via a novel reverse microemulsion process. This new synthesis technique lowered the synthesis temperature of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphors to as low as 900 °C, and also reduced the particle size to the nanometer scale (around 40 nm). In the microemulsion process, the constituent cations were trapped by numerous nano-scaled micelles, leading to a shortening of the inter-diffusion length and enhancement of the precursor reactivity. The excitation intensity and emission peaks of nanosized SrAl₂O₄: Eu²⁺, Dy³⁺ phosphors significantly increased with increasing heating temperatures.     

Photoluminescence properties of the Yb:Er co-doped Al2O3 thin film fabricated by microwave ECR plasma source enhanced RF magnetron sputtering

The Yb:Er co-doped Al₂O₃ thin film was deposited on oxidized silicon wafers by microwave ECR plasma source enhanced RF magnetron sputtering, and annealed from 800 °C to 1000 °C. The photoluminescence at 1.53 μm of thin film was obtained under room temperature. The mixture phase structure of γ and θ is observed by XRD, and the compositions of the thin film are investigated by EPMA. The maximum PL intensity was achieved with O₂:Ar at 1:1, annealing temperature at 900 °C, and experimental ratio of Yb:Er at 1:3.6. The energy transfer mechanism between Er and Yb ions is supported by theoretical analysis and experiment results.     

Influence of Mn doping on microstructure and DC-accelerated aging behaviors of ZnO–V2O5-based varistors

The microstructure, electrical properties, dielectric characteristics, and DC-accelerated aging behavior of the ZnO–V₂O₅–MnO₂ system sintered were investigated for MnO₂ content of 0.0–2.0 mol% by sintering at 900 °C. For all samples, the microstructure of the ZnO–V₂O₅–MnO₂ system consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the ZnO–V₂O₅ system was found to restrict the abnormal grain growth of ZnO. The nonlinear properties and stability against DC-accelerated aging stress improved with the increase of MnO₂ content. The ZnO–V₂O₅–MnO₂ system added with MnO₂ content of 2.0 mol% exhibited not only a high nonlinearity, in which the nonlinear coefficient is 27.2 and the leakage current density is 0.17 mA/cm², but also a good stability, in which %ΔE_1 mA = −0.6%, %Δ = −26.1%, and %Δtan δ = +22% for DC-accelerated aging stress of 0.85E_1 mA/85 °C/24 h.     

Low-temperature synthesis of nanocrystalline ZnGa2O4:Tb phosphors via the Pechini method

The synthesis of trivalent terbium doped ZnGa₂O₄ nanosized new phosphors by the Pechini method was reported. Well-crystallized ZnGa₂O₄:Tb³⁺ phosphors were obtained at low-temperature about 550 °C. The phosphors formed porous agglomerates which consist of spherical nanocrystallites with a uniform size at about 30 nm. The photoluminescence of the phosphors included both the luminescence of ZnGa₂O₄ host and characteristic emission of Tb³⁺, and the excitation spectra showed an energy transfer from the host lattice to the activator. The Tb³⁺ emission from the phosphors prepared by the Pechini process was more intensive than that of phosphors by solid-state reaction process.     

Influence of processing conditions on the luminescence of YVO4:Eu nanoparticles

Single-phase YVO₄:Eu³⁺ nanopowders were synthesized by sol–gel combustion method using citric acid as a chelating agent and reducer. The microstructures and photoluminescence (PL) properties of the as-prepared YVO₄:Eu³⁺ nanopowders were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and PL spectroscopy. The luminescence intensities of the YVO₄ nanoparticles doped with 5 mol% Eu³⁺ ions strongly depended on the calcination temperature, the molar ratio of citric acid to nitrates and the amounts of the Li⁺ additive.     

Synthesis, phase transformation and dielectric properties of sol–gel derived Bi2Ti2O7 ceramics

Sol–gel derived Bi₂Ti₂O₇ ceramic powders have been prepared from methoxyethoxides of bismuth and titanium (molar ratio of Ti/Bi = 1.23 and water/alkoxides = 1.31). The Bi₂Ti₂O₇ phase was stable at a low temperature (700 °C), but it then transformed into mixed phases of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ at 850–1150 °C. The single phase of Bi₂Ti₂O₇ reoccurred at 1200 °C. Dielectric properties and ferroelectric behavior of samples sintered at 1150 and 1200 °C were examined. Under frequency of 1 MHz, samples sintered at 1150 and 1200 °C had a dielectric constant of 101.3 and 104.2, and a loss tangent of 0.0193 and 0.0145, respectively. Only the sample sintered at 1150 °C showed ferroelectric behavior, where remanent polarization is 3.77 μC cm⁻² and coercive field is 24 kV cm⁻¹. Thus, the Bi₂Ti₂O₇ did not exhibit ferroelectricity, but the mixed phase of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ did.     

Effect of PWVA/Sb2O3 complex inhibitor on the corrosion behavior of carbon steel in 55%LiBr solution

The inhibition performance of PWVA/Sb₂O₃ complex inhibitor on carbon steel was studied in 55%LiBr + 0.07 mol L⁻¹ LiOH solution. Results indicated that the complex inhibitor decreased both anodic and cathodic polarization current density and widened the passive potential region of carbon steel in test solution and can be classified as mixed inhibitor. The complex inhibitor exhibited excellent inhibition performance on carbon steel when the concentrations of PWVA and Sb₂O₃ were 300 and 200 mg L⁻¹, respectively. With the solution temperature increasing from 145 to 240 °C, the corrosion rates of carbon steel increased from 4.71 to 120.66 μm y⁻¹. In solution containing the complex inhibitor, the relationship between relative coverage ratio of inhibitor on carbon steel surface and inhibition efficiency at 145 °C was obtained as the equation μ = 0.94η, it was a direct proportion. This result proved that the complex inhibitor inhibited the corrosion of carbon steel by geometric blocking effect. When solution temperature was 160 °C, the adsorption Gibbs free energy of PWVA and Sb₂O₃ on carbon steel were −49.59 and −44.29 kJ mol⁻¹, respectively. It indicated that the adsorption processes of PWVA and Sb₂O₃ on carbon steel surface were spontaneous processes. As a strong oxidant, PWVA facilitated the compact passive film comprising of FeO, Fe₂O₃ and Fe₃O₄ forming on the surface and itself was reduced to heteropoly blue. Sb₂O₃ adsorbed on carbon steel surface formed an adsorption film. PWVA and Sb₂O₃ behaved synergistic effect. The corrosion resistance performance of carbon steel in 55%LiBr + 0.07 mol L⁻¹ LiOH solution was improved by PWVA/Sb₂O₃ complex inhibitor.     

YVO4∶Eu3+,Bi3+红色荧光粉的水热合成及其荧光性能

以Y₂O₃、Eu₂O₃、Bi(NO₃)₃·H₂O、浓HNO₃、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO₄: Eu³⁺, Bi³⁺纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明：合成的样品为YVO₄: Eu³⁺, Bi³⁺纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO₄: Eu³⁺, Bi³⁺纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁⁵D₀→⁷F₂),在594 nm有较弱的橙光发射(磁偶极跃迁⁵D₀→⁷F₁)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO₄: Eu³⁺, Bi³⁺纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO₄: Eu³⁺, Bi³⁺纳米晶的发光机理。     

Insertion/extraction reactions of lithium with LiV2O4

Lithium has been inserted into, and extracted from, the spinel Li_1.0V₂O₄ both electrochemically and chemically. Electrochemical and structural data show that in the system Li_1+xV₂O₄, for 0 < x ≤ 0.5, Li⁺ ions are inserted into the interstitial octahedral sites of the A_tet[B₂]_octX₄ spinel structure. At x ≈ 0.5, Li⁺ ions in the tetrahedral A-sites are displaced into the remaining octahedral sites to yield, at x = 1, a rocksalt phase Li₂V₂O₄; the [B₂]X₄ framework is unperturbed by the lithiation process. This framework also remains intact when Li⁺ ions are removed from Li_1.0V₂O₄ to a composition Li_0.67V₂O₄. Further extraction of lithium from the structure is accompanied by migration of some vanadium ions from the B-sites to the interstitial octahedral sites of the spinel structure. This process reduces the crystal symmetry from cubic to trigonal symmetry. In Li_0.27V₂O₄ the structure resembles that of Li_0.22VO₂, obtained by delithiation of layered LiVO₂, in which the vanadium cations are distributed in a 2:1 ratio between alternate cubic-close-packed oxygen layers; in the LiV₂O₄ spinel this ratio is 3:1.     

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.