Eu3+离子在Ca2PbO4一维结构基质中的发光研究

A Eu³⁺-doped Ca₂PbO₄ with one-dimensional structure was prepared with a solid-state reaction method and its characteristics were investigated. The XRD results show that the substitution of Ca²⁺ by Eu³⁺ has no influence on the structure of Ca₂PbO₄. Under the excitation of ultraviolet light， the Ca₂PbO₄:Eu³⁺ phosphor exhibits strong red emission at about 618 nm which is assigned to the ⁵D₀- ⁷F₂ electric-dipole transition. The compounds Sr₂CeO₄ and Ca₂SnO₄ have the same crystal symmetry as that of Ca₂PbO₄ and it is found that the emission intensity of Ca₂PbO₄∶Eu³⁺ is higher than that of Sr₂CeO₄∶Eu³⁺ and lower than that of Ca₂SnO₄∶Eu³⁺. The excitation spectrum of Ca₂PbO₄∶Eu³⁺ appears to be a broad band with two peaks at about 289 nm and 340 nm. The former peak is attributed to the Eu³⁺-O₂- charge transfer transition， while the latter one may be related to the absorption of Ca₂PbO₄ host or its crystal defects.     

Eu3+在La2O2S中的长余辉发光

The new Eu³⁺ doped lanthanum oxysulfide phosphors,which have the orange-red long afterg low emission,were synthesized by solid-state reaction method.The synthesized phosphors were characterized by X-ray diffraction.The excitation and emission spectra,afterglow spectra and afterglow decay curves were examined.XRD confirmed the phosphor as pure phase La₂O₂S.The phosphors showed typical transitions ⁵D_J(J=0,1) → ⁷J_J(J=0,1,2,3,4)of Eu³⁺.The photoluminescence spectra and afterglow spectra presented the regular alteration with various Eu³⁺ concentration, due to cross relaxation between energy levels of Eu³⁺. In addition, we studied the effects of activator concentration and dopants species on the afterglow property. The data showed afterglow result was the best with 2 % Eu³⁺ and doped with Mg²⁺ and Zr⁴⁺. A prominent phosphorescence can be seen in this phosphor after illuminated with UV light.     

助熔剂法制备的LaMgAl11O19∶Eun+(n=2，3)的发光特性

LaMgAl₁₁O₁₉∶Euⁿ⁺(n=2,3) was synthesized by solid state reaction using H₃BO₃ as a flux at 1 400 ℃ for 4 hours. And their luminescent properties was investigated under UV and VUV excitation. Strong pure blue emission due to d-f transition of Eu²⁺ was observed in LaMgAl₁₁O₁₉∶Eu²⁺ both in 254 nm and 147 nm excitation. At the same time, red emission due to ⁵D₀ → ⁷F_J (J=0, 1, 2, 3, 4) transition of Eu³⁺ also observed in LaMgAl₁₁O₁₉∶Eu³⁺. The dependence of emission intensity of blue/red emission on Eu²⁺ / Eu³⁺-content was evaluated. The result indicated that the blue emission intensity was arrived optimum when Eu²⁺-content was 0.10 mol·mol^-1under both UV and VUV excitation while red emission intensity reached optimum when Eu³⁺-content was 0.125 mol·mol^-1 under UV excitation. This suggests that LaMgAl₁₁O₁₉∶Eu²⁺ phosphors could be potential blue phosphor for the application in PDP.     

稀土红色荧光粉SrZnO2∶Eu3+的发光性能

A series of novel luminescent materials, SrZnO₂∶M (M=Eu³⁺, or Eu³⁺ + Li⁺) have been synthesized by high-temperature solid-state reaction. The structure and luminescence properties of SrZnO₂∶Eu³⁺ phosphor were studied through XRD, photoluminescence and Raman spectroscopy. The excitation spectra show a broad intense band and a number of small peaks corresponding to the inner 4f-shell excitations of Eu³⁺ (the strongest one is at 395 nm for ⁷F₀-⁵L₆). After SrZnO₂∶Eu³⁺ phosphor was co-doped with Li⁺ ions, its charge transfer band extended to longer wavelengths. This resulted in increase of luminescent quantum efficiency of the sample. SrZnO₂∶Eu³⁺,Li⁺ phosphor can be efficiently excited by longer UV. From the fluorescence spectrum of SrZnO₂∶Eu³⁺ phosphor, apart from transition emissions of ⁵D₀→ ⁷F_J (J=0～4), the transition emissions from ⁵D₁ → ⁷F_J (J=0～2) have been observed. For the SrZnO₂∶Eu³⁺ phosphor, under excitation of UV, the dominant emission is at about 612 nm, due to the ⁵D₀→ ⁷F₂ hypersensitive transition. The incorporation of Li⁺ ions greatly enhanced the luminescence intensity and made emission peak from ⁵D₀ → ⁷F₂ transition red-shifted.     

Eu3+在Ba2TiSi2O8中的发光

The barium titano-silicate phosphors doped with Eu³⁺ were synthesized by high temperature solid state reaction. The structures of as-synthesized samples were characterized by powder XRD. The maximum peaks of emission spectra of Ba₂TiSi₂O₈ and Ba₂TiSi₂O₈∶Eu³⁺ were respectively located at 450 and 618 nm, coming from the transitions of charge-transfer bands of Ti⁴⁺-O^2- and forced electric-dipole transition ⁵D₀-⁷F₂ of Eu³⁺. The luminous mechanisms of Ba₂TiSi₂O₈ and Ba₂TiSi₂O₈∶Eu³⁺ were suggested. The effects of concentration of Eu³⁺ on the luminous performance of Ba₂TiSi₂O₈∶Eu³⁺ were also studied and the results showed that the optimum concentration of Eu³⁺ was 0.12 mol per mole of matrix.     

球形La2O3∶Eu纳米晶的制备及其发光特性

The spheric La₂O₃∶Eu nanocrystals were prepared using NH₃·H₂O-NH₄HCO₃ mixture as precipitant. The material was characterized by FTIR, XRD and TEM techniques. The luminescence properties of Eu³⁺ in spheric La₂O₃ were measured by three dimension spectra, emission and excitation spectra. The results indicate that the La₂O₃∶Eu nanocrystals are in hexagonal phase by annealing at 800 ℃, the crystal size is about 30 nm. The maximum emission and excitation wavelength were determined by three dimensional spectroscopy to be at 591 nm and 394 nm, respectively. In emission spectrum the band at 591 nm and 612 nm are corresponding to ⁵D₀-⁷F₁ and ⁵D₀-⁷F₂ transition of Eu³⁺ ions. With increasing in annealing temperature the differences of intensity of the two transitions are increased. This phenomenon shows that the luminescence intensity of La₂O₃∶Eu nanocrystals can be tuned by changing annealing temperature.     

沉淀法合成纳米晶长余辉材料Y2O2S∶Eu3+，Ti

The long-lasting phosphorescent materials, yttrium oxysulfides doped by Eu and Ti, were systhesized by coprecipitation with their subsequent thermal decomposition in the presence of sulphur. The products were characterized by XRD, TEM, phosphorescent spectra, and thermoluminescence. The XRD results indicate that the lowest synthesis temperature is 700 ℃. From the TEM, the average diameter of particles was in the range of 60～120 nm, and augmented with the increase of temperature. The materials under UV excitation presented well afterglow from the transition of ⁵D_0,1 → ⁷F_J of Eu³⁺, and the persistent time was about 2 h. The long-lasting afterglow mechanism was discussed, too.     

凝胶-燃烧法合成YAG∶Eu3+纳米荧光材料的结构和发光性能

Y₃Al₅O₁₂∶Eu nanophosphors were synthesized by a gel combustion method. The structure of phosphors was characterized by XRD and FTIR. YAG phase came to occur when YAG∶Eu precursors were sintered at 800 ℃, although the phase was mainly amorphous. The organic groups pyrolyzed completely and pure YAG phase was obtained in the samples sintered at 900 ℃. In the formation of YAG phase, no intermediate phases such as YAP and YAM were detected. Both ⁵D₀ → ⁷F₁ orange and ⁵D₀ → ⁷F₂ red emission could be observed for all the sintered samples. However, the emission of amorphous samples was greatly different from that of crystalline ones. The former was mainly ⁵D₀→ ⁷F₂ red emission, but the latter was ⁵D₀ → ⁷F₁ orange emission. As sintering temperature rises, the ratio of orange to red for phosphors increases. Eu could be doped up to 8% in YAG host lattice, and fluorescence quenching was absent. It indicated that the gel combustion synthesis method can increase emission intensity and quenching concentration due to a good distribution of Eu³⁺ activators in Y₃Al₅O₁₂ matrix.     

Eu3+掺杂SiO2-B2O3-NaF玻璃的制备及发光性质

The Eu-doped SiO₂-B₂O₃-NaF glass was prepared by sol-gel process, using tetraethoxy Silicane, boric acid and sodium fluoride as starting materials, 0.10 mol·L^-1 EuCl₃ solution as the dopant. The luminescent properties of Eu³⁺ doped SiO₂-B₂O₃-NaF phosphors were investigated. The phosphors showed prominent luminescence in pink, the strong emission of Eu³⁺ comes from electronic transition of ⁵D₀- ⁷F₁（591 nm）and ⁵D₀- ⁷F₂（615 nm）,which derived from two transition modes of magnetic-dipole and electric-dipole .The peak intensity of 591nm in SiO₂-B₂O₃-NaF matrix is much stronger than it in the other matrixes, it means that SiO₂-B₂O₃-NaF has sensitization on the transition of ⁵D₀- ⁷F₁ (Eu³⁺). If there are broad bonds in the range of 275～380 nm in the excitation spectrum of Eu³⁺ -doped SiO₂-B₂O₃-NaF glass, the emission peak intensity should be intensified. It is because the electron migration CT band of O^2--Eu³⁺. For all Eu³⁺ concentrations used, the investigation found that when the mass of fraction got to 29.19×10^-3, the luminescence intensity reached the summit. And there is a phenomenon of concentration quenching. Investigation with the same concentration of Eu³⁺ at different annealed temperature, we found that the sample annealed at 400 ℃, the luminescence intensity achieved its maximum value, and Eu³⁺ in this matrix had a phenomenon of temperature quenching. The structural characterization of these luminescent materials was carried by used XRD and TEM. The result showed that the phosphor was in amorphous phase.     

Sr3Al2O6∶Eu2+红色发光纳米晶的新型形貌与发光性能的研究

A red luminescent Sr₃Al₂O₆∶Eu²⁺ nanocrystallites with new morphology were synthesized by sol-gel route assisted by microwave irradiation. The phosphor powders were characterized by X-ray diffraction (XRD)， scanning electron microscopy (SEM) and fluorescence spectroscopy. The results reveal that the calcination temperature of the Sr₃Al₂O₆∶Eu²⁺ phosphor crystallites greatly affects its morphology. With temperature increasing， the phosphor crystallites morphology showed primarily from nanorod-like， mixture of nanorod and flower-like to homogeneous flower-like morphology. The effects of new morphology on luminescent properties of phosphors were investigated. Uniformly dispersed flower-like Sr₃Al₂O₆∶Eu²⁺ phosphor powders showed the strongest luminescent intensity and the longest afterglow time.     

Phase relations in the K2W2O7-K2WO4-KPO3-Bi2O3 system and structure of K6.5Bi2.5W4P6O34

The phase relations in the cross-section of the K₂W₂O₇-K₂WO₄-KPO₃ containing 15 mol% Bi₂O₃ were undertaken using flux method. Crystallization fields of K_6.5Bi_2.5W₄P₆O₃₄, K₂Bi(PO₄)(WO₄), Bi₂WO₆, KBi(WO₄)₂ and their cocrystallization areas were identified. Novel phase K_6.5Bi_2.5W₄P₆O₃₄ was characterized by single-crystal X-ray diffraction: sp. gr. P−1, a=9.4170(5), b=9.7166(4), c=17.6050(7) Å, α=90.052(5)°, β=103.880(5)° and γ=90.125(5)°. It has a layered structure, which contains {K₇Bi₅W₈P₁₂O₆₈}_∞ layers stacked parallel to ab plane and sheets composed by potassium atoms separating these layers. Sandwich-like {K₇Bi₅W₈P₁₂O₆₈}_∞ layers are assembled from [W₂P₂O₁₃]_∞ and [BiPO₄]_∞ building units, and are penetrated by tunnels with K/Bi atoms inside. FTIR-spectra of K₂Bi(PO₄)(WO₄) and K_6.5Bi_2.5W₄P₆O₃₄ were discussed on the basis of factor group theory.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

Solubility in the Na2Cr2O7-(NH4)2Cr2O7-K2Cr2O7-H2O system

Solubility in the Na₂Cr₂O₇-(NH₄)₂Cr₂O₇-K₂Cr₂O₇-H₂O four-component water-salt system at 25, 50, and 75°C was studied for the first time. Phase field boundaries for individual salts and potassium and ammonium dichromate solid solutions, monovariant lines, and invariant points were determined. Experimental data were used to optimize the looped isohydric process of potassium dichromate preparation involving additional salts.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

NaBO2-NaCl-Na2CO3, NaBO2- Na2CO3-NaMoO4, NaBO2- Na2CO3-NaWO4, and NaBO2-NaCl-Na2WO4 ternary systems

The phase diagrams of the NaBO₂-NaCl-Na₂CO₃, NaBO₂-Na₂CO₃-Na₂MoO₄, NaBO₂- Na₂CO₃-Na₂WO₄, and NaBO₂-NaCl-Na₂WO₄ ternary systems were studied by a calculation-experimental method and differential thermal analysis. The coordinates of ternary eutectics were determined: E ₁: 612°C, 16 mol % NaBO₂, 42 mol % NaCl, and 42 mol % Na₂CO₃; E ₂: 568°C, 12 mol % NaBO₂, 28 mol % Na₂CO₃, and 60 mol % Na₂MoO₄; E ₃: 575°C, 12 mol % NaBO₂, 32 mol % Na₂CO₃, and 56 mol % Na₂WO₄; E ₄: 628°C, 8 mol % NaBO₂, 20 mol % NaCl, and 72 mol % Na₂WO₄; and E ₅: 655°C, 9 mol % NaBO₂, 53 mol % NaCl, and 38 mol % Na₂WO₄.     

Structural chemistry of Sr3Cr2WO9, Ca3Cr2WO9, and Ba3Cr2WO9

We have studied the preparation and crystallographic structure of three perovskite-type compounds: Sr₃Cr₂WO₉, cubic, the lattice parameter of which is a = 7.812Å; Ca₃Cr₂WO₉, tetragonal, the lattice parameters of which are a = 5.408 Å and c = 7.635Å; and Ba₃Cr₂WO₉, hexagonal, the lattice parameters of which are a = 5.691 Å and c = 13.957Å. We have compared these three structures and shown the relationship between the dimensions of the alkaline-earth metal and the existence of the different structures.     

SnSbBiS4-SnS and SnSbBiS4-Sn2Sb6S11 sections of the SnS-Sb2S3-Bi2S3 ternary system

SnSbBiS₄-SnS and SnSbBiS₄-Sn₂Sb₆S₁₁ sections were studied by physicochemical methods (DTA, X-ray powder diffraction, microstructure observation, and microhardness measurements). These sections were found to be eutectic quasi-binary sections of the SnS-Sb₂S₃-Bi₂S₃ ternary system. Solid solution regions based on the initial components were found on either side of the sections. Alloys in the solid solution region are p-type semiconductors.     

Extension of the La7Mo7O30 structural type with La7Nb3W4O30 and La7Ta3W4O30 compounds

Two compounds of formula La₇A₃W₄O₃₀ (with A=Nb and Ta) were prepared by solid-state reaction at 1450 and 1490 °C. They crystallize in the rhombohedric space group R-3 (No. 148), with the hexagonal parameters: , and , . The structure of the materials was analyzed from X-ray, neutron and electronic diffraction. These oxides are isostructural of the reduced molybdenum compound La₇Mo₇O₃₀, which are formed of perovskite rod along [111]. An order between (Nb, Ta) and W is observed.     

Theoretical study of polyoxide clusters B20O30, Al20O30, V20O50, Si20O30H20, and Si20O30F20

The structural, electronic, and vibrational characteristics and energies of the isolated polyoxide clusters B₂₀O₃₀, Al₂₀O₃₀, V₂₀O₅₀, Si₂₀O₃₀H₂₀, and Si₂₀O₃₀F₂₀ and their complexes with the H⁻ ion and ammonia complexes Al₂₀O₃₀ · nNH₃ have been calculated by the density functional theory B3LYP method with different basis sets. The computation results show that the symmetric closo structure I _h with oxygen bridges located above the centers of the faces of an empty [M₂₀] dodecahedron is more favorable for V₂₀O₅₀, Si₂₀O₃₀H₂₀, and Si₂₀O₃₀F₂₀. For B₂₀O₃₀, the cage closo isomer is also more favorable than the other isomers, but its structure is severely distorted as compared to a dodecahedron and has a symmetry close to C ₃ . For Al₂₀O₃₀, the I _h structure corresponds to a high-lying local minimum of the potential energy surface. For Al₂₀O₃₀, a set of unusual puckshaped isomers of symmetry C _i , with different numbers of four-coordinate atoms ^IVAl and three-coordinate atoms ^IIIO, was localized; these structures are more than 90 kcal/mol more favorable than the dodecahedron I _h . The most favorable isomer of Al₂₀O₃₀ contains twelve four-coordinate atoms ^IVAl and four five-coordinate atoms ^VAl. The energies of dissociation of the most favorable M₂₀O₃₀ clusters into the M₂O₃ (C _2v ) and M₄O₆ (T _d ) fragments and, in the case of Al₂₀O₃₀, also into the Al₈O₁₂ (O _h ) and Al₁₂O₁₈ (D _3d ) fragments, have been estimated. The conclusion has been drawn that these clusters can, in principle, exist and can be experimentally detected in the isolated state. Analogous calculations have been performed for ammonia complexes Al₂₀O₃₀ · nNH₃ with n varying from 1 to 20. The effect of solvation on the relative stability of the dodecahedral and puckshaped isomers of the Al₂₀O₃₀ cluster is observed. The isomers with ammonia molecules in their first coordination sphere become much closer to one another on the energy scale; however, the dodecahedron remains a considerably less favorable intermediate. Original Russian Text ? O.P. Charkin, N.M. Klimenko, D.O. Charkin, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 624–635.