Identification of charge‐transfer transition between Gd3+ to O2− in gadolinium‐containing oxide phosphors in VUV region

Abstract— The broad bands at around 155 nm for GdAl₃(BO₃)₄:Eu, at 184 nm for Ca₄GdO(BO₃)₃:Eu, at 183 nm for Gd₂SiO₅:Eu, and at 170 nm for GdAlO₃:Eu were observed. These bands were assigned to the charge‐transfer (CT) transition of Gd³⁺‐O^2?. In the excitation spectrum of (Gd,Y)BO₃:Eu, a broadened excitation band was observed in VUV region. It could be considered that this band was composed of two bands at about 160 and 166 nm. The preceding band was assigned to the BO₃ group absorption. The later one at about 166 nm could be assigned to the CT transition of Gd³⁺‐O^2?, according to the result of GdAl₃(BO₃)₄:Eu, Ca₄GdO(BO₃)₃:Eu, Gd₂SiO₅:Eu, and GdAlO₃:Eu. The excitation spectra overlapped between the CT transition of Gd³⁺‐O^2? and BO₃ groups absorption. It caused the emission of Eu³⁺ to take place effectively in the trivalent europium‐doped (Gd,Y)BO₃ host lattice under 147‐nm excitation.     

Enhanced PL and VUV absorption of BaZr(BO3)2:Eu3+ by Al3+ incorporation

Abstract— The photoluminescence (PL) and vacuum‐ultraviolet excitation (VUV) properties of BaZr(BO₃)₂ doped with the Eu³⁺ activator ion were studied as a new red phosphor for PDP applications. The excitation spectrum shows strong absorption in the VUV region with an absorption band edge at 200 nm. The charge‐transfer excitation band of Eu³⁺ was enhanced by co‐doping with an Al³⁺ ion into the BaZr(BO₃)₂ lattices. The PL spectrum shows the strongest emission at 615 nm, corresponding to the electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺ in BaZr(BO₃)₂, which results in good red‐color purity.     

A study on the chromaticity shifts of blue phosphor for color plasma displays

The dependency of the chromaticity shifts on the concentration of Eu²⁺ doped in BaMgAl₁₀O₁₇ (BAM) was investigated under heat‐treatment and vacuum ultraviolet (VUV) irradiation. The Eu²⁺ ions in BAM show an asymmetrical broad emission band with a maximum at ～452 nm under excitation of VUV light at room temperature, showing that multiple crystalline cationic sites exist in the host. It was found that the chromaticity shifts greatly decrease with increasing heat‐treatment temperature. Regardless of the Eu²⁺ concentration, the chromaticity shifts caused by heat‐treatment are greater than that caused by VUV irradiation. Compared with conventional BAM, a solid solution of BAM with barium aluminate as a powder and film was also studied, and very few chromacity shifts were observed. It is suggested that the distribution of Eu²⁺ ions in different sites in a BAM lattice results in different chromaticity coordinates. By increasing the Eu²⁺ concentration in BAM, or under heat‐treatment and VUV irradiation, the emission band shifts towards longer wavelengths.     

Thermodynamic investigation on the Al2O3–BaO binary system

The Al₂O₃–BaO binary system has been studied using the CALPHAD technique in this paper. The modeling of Al₂O₃ in the liquid phase is modified from the traditional formula with the liquid phase represented by the ionic two-sublattice model as (Al³⁺, Ba²⁺)_P (AlO₂¹⁻, O²⁻)_Q. Based on the measured phase equilibrium data and experimental thermodynamic properties, a set of thermodynamic functions has been optimized using an interactive computer-assisted analysis. A comparison between the calculated results and experimental data is presented.     

A Faster and More Space-Efficient Algorithm for Inferring Arc-Annotations of RNA Sequences through Alignment

The nested arc-annotation of a sequence is an important model used to represent structural information for RNA and protein sequences. Given two sequences S₁ and S₂ and a nested arc-annotation P₁ for S₁, this paper considers the problem of inferring the nested arc-annotation P₂ for S₂ such that (S₁, P₁) and (S₂, P₂) have the largest common substructure. The problem has a direct application in predicting the secondary structure of an RNA sequence given a closely related sequence with known secondary structure. The currently most efficient algorithm for this problem requires O(nm³) time and O(nm²) space where n is the length of the sequence with known arc-annotation and m is the length of the sequence whose arc-annotation is to be inferred. By using sparsification on a new recursive dynamic programming algorithm and applying a Hirschberg-like traceback technique with compression, we obtain an improved algorithm that runs in min{O(nm² + n²m),O(nm² log n), O(nm³)} time and min{O(m² + mn), O(m² log n + n)} space.     

Single-phase Ce3+–Mn2+–Tb3+ tri–codoped barium–yttrium–silicate phosphors

Ce³⁺–Mn²⁺–Tb³⁺ cooperative barium–yttrium-orthosilicate phosphors composed of Ba_{9-3m/2-n-3p/2}Ce_mMn_nTb_pY₂Si₆O₂₄ (m = 0.005–0.4, n = 0–0.5, p = 0–0.5) were prepared using a solid-state reaction. The X-ray diffraction patterns of the resultant phosphors were examined to index the peak positions. The photoluminescence (PL) excitation and emission spectra of the Ce³⁺–Mn²⁺–Tb³⁺ activated phosphors were clearly monitored. The dependence of the luminescent intensity of the Mn²⁺–Tb³⁺ co-doped Ba_9-3m/2Ce_mY₂Si₆O₂₄ host lattices on Ce³⁺ content (m = 0.025, 0.1) was also investigated. Co-doping Mn²⁺ into the Ce³⁺–Tb³⁺ co-doped host structure enabled energy transfer from Ce³⁺ to Mn²⁺; this energy transfer mechanism is discussed. The phosphors of Ce³⁺–Mn²⁺–Tb³⁺ doped Ba₉Y₂Si₆O₂₄ host lattice were prepared for efficient white-light emission under NUV excitation. With these phosphors, the desired CIE values including white region of the emission spectra were achieved.     

Sublimation enthalpies of terbium and lutetium triiodides and formation enthalpies of their monomer and dimer molecules

The sublimation of terbium and lutetium triiodides was studied by Knudsen effusion mass spectrometry. The temperature dependencies of partial vapor pressures [atm] of the monomer and dimer molecules were determined as: lnp(TbI₃) = – (31.74 ± 0.24)× 10³/T + (21.43 ± 0.29) for 743–906 K; lnp(Tb₂I₆) = – (38.66 ± 0.38)× 10³/T + (25.63 ± 0.46) for 786–906 K; lnp(LuI₃) = – (31.48 ± 0.25)× 10³/T + (22.28 ± 0.30) for 721–951 K; and lnp(Lu₂I₆) = – (36.95 ± 0.37)× 10³/T + (25.21 ± 0.43) for 796–950 K. On the basis of a joint analysis of all literature data, the sublimation enthalpies [kJ mol^–1] at 298.15 K are recommended as 281 ± 3 (TbI₃), 346 ± 30 (Tb₂I₆), 279 ± 12 (LuI₃), and 340 ± 30 (Lu₂I₆). The standard formation enthalpies [kJ mol^–1] of the gaseous species at 298.15 K are –343 ± 4 (TbI₃), –902 ± 30 (Tb₂I₆),–326 ± 12 (LuI₃), and –870 ± 30 (Lu₂I₆).     

The numerical solution of fourth order mildly quasi-linear parabolic initial boundary value problem of second kind

In this article, we report on three-level implicit stable finite difference formulas of O(k ² + h ²) and O(k ² + h ⁴) for the numerical integration of certain mildly quasi-liner fourth order parabolic partial differential equations in one-space dimension. The numerical solution of u _xx is obtained as a by-product of the method. In all cases, we use only (3 + 3 + 3)-grid points and a single computational cell. Difference schemes for the fourth order linear parabolic equation in polar coordinates are also discussed. The stability analysis for the model linear problem is given as a representative example. Numerical results are presented to demonstrate the order and accuracy of the proposed methods.     

Nanoplates of α-SnWO4 and SnW3O9 prepared via a facile hydrothermal method and their gas-sensing property

Nanoplates of α-SnWO₄ and SnW₃O₉ were selectively synthesized in large scale via a facile hydrothermal reaction method. The final products obtained were dependent on the reaction pH and the molar ratio of W⁶⁺ to Sn²⁺ in the precursors. The as-prepared nanoplates of α-SnWO₄ and SnW₃O₉ were characterized by X-ray powder diffraction (XRD), N₂-sorption BET surface area, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The XPS results showed that Sn exists in divalent form (Sn²⁺) in SnW₃O₉ as well as in α-SnWO₄. The gas-sensing performances of the as-prepared α-SnWO₄ and SnW₃O₉ toward H₂S and H₂ were investigated. The hydrothermal prepared α-SnWO₄ showed higher response toward H₂ than that prepared via a solid-state reaction due to the high specific surface area. The gas-sensing property toward H₂S as well as H₂ over SnW₃O₉ was for the first time reported. As compared to α-SnWO₄, SnW₃O₉ exhibits higher response toward H₂S and its higher response can be well explained by the existence of the multivalent W (W⁶⁺/W⁴⁺) in SnW₃O₉.     

Monoid-labeled transition systems

Given a -complete (semi)lattice , we consider -labeled transition systems as coalgebras of a functor ⁽⁻⁾, associating with a set X the set ^X of all -fuzzy subsets. We describe simulations and bisimulations of -coalgebras to show that L⁽⁻⁾ weakly preserves nonempty kernel pairs iff it weakly preserves nonempty pullbacks iff L is join infinitely distributive (JID).Exchanging for a commutative monoid , we consider the functor ⁽⁻⁾_ω which associates with a set X all finite multisets containing elements of X with multiplicities m M. The corresponding functor weakly preserves nonempty pullbacks along injectives iff 0 is the only invertible element of , and it preserves nonempty kernel pairs iff is refinable, in the sense that two sum representations of the same value, r₁ + … + r_m = c₁ + … + c_n, have a common refinement matrix (m_{(i, j)}) whose k-th row sums to r_k and whose l-th column sums to c_l for any 1≤ k ≤ m and 1 ≤ l ≤ n.     

Red phosphor Li2Mg2(WO4)3: Eu3+ with lyonsite structure for near ultraviolet light-emitting diodes

A series of Eu³⁺-activated Li₂Mg₂(WO₄)₃ (LMW) materials were synthesized by high temperature solid state reactions. The phosphor can be effectively excited by 394 nm near ultraviolet light and emit intense red light with high color purity. Prepared phosphors can be indexed to LMW with particular lyonsite structure. The occupation of Eu³⁺ in LMW is selective. Most of Eu³⁺ comes into ¹A sites without inversion symmetry. The present research suggests that LMW is a suitable host for luminescence applications and Eu³⁺-activated LMW is a promising phosphor for phosphor-converted white light-emitting diodes.     

Thermodynamic assessment of the CaO–Cu2O–FeO–Fe2O3 system

Thermodynamic assessment of the CaO–Cu₂O–FeO–Fe₂O₃ system is presented. Effects of temperature and P(O₂) on the phase equilibria involving slag, solubility of copper and the Fe³⁺/Fe²⁺ ratio in slag have been modeled using available experimental data. Subsolidus phase equilibria and concentration of iron in liquid copper were evaluated as well. Different ways of representing phase equilibria in a quaternary system are illustrated. The slag model, [Ca²⁺, Cu⁺, Fe²⁺, Fe³⁺][O²⁻], was developed using the Modified Quasichemical Model (MQM). Liquid metal phase is modeled using the MQM, but as a separate solution, (Cu^I, Fe^II, O^II). Spinel phase is modeled using the Compound Energy Formalism (CEF) and takes into account the solubility of copper and calcium. A thermodynamic database produced in the present study can be used for predictions in pyrometallurgical processing of copper involving calcium ferrite slags. The database is internally consistent with the binary and ternary sub-systems published earlier, as well as with higher-order systems. It works in the environment of FactSage, ChemApp, ChemSheet and SimuSage software packages.     

Investigation of spectroscopic properties of Sm-Eu codoped phosphate glasses

Phosphate glasses with chemical compositions of 74.5NaH₂PO₄–20ZnO–5Li₂O–0.5Sm₂O₃ and 74NaH₂PO₄–20ZnO–5Li₂O–0.5Sm₂O₃–0.5Eu₂O₃ were synthetized by melt quenching method. We investigated the influence of Sm³⁺/Eu³⁺ doping on the optical properties of phosphate glasses. X-ray Diffraction indicates that the samples have an amorphous structure. DSC measurements show a good thermal stability of phosphate glasses. Using the absorption spectra, Judd–Ofelt analysis was applied to absorption bands of Sm³⁺ (4f⁵) to carry out the three phenomenological parameters of Judd–Ofelt (JO). According to the obtained values of Ω₂, Ω₄ and Ω₆, some radiative properties were theoretically determined. We report both the photoluminescence (PL) and the PL lifetime measurements of a prominent emission transition ⁴G_5/2 → ⁶H_5/2 (604 nm) of Sm³⁺ both in absence and in presence of Eu³⁺. It is shown that Eu³⁺ ions act as sensitizers for Sm³⁺ ions and contribute largely to the improvement of the radiative properties of phosphate glasses. An improvement of the PL lifetime value after adding Eu³⁺ ions (4.58 ms) is reported. The predicted lifetime (τ_rad) calculated by Judd–Ofelt theory and the experimental lifetime (τ_meas) for the prepared phosphate glasses were compared with those of other works. Photoluminescence (PL) intensity of ⁴G_5/2 → ⁶H_5/2 (604 nm), ⁴G_5/2 → ⁶H_7/2 (567 nm), ⁴G_5/2 → ⁶H_9/2 (650 nm) and ⁴G_5/2 → ⁶H_11/2 (706 nm) and the quantum efficiency (η) for the excited ⁴G_5/2 level were enhanced after adding Eu³⁺. The radiative properties obtained for (Sm, Eu) codoped phosphate glasses suggest that the present material can be a potential candidate for the development of color display devices.     

Hydrogen sensing and mechanism of M-doped SnO2 (M = Cr, Cu and Pd) nanocomposite

The microstructure of M-doped SnO₂ (M = Cr³⁺, Cu²⁺ and Pd²⁺) prepared by the sol–gel method and their gas-sensing performance were investigated. In particular, we focus on the effects of metallic ions on the hydrogen sensing behavior of the SnO₂-based sensor. It is found that hydrogen gas response of SnO₂ can be enhanced evidently by adding Pd²⁺, while such effect from Cr³⁺ and Cu²⁺ exhibits somewhat slight. A theoretical study based on first principles calculation shows that SnO₂–Pd (1 1 0) surface enable adsorb more H₂ gas and receive larger electrons from adsorbed H₂ molecule, thereby holding the potential for the improvement of gas response to hydrogen.     

Single quantum dot-micelles coated with gemini surfactant for selective recognition of a cation and an anion in aqueous solutions

The synthesis of quantum dot coated with cetyltrimethyl ammonium bromide (CTAB) and gemini surfactant [C₁₂H₂₅N⁺(CH₃)₂(CH₂)₄(CH₃)₂N⁺C₁₂H₂₅]·2Br⁻ (C_12-4-12) in aqueous solution have been described. It is characterized by photoluminescent spectroscopy, UV–vis spectroscopy and transmission electron microscopy (TEM), etc. In comparison with CTAB-coated QDs, the QDs coated with C_12-4-12 respond selectively to both transition metal ion copper and fluoride ion in aqueous media. When Cu²⁺ is bound to C_12-4-12-coated QD micelles, the fluorescence intensity is quenched. Linear relationships are found between the relative fluorescence intensity and the concentration of Cu²⁺ in the range 0–500 μM, which is best described by a Stern–Volmer-type equation. Meanwhile, it is found that F⁻ enhanced the luminescence of the C_12-4-12-coated QD micelles in a concentration dependence that is described by a Langmuir binding isotherm equation in the range 0–300 μM. The limits of detection of Cu²⁺ and F⁻ are 1.1 and 0.68 μM, respectively. The possible mechanism is discussed.     

Effect of alkali metal ions co-doping on the structure and luminescent properties of phosphor Zn3(BO3)2:Eu3+

A series of the Zn₃(BO₃)₂:Eu³⁺ without or with alkali metal ions doping at a low sintering temperature were synthesized by the solid-state reaction method. The XRD pattern shows that all samples exhibit Zn₃(BO₃)₂ crystalline phase. The samples co-doped with alkali metal ions have better crystallinity compared with the un-compensated ones. The different charge compensation approaches have no influence on the shape and position of the emission and excitation spectra. However, the luminescent intensity of samples has been obviously enhanced with different alkali metal ions co-doping. The introduction of Li⁺ can increase the red emission of Eu³⁺ compared with the others. Thus, the volume compensation and the equilibrium of mole number can be taken into consideration by charge compensated (CC) approaches.     

Design and characterization of new lanthanide fluorides and their optical properties

Three kinds of lanthanide phosphors (La_xLu_1−xF₃: Eu³⁺, LaF₃–CaF₂:Eu³⁺ and LaF₃: Eu³⁺) have been successfully synthesized based on three different ways such as molten salts, co-precipitation, supersonic and microwave irradiations. The as-prepared powder materials all exhibited red luminescence. Their crystal structures or morphologies were studied by means of X-ray powder diffraction and scanning electronic microscope. Eu³⁺-doped LaF₃–CaF₂ phosphor can be emissive under excitation at longer wavelengths (466 and 533 nm) excitations. Supersonic and microwave irradiations have shortened the reaction time of LaF₃: Eu³⁺ crystals in 40 min under very low temperature (50 °C).     

A new long-lasting phosphor Zr and Eu co-doped SrMg2(PO4)2

Zr⁴⁺- and Eu³⁺-codoped SrMg₂(PO₄)₂ phosphors were prepared by conventional solid-state reaction. Under the excitation of ultraviolet light, the emission spectra of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.0005-0.07) are composed of a broad emission band peaking at 500 nm from Zr⁴⁺-emission and the characteristic emission lines from the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3 and 4) transitions of Eu³⁺ ions. These phosphors show the long-lasting phosphorescence. The emission color varies from red to white with increasing Zr⁴⁺-content. The white-light emission is realized in single-phase phosphor of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.07) by combining the Zr⁴⁺- and Eu³⁺-emission. The duration of the persistent luminescence of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.07) reaches nearly 1.5 h. The time at which the long-lasting phosphorescence intensity is 50% of its original value (T_0.5) is 410 s. The afterglow decay curves and the thermoluminescence spectra were measured to discuss this long-lasting phosphorescence phenomenon. The co-doped Zr⁴⁺ ions act as both the luminescence centers and trap-creating ions.     

Calculation of ternary mixing properties of melts and minerals from the bounding binaries

Among the several methods that have been used to predict thermodynamic properties of ternary alloys and oxides from three binary data, we used the models proposed by Kohler(1), Toop(2), and Muggianu (3) in order to evaluate the possibility of the application of these methods to geologically important systems, such as zeolites, clay minerals and silicate glasses. These models can represent the ternary excess Gibbs energy of the NaCl-KCl-H₂O and Ca-Mg-Fe²⁺ garnet (Ca₃Al₂Si₃O₁₂ - Mg₃Al₂Si₃O₁₂ - Fe₃Al₂Si₃O₁₂) systems relatively well without a ternary correction term. The deviation from the reference data increases in the central region of the composition triangle. Toop's model with constant mole fractions of NaCl and Mg best simulated the ternary systems among the models. The path independent Muggianu model was applied to diopside (CaMgSi₂O₆) -jadeite (NaAlSi₂O₆) - acmite (NaFe³⁺Si₂O₆) ternary as an example. Although there exists intrinsic uncertainty in calculation without the ternary interaction term, these models, especially, Muggianu and Kohler can be good approximation methods for prediction of the ternary excess properties of the natural mineral solid solutions, devoid of ternary experimental thermodynamic data.     

Synthesis of Bi and Gd doped ZnB2O4 for evaluation as potential materials in luminescent display applications

A series of Bi³⁺ and Gd³⁺ doped ZnB₂O₄ phosphors were synthesized with solid state reaction technique. X-ray diffraction technique was employed to study the structure of prepared samples. Excitation and emission spectra were recorded to investigate the luminescence properties of phosphors. The doping of Bi³⁺ or Gd³⁺ with a small amount (no more than 3 mol%) does not change the structure of prepared samples remarkably. Bi³⁺ in ZnB₂O₄ can emit intense broad-band purplish blue light peaking at 428 nm under the excitation of a broad-band peaking at 329 nm. The optimal doping concentration of Bi³⁺ is experimentally ascertained to be 0.5 mol%. The decay time of Bi³⁺ in ZnB₂O₄ changes from 0.88 to 1.69 ms. Gd³⁺ in ZnB₂O₄ can be excited with 254 nm ultraviolet light and yield intense 312 nm emission. The optimal doping concentration of Gd³⁺ is experimentally ascertained to be 5 mol%. The decay time of Gd³⁺ in ZnB₂O₄ changes from 0.42 to 1.36 ms.