Luminescence studies on Eu<Superscript>2+</Superscript> and Tb<Superscript>3+</Superscript> doped Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> phosphors

Eu²⁺ and Tb³⁺ doped Ca₂MgSi₂O₇ phosphors were synthesized by conventional solid-state reaction. The phase formation was confirmed by X-ray powder diffraction technique and refined lattice parameters were calculated by rietveld refinement process using Celref v3. The photoluminescence (PL) excitation and emission spectra were investigated. The phosphors exhibited broaden green emitting luminescence peaking at 520 nm when excited at 374 nm source. Morphological studies were carried out using Scanning electron microscopy (SEM) images of the sample with optimum PL emission. The dependence of photoluminescence intensity on co-dopant concentration and the kinetic parameters were also reported. Time resolved fluorescence spectroscopy (TRFS) is used to investigate the decay in luminescence signals with respect to time. The sample proved to be a good long lasting material, which makes it useful in emergency signs, textile printing, textile exit sign boards and electronic instrument dial pads etc.     

Crystal and molecular structure of uranyl acetylacetonate dimer, [UO<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>7</Subscript>O<Subscript>2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>

The crystal and molecular structure of uranyl acetylacetonate dimer was determined by single crystal X-ray diffraction. The compound crystallizes in the tetragonal system, a = 7.9420(2), c = 40.1240(13) Å (at 100 K), Z = 4, space group P4₁2₁2. Dimeric uranyl acetylacetonate molecules in the crystal are formed by bridging bonding of one of O atoms of the acetylacetonate ligands with U atoms, so that the coordination polyhedra of U atoms (distorted pentagonal bipyramids) share a common equatorial edge. The dimer has a nonplanar structure, being significantly bent along the conventional line connecting the bridging O atoms.     

Electrical Conductivity of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> Crystals Doped with Ca<Superscript>2+</Superscript>, Pb<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript>, and Ba<Superscript>2+</Superscript>

Single crystals of Bi₂WO₆ (a layered perovskite-like compound) doped with Ca²⁺, Pb²⁺, Sr²⁺, and Ba²⁺ on the Bi³⁺ site are grown, and their oxygen ionic conductivity is measured along the polar axis. The intrinsic conductivity of the doped crystals differs insignificantly from the conductivity of undoped Bi₂WO₆, indicating that the oxygen ions in the Bi₂O₂ layers contribute little to the oxygen ionic conductivity of the crystals. The sharp change in the activation energy for conduction at 600°C attests to a transition from one conduction mechanism to another in going from low to high temperatures.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 863–865.Original Russian Text Copyright © 2005 by Kharitonova, Voronkova, Yanovskii.     

Hollow click-based porous organic polymers for heterogenization of [Ru(bpy)<Subscript>3</Subscript>]<Superscript>2+</Superscript> through electrostatic interactions

A facile approach for the heterogenization of transition metal catalysts using non-covalent interactions in hollow click-based porous organic polymers (H-CPPs) is presented. A catalytically active cationic species, [Ru(bpy)₃]²⁺ (bpy = 2,2’-bipyridyl), was immobilized in H-CPPs via electrostatic interactions. The intrinsic properties of [Ru(bpy)₃]²⁺ were well retained. The resulting Rucontaining hollow polymers exhibited excellent catalytic activity, enhanced stability, and good recyclability when used for the oxidative hydroxylation of 4-methoxyphenylboronic acid to 4-methoxyphenol under visible-light irradiation. The attractive catalytic performance mainly resulted from efficient mass transfer and the maintenance of the chemical properties of the cationic Ru complex in the H-CPPs.

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Persistent luminescence of Zn<Subscript>2</Subscript>GeO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>/Pr<Superscript>3+</Superscript> phosphors

Zn₂GeO₄, Zn₂GeO₄:Mn²⁺, Zn₂GeO₄:Pr³⁺ and Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors were fabricated by a solid state reaction. The phase and luminescent properties of the fabricated phosphors were investigated. The XRD patterns show that all of the fabricated phosphors have an orthorhombic structure. The fabricated Zn₂GeO₄ shows an emission band in the range of 350–550 nm. The fabricated Zn₂GeO₄:Mn²⁺ and Zn₂GeO₄:Pr³⁺ phosphors show emission bands corresponding to Mn²⁺ and Pr³⁺ ions, respectively. The fabricated Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor shows the emission band results from Mn²⁺ and the codoped Pr³⁺ enhances the emission intensity of Mn²⁺. Moreover, Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor exhibits longer decay time than that of Zn₂GeO₄:Mn²⁺. The higher intensity and longer lifetime of Mn²⁺ emission are induced by the energy transfer from Pr³⁺ of various vacancies to Mn²⁺ in Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors.     

Synthesis and thermoluminescence properties of CdB<Subscript>4</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript> and CdB<Subscript>4</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>2+</Superscript>

Polycrystalline samples of undoped, terbium-doped (CdB₄O₇:Tb³⁺), and manganese-doped (CdB₄O₇:Mn²⁺) cadmium tetraborate have been prepared by solid-state reactions at 850°C. Using differential scanning calorimetry and X-ray diffraction, we have determined the melting point of CdB₄O₇ (t _m = 976°C) and shown that this compound melts incongruently. The observed monotonic decrease in the orthorhombic cell parameters of the doped materials indicates the formation of substitutional solid solutions (sp. gr. Pbca). The thermoluminescence intensity of the doped materials has been shown to depend on the nature and concentration of the activators and the irradiation time.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

Influence of Mg<Superscript>2+</Superscript>/Ga<Superscript>3+</Superscript> doping on luminescence of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphors

Mg²⁺/Ga³⁺ doped Y₃Al₅O₁₂:Ce³⁺ phosphors were synthesized through a solid state reaction. The phase and luminescent of the synthesized phosphors were investigated. For Ga³⁺ codoped Y_2.96Ce_0.04Al_(5?x)Ga_xO₁₂ phosphors, the emission intensity increases with the increase of Ga³⁺ concentration up to Y_2.96Ce_0.04Al_4.80Ga_0.20O₁₂ and then decreases with a further increase of Ga³⁺ concentration, but the emission peak shifts to shorter wavelength continuously in the Ga³⁺ doping concentration range of 0.05–0.25. For Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors, the emission intensity decreases and the emission peak shifts to longer wavelength continuously in the Mg²⁺ doping concentration range of 0.02–0.12. The emission spectra of Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors demonstrate that the codoped Mg²⁺/Ga³⁺ ions not only induce the enhancement of Y_2.96Ce_0.04Al₅O₁₂ emission intensity but also lead to the red shift of Y_2.96Ce_0.04Al₅O₁₂ emission peak. The decay lifetimes decrease in Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al₅O₁₂ phosphors due to defects formed by substitutions of Y³⁺ by Mg²⁺/Ga³⁺.     

Synthesis and properties of laser-active liquids POCl<Subscript>3</Subscript>-SbCl<Subscript>5</Subscript>-<Superscript>235</Superscript>UO<Stack><Subscript>2</Subscript><Superscript>2+</Superscript></Stack>-Nd<Superscript>3+</Superscript>

The effect of the synthesis conditions on the properties of inorganic laser-active liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ is considered. The kinetic dependences of the U(IV) content and decay time of the Nd³⁺ luminescence in POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions for various synthesis procedures at 380 K have been obtained. In POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions, nonradiative energy transfer Nd³⁺ → U⁴⁺ is observed, and quenching of the Nd³⁺ luminescence is described by the Stern-Volmer law: k _q = (6.4 ± 0.6) × 10⁵ l mol^?1 s^?1. Laser liquids POCl₃-SbCl₅-²³⁵UO ₂ ²⁺ -Nd³⁺ with neodymium concentration of up to 0.7 M, uranyl concentration of up to 0.1 M, and decay time of the Nd³⁺ luminescence of up to 220 μs have been prepared for the first time.     

Spectral parameters of Er<Superscript>3+</Superscript> ion in Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>:KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The spectral parameters of Er³⁺ in Yb³⁺/Er³⁺:KY(WO₄)₂ crystal with space group C2/c have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained: the intensity parameters are: ₂ = 6.33 × 10^–20 cm², ₄ = 1.35 × 10^–20 cm², ₆ = 1.90 × 10^–20 cm². The radiative lifetime and the fluorescence branch ratios were calculated. The emission cross section _e (at 1536 nm) is 2.0 × 10^–21 cm².     

Recombination luminescence of CaI<Subscript>2</Subscript> crystals activated with Eu<Superscript>2+</Superscript>, Gd<Superscript>2+</Superscript>, Tl<Superscript>+</Superscript>, Pb<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript>

The spectral characteristics of thermostimulated luminescence, steady-state roentgenoluminescence and photostimulated luminescence (PSL) buildup and decay kinetics, and the effect of IR irradiation on the roentgenoluminescence yield and glow curves of CaI₂:Eu²⁺, CaI₂:Gd²⁺, CaI₂:Tl⁺, CaI₂:Pb²⁺, CaI₂:Mn²⁺, and CaI₂: Pb²⁺, Mn²⁺ crystals grown by the Bridgman-Stockbarger method have been studied in the temperature range 90–295 K. Coupled with earlier data, the present results on the influence of oxygen and hydrogen impurities on the spectral characteristics of CaI₂ indicate that the activation of calcium iodide with Eu²⁺, Gd²⁺, Tl⁺, Pb²⁺, and Mn²⁺ leads to the formation of cation impurity-native defect complexes, which act as carrier traps and are responsible for the thermostimulated luminescence in the range 150–295 K. IR exposure after 90-K x-ray excitation gives rise to flash PSL and influences the thermostimulated luminescence light sum. The nature of the emission and trapping centers involved and the mechanisms of recombination luminescence excitation in the crystals are discussed.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Hydrothermal synthesis and photoluminescence properties of Y<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>:Tb<Superscript>3+</Superscript> phosphors

This article presents the synthesis and photoluminescence (PL) properties of Y₂Zr₂O₇:Tb³⁺. The Tb³⁺-doped Y₂Zr₂O₇ zirconates were successfully synthesized by a hydrothermal process at 200 °C for 20 h. X-ray diffractometer (XRD) patterns revealed that all of the products were phase-pure with the fluorite structure. PL study showed that the Y₂Zr₂O₇:Tb³⁺ phosphors exhibited obvious PL emission peaks which located at 490, 545, 585, and 623 nm; the dominant emission located at 545 nm is assigned to ⁵D₄ → ⁷F₅ transition. Furthermore, Tb³⁺-doping concentration strongly affected the PL properties, and the quenching concentration is 5 at.%.     

Synthesis and crystal structure of Cu<Subscript>2</Subscript>{(UO<Subscript>2</Subscript>)<Subscript>3</Subscript>[(S,Cr)O<Subscript>4</Subscript>]<Subscript>5</Subscript>}(H<Subscript>2</Subscript>O)<Subscript>17</Subscript>

Cu₂{(UO₂)₃[(S,Cr)O₄]₅}(H₂O)₁₇ crystals were prepared by evaporation of aqueous solutions. The crystal structure was solved by the direct method and refined to R ₁ = 0.064 (wR ₂ = 0.177) for 8120 reflections with ¦F _hkl¦ 4 ¦F _hkl¦. Rhombic system, space group Pbca, a = 18.0586(8), b = 19.9898(9), c = 20.5553(8) Å, V = 7420.2(6) ų. The structure is based on {(UO₂)₃[(S,Cr)O₄]₅}^4– anionic layers, formed by combination of UO₇ pentagonal bipyramids and TO₄ tetrahedra through common vertices. The { (UO₂)₃ [(S,Cr)O₄]₅}^4– layers are parallel to the (010) plane. The Cu²⁺ (H₂O)₆ octahedra and additional water molecules are located in the interplanar space and provide binding of the layers in the structure by hydrogen bonds. Based on the occupancy of tetrahedral positions, more accurate chemical formula of the compound should be written as Cu₂{(UO₂)₃[(S_0.804 Cr_0.196)O₄]₅} (H₂O)₁₇.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 408–411.Original Russian Text Copyright © 2004 by Krivovichev, Burns.     

Luminescent properties of Pb<Superscript>2+</Superscript>- and Mn<Superscript>2+</Superscript>-activated CdI<Subscript>2</Subscript> crystals

The luminescent properties of CdI₂, CdI₂:Pb²⁺, CdI₂:Mn²⁺, and CdI₂:Pb²⁺,Mn²⁺) crystals have been studied at temperatures from 85 to 295 K under optical and x-ray excitation. Analysis of new and earlier spectroscopic data suggests that the 560-nm luminescence of CdI₂:Pb²⁺ and CdI₂:(Pb²⁺,Mn²⁺) crystals under excitation on the long-wavelength component of the A absorption band of Pb²⁺ centers is due to Pb²⁺-bound anion excitons. The 640-to 660-nm emission of these crystals is attributable to α centers. The manganese luminescence in the codoped material originates from both intracenter Mn²⁺ excitations and a sensitized process due to energy transfer from the host and Pb²⁺-related centers. The mechanisms of recombination and energy transfer processes in cadmium iodide crystals codoped with Pb²⁺ and Mn²⁺ are discussed.     

Luminescence of Pb<Superscript>2+</Superscript> in MAl<Subscript>2</Subscript>B<Subscript>2</Subscript>O<Subscript>7</Subscript> (M = Ca,Sr)

Pb²⁺ doped SrAl₂B₂O₇ was prepared by solution combustion synthesis. The synthesized material was determined by powder XRD. The photoluminescence properties of the synthesized phosphor were investigated at room temperature using a spectrofluorometer. The emission peak of Pb²⁺ doped SrAl₂B₂O₇ was observed at 420 nm upon excitation at 277 nm. The Stokes shift of SrAl₂B₂O₇:Pb²⁺ was calculated to be 12 292 cm⁻¹. The luminescence behavior of Pb²⁺ in both SrAl₂B₂O₇ and CaAl₂B₂O₇ was discussed. The text was submitted by the authors in English.     

Phase conversion and spectral properties of long lasting phosphor Zn<Subscript>3</Subscript> (PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Mn<Superscript>2+</Superscript>, Ga<Superscript>3+</Superscript>

A red long lasting phosphor Zn₃(PO₄)₂:Mn²⁺,Ga³⁺ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from α-Zn₃(PO₄)₂, β-Zn₃(PO₄)₂ toγ-Zn₃(PO₄)₂ occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.     

Synthesis,tunable luminescence and thermal stability of Mg<Subscript>2</Subscript>Al<Subscript>4</Subscript>Si<Subscript>5</Subscript>O<Subscript>18</Subscript>:Ce<Superscript>3+</Superscript>/Mn<Superscript>2+</Superscript> phosphors

Ce³⁺/Mn²⁺ singly doped and codoped Mg₂Al₄Si₅O₁₈ phosphors were synthesized by a solid state reaction. The phase, luminescent properties and thermal stability of the synthesized phosphors were investigated. Ce³⁺ and Mn²⁺ singly doped Mg₂Al₄Si₅O₁₈ phosphors show emission bands locating in blue and yellow–red regions, respectively. In Ce³⁺ and Mn²⁺ codoped Mg₂Al₄Si₅O₁₈, tunable luminescence was obtained because of the energy transfer from Ce³⁺ to Mn²⁺. In Mg₂Al₄Si₅O₁₈:Ce³⁺/Mn²⁺ phosphors with a fixed Ce³⁺ concentration, energy transfer efficiency increases with the increasing Mn²⁺ concentration, which is confirmed by the continually decreasing intensity and shortening decay time of Ce³⁺ emission. Moreover, the luminescent properties and thermal stability provide a great significance on the applications in the field of light emitting diodes.     

The influence of activation of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> polycrystalline matrices by Bi<Superscript>3+</Superscript> ions on the luminescence of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

The influence of activation of the Y₂O₃ matrix of the Y₂O₃:Eu³⁺ phosphor by Bi³⁺ ions on the luminescence of Eu³⁺ and Bi³⁺ ions in it and on conditions of the excitation energy transfer to luminescence centers is studied. It is shown that the presence of Bi³⁺ ions leads to the appearance of recombination luminescence with participation of bismuth ions at low concentrations (up to 6–8 at %) of the dominant activator europium and to an increase in the threshold of intrinsic concentration quenching of its luminescence.     

Photoluminescence of Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>:Sm<Superscript>2+</Superscript> crystals

The photoluminescence spectra of Ga₂S₃:Sm²⁺ crystals have been measured in a wide temperature range (77–450 K). The results have been used to identify the mechanisms of the luminescence and energy transfer from the host to the rare-earth ion.