Stability of divalent/trivalent oxidation state of europium in some Sr-based inorganic compounds

This work investigates the stability of Eu²⁺ and Eu³⁺ in some Sr-based inorganic compounds. Generally reducing condition is adopted in order to obtain Eu²⁺, however, the Eu doped SrAl₂O₄/SrLaAlO₄ case indicates that for some compounds Eu³⁺ is stabilized even in reducing atmosphere. Bond valence method is applied to explain this phenomenon and it reveals that crystal structure also determines the valence state of europium cations along with reducing/oxidizing condition. An analysis of other Eu doped Sr-based materials is performed which shows the relationship between Eu²⁺/Eu³⁺ stability and the Global Instability Index (GII). This research provides a guideline for synthesizing specific novel Eu²⁺/Eu³⁺ phosphors.     

Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2

The surface composition and chemical environment of LiCoO₂, hexagonal LiNiO_2, cubic LiNiO₂, and the mixed transition metal oxide LiNi_0.5Co_0.5O₂ have been determined by Auger electron and X-ray photoelectron spectroscopies. While the LiCoO₂ surface properties can easily be extrapolated from bulk composition, the nickel-containing materials are less straightforward. Their surface concentration tends to be depleted in lithium relative to that of the bulk and shows an atypical chemical environment for the constituent elements. The Ni 2p XPS photoemission suggests a near “ NiO-like” selvedge through the XPS binding energies and satellite structure which are essentially identical to that of NiO; the spectrum appears fairly insensitive to lithium concentration. Although there is little evidence for higher binding energy Ni³⁺ species or for an electron poor Ni^2.δ+-derived band structure in the XPS, the lattice oxygen is very electron-rich and yields among the lowest binding energies reported for a transition metal oxide. The nickel-containing lithium oxide selvedge is thus not simply “NiO” and the surface lithium cations have a measurable effect on the electronic structure even in their more highly depleted levels. This is explained in the context of the charge-transfer model of the oxide band structure.     

Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

Using of chelating resin to study the kinetic desorption of Eu(III) from humic acid-Al2O3 colloid surfaces

The association of organic-inorganic colloid-borne trace elements was investigated. Radionuclide ^152+154Eu(III) was chosen as a representative and chemical homologue for trivalent lanthanide and actinide ions present in radioactive nuclear waste. Effect of pH and contact time of organic-inorganic/Eu(III) on the kinetic dissociation of Eu(III) from HA-Al₂O₃ colloids was studied. The kinetic desorption behavior of sorbed ^152+154Eu(III) from humic acid-γ-Al₂O₃ colloids was studied at pH values of 4.5 ± 0.2, 5.3 ± 0.2 and 6.5 ± 0.2, respectively, by the addition of the chelating resin. The experimental results suggest that the fractions of irreversible sorption of radionuclide ^152+154Eu(III) to HA-Al₂O₃ colloids increase with increasing pH values, and are independent of aging time. At least two different species, “weak” and “strong” dissociation fractions, are required to simulate the kinetic desorption of ^152+154Eu(III) from HA-Al₂O₃ colloids. The species of Eu(III) sorbed on HA-Al₂O₃ colloids move from “weak” sites to “strong” sites with increasing aging time, whereas the fractions of irreversible sorption are independent of aging time. The results are important for the evaluation of radionuclides’ behavior in the environment.     

One-step reverse precipitation synthesis of water-dispersible superparamagnetic magnetite nanoparticles

A convenient method for preparation of pure and doped yttrium oxide was developed, which is based on irradiation of solutions containing yttrium nitrate and ammonium formate with UV light or accelerated electrons. Solid phase formed under irradiation was consequently calcined at 500?°C or higher temperatures to obtain nanocrystalline yttrium oxide. Addition of small amount of cerium(III) or europium(III) nitrates to irradiated solutions resulted in doping of yttrium oxide with Ce(III) or Eu(III) ions. Under both types of irradiation, the method yields material with high specific surface area, consisting of spherical nanoparticles 25?C100?nm in diameter depending on preparative conditions and post-radiation treatment and with narrow size distribution. In the doped oxides (Y₂O₃:Ce or Y₂O₃:Eu), radioluminescence spectra typical for Ce³⁺ or Eu³⁺ doped oxide structures were observed.     

X-ray photoelectron spectroscopy of rare-earth compounds

A variety of rare-earth (RE) compounds (oxides, sulfates and oxalates) have been studied by X-ray photoelectron spectroscopy. Except for Eu, the binding energies (BE's) of the RE 3d and 4d peaks for the sulfates and oxalates are respectively almost equal to and 1.3–3.1 eV higher than those for the oxides. In the Eu 3d spectrum of europium(II) oxalate, distinct shake-down satellite peaks are present, and the BE's of these peaks are 1̃0 eV lower than the parent ones. For the oxides, appreciable differences are found in the BE's of the O 1s peaks, and a specific “inclined W” form is observed in plots of BE versus 1/R (where R is the mean distance from the oxygen atom to the neighboring RE atom) and versus the RE oxidation-reduction potential (ORP). No characteristic differences are seen in the BE's (C 1s, S 2s and S 2p) of the other ligands.     

Influences of compositions and ligands on photoluminescent properties of Eu(III) ions in composite europium complex/PMMA systems

Three kinds of europium complexes; Eu(phen)₂Cl₃(H₂O)₂, Eu(DN-bpy)phenCl₃(H₂O)₂ and Eu(DB-bpy)phenCl₃(H₂O)₂ (phen: 1,10-phenanthroline, DN-bpy: 4,4′-Dinonyl-2,2′-dipyridyl, DB-bpy: 4,4′-Di-tert-butyl-2,2′-dipyridyl) were prepared and then incorporated into polymethyl methacrylate (PMMA) matrix with different molar ratios of CO groups/Eu³⁺ ions. The final solid composites were formed by a self-assembly process among Eu³⁺ ion, the ligands and PMMA during the solvent evaporation process, and then the ligands re-coordinate to Eu(III). It was found that the ligands affect not only the emission properties of the pure complexes, but also the miscibility of the complexes and PMMA. More than one kind of symmetric sites of Eu³⁺ ions were formed in the composites due to the coordination of CO in PMMA to Eu³⁺ ions. The micro-environments of Eu(III) in the composites were changed with the compositions and the ligands, leading to the change in the crystalline structure, and consequently, the emission characteristics.     

Valence band states of semi-magnetic semiconductors: Cd1-xMnxTe

Valence band electron states of Cd_1-xMn_xTe mixed crystals were determined over the composition range 0?x?0.7 by ultra-violet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). A peak at 3.5 eV binding energy (BE) whose magnitude increases with the manganese mole fraction x was identified as originating from the Mn 3d⁵ level. A previously reported structure at 6.5 eV BE was also observed for x>0.4; it is, however, believed to be a satellite of the 3.5 eV peak originating from a shake-up process.     

Quadrupole interactions at europium sites in Eu3V2O7 and Eu2VO4

The electric-quadrupole interactions at the Eu sites in Eu₃V₂O₇ and Eu₂VO₄ oxides have been studied at room temperature with¹⁵¹Eu Mössbauer spectroscopy. Both divalent and trivalent Eu ions were found in the oxides. The fraction of Eu²⁺ is 17.1(8)% in Eu₃V₂O₇ and 39.0(1.6) % in Eu₂VO₄. The values of the quadrupole coupling constant, eV_zzQ_g, obtained from the fits using a full Hamiltonian method are ?6.594(50) and ?8.043(65) mm/s for Eu³⁺, and ?13.168(402) and ?18.032(134) mm/s for Eu²⁺, respectively in Eu₃V₂O₇ and Eu₂VO₄. The magnitude of eV_zzQ_g in Eu₂VO₄ is the largest ever reported for Eu²⁺ in any Eu oxide system.     

Photoelectron spectroscopic investigation of transformation of trifluoroacetate precursors into superconducting YBa2Cu3O7−δ films

X-ray photoelectron spectroscopy (XPS) has been used to investigate the evolution of surface chemistry of YBa₂Cu₃O_7−δ (Y123) films prepared by the metalorganic deposition (MOD) process using trifluoroacetate (TFA) precursors. Detailed XPS core-level spectra obtained from the samples quenched from various points during the calcining and firing stages have been reported for the first time and are used to identify surface species. The XPS data show evidence of formation of intermediate phases such as Y-O-F, BaF₂, and CuO during the calcining process, which are the decomposition products of yttrium, barium, and copper trifluoroacetates, respectively. The TFA precursors are completely decomposed at the end of calcination. The change of binding energies for Y 3d_5/2, Ba 3d_5/2, and O 1s during the firing process indicates that Y123 starts to form at 800 °C after 0.5 h firing. Based on the experimental results, an alternative mechanism of the chemical evolution from precursor to final film in the TFA-MOD process is proposed.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

Cathodic electrodeposition of mixed oxide thin films

Cathodic electrodeposition is a rather unexplored route for the synthesis of mixed oxides. Two different mechanisms are generally reported which lead to oxide thin film formation: (i) the direct reduction of the oxidation state of the metallic elèment, (ii) an interfacial pH increase and local supersaturation followed by oxide precipitation. We emphasize the major requirements for mixed thin film formation via electrosynthesis and present results obtained with two different systems of special interest. The first, ZnO/Eu(OH)_x, is based on the second mechanism. The second, TiO₂/WO₃, is a mixed mechanism process. We describe the conditions under which europium oxide can be deposited cathodically. This oxide is obtained by co-deposition with zinc oxide. After a heat treatment at 400 °C, X-ray diffraction shows that the films are mainly made of monoclinic Eu₂O₃. The successful WO₃–TiO₂ mixed film electrodeposition in a wide compositional range is also reported.     

Quantitative determination of Eu and Eu content in (Eu,Y)-Si-Al-O-N glasses by magnetic measurements

This paper describes a method to determine the oxidation state of europium by means of magnetic measurements. The feasibility of this method is demonstrated using Eu-doped Y-Si-Al-O-N glasses as a model system. Magnetic measurements at (Eu,Y)-Si-Al-O-N glasses show that Eu is completely present as divalent ion for low Eu concentrations (Eu_0.152Y_15.0Si_14.7Al_8.7O_54.1N_7.4). At high Eu concentrations (Eu_15.2Si_14.7Al_8.7O_54.1N_7.4) a maximum of 5 at.% could be present as Eu³⁺.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Mexiletine

The 60 MHz ¹H NMR spectra of mexiletine, 1-(2,6-dimethylphenoxy)-2-propanamine, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent, tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) europium(III), 2, Eu(FOD)₃, and the chiral reagents tris[3-(trifluoromethylhydroxymethylene)-d-camphorato]europium(III), 3, Eu(FACAM)₃, and tris[3-(heptafluoropropylhydroxymethylene)-d-camphorato]europium(III), 4, Eu(HFC)₃. Substantial lanthanide-induced shifts were seen for the proton signals of 1 with each reagent. Appreciable enantiomeric shift differences were seen for both methyl signals and for each of the CH₂CH proton signals using 3 and 4 that should permit direct determinations of enantiomeric excess for samples of 1. A predominant conformation for 1 is suggested based on observed splittings of the CH₂ proton signals and their relative lanthanide-induced shifts.     

Eu substitution and particle size control of Y2O2S for the excitation by UV light emitting diodes

Yttrium oxysulfide doped with europium (Y₂O₂S:Eu³⁺) red phosphor is used in UV light emitting diodes (LEDs) by mixing with blue and green phosphors to generate white light which are important for the application in general lighting. Here, we demonstrate the effect of shape and size and the concentration of activator (Eu) of red Y₂O₂S phosphor.     

Photoluminescence of (Ba1−xEux)Si6N8O (0.005≤x≤0.2) phosphors

Eu²⁺-doped BaSi₆N₈O phosphors (Ba_1−xEu_xSi₆N₈O, 0.005≤x≤0.2) were synthesized by gas-pressure sintering of the powder mixture of BaCO₃, Si₃N₄, and Eu₂O₃ at 1750 °C under 0.5 MPa N₂. The fired powder consists of a major BaSi₆N₈O phase and a trace amount of impurity phases. The structural result of the BaSi₆N₈O powder, refined by the Rietveld method, agrees well with that of single crystals. A wide blue luminescence band peaking at about 500 nm is observed in BaSi₆N₈O:Eu²⁺, upon excitation with the ultraviolet light of 310 nm. Although Eu is covalently bonded to six nearest neighbor nitrogen atoms, the luminescence of Eu²⁺ is not significantly redshifted but shows a very narrow excitation spectrum at high energies. The origin of the short-wavelength luminescence is mainly ascribed to a small crystal-field splitting as a result of extremely long distances between europium and nitrogen ligands in BaSi₆N₈O:Eu²⁺.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Methastyridone, 2,2-Dimethyl-5-(2-Phenylethenyl)-4-Oxazolidinone

Abstract

The 60 MHz ¹H NMR spectra of methastyridone, 2,2-dimethyl-5-(2-phenylethenyl)-4-oxazolidinone, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 2, Eu(FOD)₃, and the chiral reagent tris[3-(heptafluoropropylhydroxy-methylene)-d?camphorato]europium(III), 3, Eu(HFC)₃.     

Luminescence study of some yttrium tantalate-based phosphors

Yttrium tantalate (YTaO₄), yttrium niobium-tantalate (YTaNbO₄), yttrium niobate (YNbO₄), europium and terbium activated yttrium tantalate (YTaO₄:Eu, YTaO₄:Tb) and europium activated yttrium niobate (YNbO₄:Eu) phosphors were prepared by solid-state reaction, from a homogeneous mixture consisting of Y₂O₃, Eu₂O₃, Tb₄O₇, Ta₂O₅, Nb₂O₅ and Na₂SO₄ as flux. Photoluminescence (PL), thermally stimulated luminescence (TSL), X-ray diffraction (XRD) and scanning electron microscopy (SEM) of yttrium tantalate based phosphors are reported. In the present study TSL characteristics of these phosphors were first investigated and reported after exposure to beta, UV (311 nm) and X-ray radiations.     

Synthesis, characterization, and luminescent properties of Lu2O3:Eu phosphors

Eu-doped lutetia (Lu₂O₃:Eu) nano-phosphors were synthesized by the sol-gel combustion process from a mixed aqueous solution of europium and lutetium nitrates, using organic glycine as the fuel. Powder X-ray diffraction shows that cubic Lu₂O₃:Eu crystallites are directly obtained by the sol-gel combustion process without further calcination. Electron microscopy reveals that the as-prepared phosphors are agglomerated and have a fluffy, fine, and porous morphology, consisting of primary particle size of 8-10 nm. The excitation spectrum is characterized by three dominant bands centered at 395, 466, and 534 nm, respectively. Both the photoluminescent and radioluminescent spectra are very similar and exhibit intense emission peaks centered at 612 nm due to ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The energy transfer from Lu₂O₃ host to Eu³⁺ activator is more efficient in the case of calcined phosphors than for the as-prepared phosphors due to their improved lattice perfection.     

Magnetic,electronic and structural properties of ZnxFe3−xO4

A series of samples Zn_xFe_3−xO₄ have been prepared by the chemical coprecipitation technique and characterized by X-ray diffraction (XRD), vibrating sample magnetometry (VSM) and X-ray photoelectron spectroscopy (XPS). XRD demonstrates all the samples of Zn_xFe_3−xO₄ have a spinel structure same as Fe₃O₄. The magnetic hysteresis loops of Zn_xFe_3−xO₄ obtained from VSM indicate that the saturation magnetization has a maximum when x is ∼1/3. The chemical states of Fe atoms and Zn atoms in zinc ferrites have been measured using XPS and Auger electron spectroscopy (AES). The Fe 2p core-level XPS spectra and Zn L₃M₄₅M₄₅ Auger peaks have been analyzed and the results have been discussed in correlation with the samples’ magnetic properties. These results suggest most of Zn atoms occupy the tetrahedral sites and a small amount of them occupy the octahedral sites.