Preparation, characterization and luminescence properties of ultrathin films containing polyoxometalates

Ultrathin multilayer films of poly(allylamine hydrochloride) (PAH) and a polyoxotungstoeuropate cluster K-13[Eu(SiW11O39)(2)] (Eu(SiW11)(2)) have been prepared by the layer-by-layer self-assembly method. The Eu(SiW11)(2)/PAH multilayer films have been characterized by X-ray photoelectron spectra and atomic force microscopy (AFM). UV-Vis measurements reveal regular film growth with each Eu(SiW11)(2) adsorption. The photoluminescent behavior of the film at room temperature was to show the characteristic Eu3+ emission pattern of D-5(o) --> F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent multilayers with polyoxometalates.

Improvement of luminescence efficiency by electrical annealing in single-layer organic light-emitting diodes based on a conjugated dendrimer

In this paper, we study the effects of electrical annealing at different voltages on the performance of organic light-emitting diodes. The light-emitting diodes studied here are single-layer devices based on a conjugated dendrimer doped with 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole as the emissive layer. We find that these devices can be annealed electrically by applying a voltage. This process reduces the turn-on voltage and enhances the brightness and efficiency. We obtained an external electroluminescence quantum efficiency of 0.07% photon/electron and a brightness of 2900 cd m(-2) after 12.4 V electrical annealing, which are about 6 times and 9 times higher than un-annealing devices, respectively. The improved luminance and efficiency are attributed to the presence of a space charge field near the electrodes caused by charging of traps.

XAFS at Eu-L-3 edge and UV-VUV excited luminescence of europium doped strontium borophosphate prepared in air

The local structure and the valences of europium in SrBPO5:Eu prepared in air were checked by means of XAFS at Eu-L-3 edge. From the EXAFS results, it was discovered that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.42 Angstrom in the host. From the XANES data, it was found that the divalent and trivalent europium coexisted in the matrix. The emission spectra excited by VUV or UV exhibited a prominent broad band due to the 4f(6)5d-4f(7) transition of Eu2+ ions, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Sr]" formed by aliovalent substitution between Sr2+ and Eu3+ ions. The VUV excitation spectra in 100-200 nm range showed that the matrix had absorption bands with the maxima at about 130 and 150 nm, respectively.

Preparation and luminescence properties of the mesoporous MCM-41s intercalated with rare earth complex

Rare earth complex Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1.10-phenanthroline) hits been incorporated into unmodified MCM-41 and modified MCM-41s by aminopropyltriethoxysilane (APTES) or N-[(3-triethoxysilyl)propyl]ethylenediamine(TEPED). Thus, the assemblies of unmodified or modified MCM-41s with rare earth (RE) complex have been obtained. XRD spectra. NMR spectra. diffuse reflectance spectra. and the luminescence spectra were used to characterize the pure RE complex and the corresponding assemblies. The assemblies have better luminescence properties under UV irradiation. and their fluorescence lifetimes on the excited state are longer than that of the corresponding pure complex. The possible mechanisms are also discussed in the context.

Synthesis and luminescence properties of oxyapatite NaY9Si6O26 doped with Eu3+, Tb3+, Dy3+ and Pb2+

Oxyapatite NaY9Si6O26 was prepared by sol-gel method. By choosing the precursors, a single phase compound was obtained. This soft chemical method lowered the reaction temperature by 100degreesC compared with the solid state method. Its morphology was studied by transmission electron microscopy (TEM). Several rare earth ions (Eu3+, Tb3+, Dy3+) and Pb2+ ion were doped in this compound. The high resolution emission spectrum of Eu3+ showed that rare earth ions occupied two yttrium sites. In spite of the charge imbalance of Pb2+ with the cations in this compound, it was found that Pb2+ could emit in UV range and transfer its excitation energy to Dy3+ ion.

VUV excited luminescence of europium activated calcium borophosphate prepared in air

XAFS (EXAFS and XANES) at Eu-L-3 edge were used to determine the local structure and the valences of europium in CaBPO5:Eu prepared in air. The results of EXAFS showed that the doped europium atoms were nine-coordinated by oxygen atoms and the distances of bond Eu-O were 2.39 Angstrom in the host lattice. XANES at Eu-L-3 edge exhibited that Eu2+ and Eu3+ coexisted in the matrix. The luminescent spectrum of the material excited by VUV at 147 nm presented a similar spectrum with that excited by f-f transition of Eu2+ at 396 nm and f-d transition of Eu2+ at 312 nm. The broad emission band due to both 4f(6)5d - 4f(7) transition of EU2+ and f - f transition of Eu3+ could be observed in emission spectra, which indicated that the trivalent europium ions were reduced in air in the matrix at high temperature by the defects [V-Cn]" formed by aliovalent substitution between Ca2+ and Eu3+ ions. The UV excitation spectrum showed the typical f-f transition of Eu3+ and f-d transition of Eu2+. The bands with the maxima at about 113 and 158 nm in VUV excitation spectrum were assigned to originate from the absorption of the host lattice.

Preparation, patterning and luminescence properties of rare earth-doped YVO4 nanocrystalline phosphor films via sol-gel soft lithography

In this presentation, nanocrystalline YVO4:A (A=Eu3+, Dy3+, SM3+, Er3+) phosphor films and their patterning were fabricated by a Pechini sol-gel process combined with a soft lithography (micro-molding in capillaries). XRD, FT-IR, AFM and optical microscope, absorption spectra, 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 400 degrees C and the crystallinity increased with the increase of annealing temperatures. Transparent nonpattemed phosphor films were uniform and crack free, which mainly consisted of grains with an average size of 90nm. Patterned crystalline phosphor film bands with different widths (5-30 mu m) were obtained. The doped rare earth ions (A) showed their characteristic emission in crystalline YVO4 phosphor films due to an efficient energy transfer from vanadate groups to them. The Sm3+ and Er3+ ions also showed upconversion luminescence in YVO4 film host. The optimum concentration for Eu3+ was determined to be 7 mol% and those for Dy3+, Sm3+, Er3+ were 2 Mol% of Y3+ in YVO4 films, respectively.

Sol-gel preparation and luminescence properties of nano-structured hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)(3)(.)phen: where HTTA=1-(2-thenoyl)-3,3,3-trifluoracetone and phen=1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu3+, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu3+ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate, the inorganic/polymer hybrid material containing Eu(TTA)(3)(.)phen has also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)(3)(.)phen.

Preparation and luminescence properties of ormosil material doped with Eu(TTA)(3)phen complex

The europium complex, Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix-SiO2/(VTMOS+PMMA) (VTMOS = vinyltrimethoxysilane, PMMA = polymethylmethacrylate) via sol-gel process, and the luminescence properties of the resultant ormosil composite phosphors [ormosil: Eu(TTA)(3)phen were investigated compared with those of the pure Eu(TTA)(3)phen complex powder. The ormosil composite materials incorporated with Eu(TTA)(3)phen show the characteristic red emission of Eu3+ ion. The Eu3+ possesses fewer emission lines and longer lifetime in the hybrid phosphor than in the pure Eu(TTA)(3)phen complex. This has been explained from the viewpoint of the surrounding environment where the Eu3+ ion lies. (C) 2000 Elsevier Science B.V. All rights reserved.

Luminescence properties of Eu(phen)(2)Cl-3 doped in sol-gel-derived SiO2-PEG matrix

Rare earth complex Eu(phen)(2)Cl-3 was introduced into a SiO2-PEG-400 hybrid material by a sol-ger method. The result indicated that Poly(ethylene glycol) (PEG) could associate with Eu3+ and change the surroundings of Eu3+ in the hybrid material, greatly improving the decay time. Transparent SiO2-PEG400 hybrid doped with a very small amount of Eu(phen)(2)Cl-3 has better mechanical properties and can retain excellent luminescence properties of the rare earth complex. (C) 2000 Elsevier Science B.V. All rights reserved.

Preparation and luminescence properties of sol-gel hybrid materials incorporated with europium complexes

Microporous silica gel has been prepared by the sol-gel method utilizing the hydrolysis and polycondensation of tetraethylorthosilicate (TEOS). The gel has been doped with the luminescent ternary europium complex Eu(TTA)(3). phen: where HTTA = 1-(2-thenoyl)-3,3,3-trifluoracetone and phen = 1,10-phenanthroline. By contrast to the weak f-f electron absorption bands of Eu3+, the complex organic ligand exhibits intense near ultraviolet absorption. Energy transfer from the ligand to Eu3+ enables the production of efficient, sharp visible luminescence from this material. Utilizing the polymerization of methyl methacrylate or ethyl methacrylate, the inorganic/polymer hybrid materials containing Eu(TTA)(3). phen have also been obtained. SEM micrographs show uniformly dispersed particles in the nanometre range. The characteristic luminescence spectral features of europium ions are present in the emission spectra of the hybrid material doped with Eu(TTA)3 phen. (C) 2000 Kluwer Academic Publishers.

Displacement and luminescence of Eu3+ in CaYBO4

CaY1-xBO4: xEu was synthesied by solid state reaction method, and the displacement and luminescence of the Eu3+ in CaYBO4 host were studied. Two luminescent centers could be observed at certain Eu3+-concentration, indicating that the Eu3+ occupies two different crystallographic sites. This result shows that the Eu3+ occupies two different Y3+ sites in CaYBO4. The investigation on Eu-O charge transfer bands indicates that the larger distortion or the lower symmetry of Eu3+ site is,the shorter wavelength of the Eu-O charge transfer band is. When the Eu3+-concentration is high (x > 0.10), Eu3+ occupies the sites of Ca2+ and is reduced to Eu2+.

Luminescence centers and valence change of Eu2+ in KCaF3

The nature of the emission centers and the valence change of Eu2+ in KCaF3:Eu2+ depends strongly on preparation conditions. Experimental results show that there are two different d-->f emission bands, located at 425 and 510 nm, respectively. Their origin, relationship, and the effect of doping concentration on them are discussed. A Eu2+-Eu3+ valence change process is proposed. (C) 2000 Elsevier Science Ltd. All rights reserved.

Synthesis, 2D NMR, electrochemistry and luminescence of ruthenium(II) complexes with 2,2 '-bipyridine and 5-(omega-bromoalkylamido)-1,10-phenanthroline

The efficient synthesis of 5-(5-bromovaleramido)-1,10-phenanthroline, 5-(6-bromohexanamido)-1,10-phenanthroline, and 5-(11-bromoundecanamido)-1,10-phenanthroline are described, which reacted with cis-Ru(bpy)(2)Cl-2. 2H(2)O and sodium hexafluorophosphate to form Ru(bpy)(2)[phen-NHCO(CH2)(n)Br](PF6)(2) (n = 4, 5 or 10; phen = 1,10-phenanthroline). The intricate H-1 NMR spectra at low field of these complexes were completely assigned in virtue of H-1-H-1 COSY technique. Cyclic voltammetry was used to study electrochemical behaviours of these complexes, and their luminescent properties were investigated with fluorescent spectra.

Studies on plant extracellular calmodulin by lanthanide luminescence probe

Plant extracellular calmodulin (CaM) has been purified from cauliflower and identified with NAD kinase(NADK) activation and inhibition effect of CaM antagonist W7, Tb-3.1 fluorescence titration showed that extracellular CaM contained four metal-binding sites, The excitation spectrum and emission specturm indicated that extracellular CaM contained one tyrosine residue which could transfer energy to bound Tb3+. Based on Forster type nonradiative energy transfer theory, the distances of Tyr-->sites III, IV have been determined, these are 1. 104 nm(Tyr --> III, site) and 1. 056 nm(Tyr --> N, site). By studing the effect of CaM antagonist W7 and CaM antibody on Tb3+-sensitized fluorescence, it was found that the binding sites of W7 and antibody were located on the c-terminal part of plant extracellular CaM which contains domain III and domain IV.