Er(3+)-Based Diureasil Organic-Inorganic Hybrids

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and Photoluminescence Behavior of the Eu3+ Ions as a Nanocoating over a Silica Stober Matrix

In this work, a SiO2 spherical were prepared by the Stober Method and then recovered with a single layer of Eu2O3 oxide (SiO2@Eu2O3) obtained by the Polymeric Precursor Method. The SiO2@Eu2O3 powder was heated treated at 100, 300, 400, 500 and 800 A degrees C. The samples were characterized by the Scanning Electonic Microscopy (SEM), Thermal Analysis (TGA/DTA), and the luminescent properties of the SiO2@Eu2O3 powders were studied by their emission and excitation spectra as well as by the lifetime measurements of the Eu3+ D-5(0) -> aEuro parts per thousand F-7(2) transition. The SEM analysis shows that the silica prepared by the Stober Method is spherical with a particle size of 460 nm. The emission spectra of the SiO2@Eu2O3 powders presented the Eu3+ characteristics bands related to the D-5(0) -> aEuro parts per thousand F-7(J) (J = 0, 1, 2, 3, 4) transitions at 577, 591, 616, 649 and 695 nm, respectively. The band related to the D-5(0) -> aEuro parts per thousand F-7(2) transition is the most intense in the spectra, and its intensity decreases with the temperature enhancement. The decay curves of the SiO2@Eu2O3 samples presented monoexponential features, and the obtained lifetime values were higher than the Eu2O3 oxide. It was possible to conclude that the D-5(0) -> aEuro parts per thousand F-7(2) hypersensitive transition is strongly dependent on the Eu3+ surrounding.

Photoluminescence of bulks and thin films of Eu3+-doped organic/inorganic hybrids

Organic-inorganic hybrids formed by polyether-based chains grafted to both ends to a siliceous backbone through urea cross-linkages (-NHC=O)NH-), named di-ureasil, have been used as host for incorporation of Eu3+ in the form of EuCl3. The bulks and the thin films, both optically transparent, were characterized by excitation, absorption and emission spectroscopy. Photoluminescence results point out that the Eu3+ ions occupy, at least, two distinct local environments. Besides, the processing method (thin films or bulks) has influence on the energy levels of the hybrid host probably due to the lower degree of organization of the thin films structure. (c) 2007 Elsevier B.V. All rights reserved.

Luminescence properties of Eu(3+)- and Mg(2+)-doped LiTaO(3) obtained via the polymeric precursor method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Enhanced luminescence of Tb3+/Eu3+ doped tellurium oxide glass containing silver nanostructures

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Optical emission and electron capture of rare-earth trivalent ions located at distinct sites in SnO(2) thin films

We present photoluminescence and decay of photo excited conductivity data for sol-gel SnO(2) thin films doped with rare earth ions Eu(3+) and Er(3+), a material with nanoscopic crystallites. Photoluminescence spectra are obtained under excitation with several monochromatic light sources, such as Kr(+) and Ar(+) lasers, Xe lamp plus a selective monochromator with UV grating, and the fourth harmonic of a Nd: YAG laser (4.65eV), which assures band-to-band transition and energy transfer to the ion located at matrix sites, substitutional to Sn(4+). The luminescence structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at grain boundary layer, where it is placed in asymmetric sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference between capture energy and grain boundary barrier is not so evident, even though the luminescence spectra are rather distinct.

New chelate complexes of trivalent Y and lanthanides (Eu, Ho, Yb) with a triazene N-oxide: Synthesis, structural characterization and luminescence properties

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spectroscopic study of lanthanide squarate hydrates

In the present investigation some spectroscopic properties of several lanthanide squarate hydrates are reported. The Raman spectra show the same distinctive Jahn-Teller intensity pattern for non-totally symmetric modes, as previously observed for the free anion. In the case of the terbium salt, the Tb3+ emission is very intense even at room temperature, revealing an efficient excitation via the ligand electronic levels. The Tb3+ dilution in Gd3+ or La3+ hosts increases this excitation efficiency without any appreciable variation in the 5D4 excited-state lifetime. However, the Eu3+ emission is very weak, with excited states located above the 5D2 level (ca. 21 550 cm-1) being completely quenched at room temperature. At lower temperatures higher-lying levels are not so efficiently quenched. The broad band observed in the UV excitation spectra of Eu3+ and Tb3+ is easily assigned to an intra-ligand transition leading to ligand-to-lanthanide ion energy transfer processes. As observed for Tb3+, Eu3+ dilution in Gd3+ or La3+ hosts also increases the relative emission intensity mediated by the ligand, without variation in the 5D0 excited-state lifetime. The Eu3+ 5D0 excitation spectra show vibronic structures that can be interpreted on the basis of the data available from the vibrational spectra. An increase in the vibronic intensities is observed as the lanthanide concentration is increased. © 1994.

Optical transition probabilities and compositional dependence of Judd-Ofelt parameters of Er3+ ions in fluoroindate glass

Fluoroindate glasses containing 1, 2, 3, and 4 mol% ErF3 were prepared in a dry box under an argon atmosphere. Absorption spectra of these glasses at room temperature were obtained. The Judd-Ofelt parameters Ωλ (λ = 2, 4, 6) for f-f transitions of Er3+ ions as well as transition probabilities, branching ratios, radiative lifetimes, and peak cross-sections for stimulated emission of each band were determined. The concentration effect on the intensities is analyzed. The optical properties of the fluoroindate glasses doped with Er3+ ions are compared with those of other glasses described in the literature. © 1995.

Short Range Order Evolution in the Preparation of SnO2 Based Materials

The evolution of Eu3+ doped SnO2 xerogels to the cassiterite structure observed during sintering was studied by means of Eu3+ spectroscopy, XRD and EXAFS at the Sn K-edge. Eu3+ ions adsorbed at the surface of colloidal particles present a broad distribution of sites, typical of oxide glasses. With sintering at 300°C, this distribution is still broadened. Crystallization is clearly observed by the three techniques with increasing sintering temperature. It is found that the addition of Eu3+ limits the crystallite growth.

Study of the binding of Eu3+ and Tb3+ to L-phenylalanine and L-tryptophan

Trivalent europium and terbium ions have ionic radii similar to that of Ca2+. So they are employed as probes of calcium binding sites in biological molecules. These ions exhibit very useful spectroscopic characteristics, chiefly a pronounced luminescence. In protein bound lanthanide, visible light emission from the lanthanide excited states can be observed when UV light is absorbed by aromatic amino acids. Subsequently, the energy is transferred to the lanthanide ion. The present work was carried out to define the binding sites of Eu3+ and Tb3+ in complexes with the aromatic amino acids L-phenylalanine and L-tryptophan. The techniques utilized were infrared and C nuclear magnetic resonance spectroscopies. It was found that trivalent europium and terbium interact with the carboxylate group of both amino acids. With L-tryptophan, the imino group of the indole ring is also involved representing another coordination site.

In(PO3)3 stabilised fluoroindate glasses

Results on thermal and optical characterization of new lanthanide containing fluoroindate glasses in the system InF3-BaF2-In(PO3)3 are presented. Good optical quality and very stable glasses presenting up to 5 mm in thickness could be prepared in this system. Thermal analysis, Raman scattering and Eu3+ luminescence were the techniques utilized. A novel method for In(PO3)3 synthesis is proposed and the dependence of physical properties and structural features on the polyphosphate content is stressed. © 1998 Elsevier Science S.A.

Study of Hybrid Silica-Polyethyleneglycol Xerogels by Eu3+ Luminescence Spectroscopy

Good optical quality Eu3+-doped silica-polyethyleneglycol hybrids were prepared by the sol-gel process. Thermomechanical analysis showed an increase of the glass transition temperature, due to the stiffness of the polymeric network, as the amount of Eu3+ increased. Europium luminescent properties were used to study structural evolution during the sol-gel transition. For lower doping concentrations dried gels present statistical distributions of Eu3+, typical of an amorphous environment, while for higher concentrations a crystalline-like environment of Eu3+ was observed. A broad emission band was observed in the visible part of the electromagnetic spectrum and assigned to the intrinsic emission from the hybrid polymeric network.

Coordination of Eu3+ ions in siliceous nanohybrids containing short polyether chains and bridging urea cross-links

Infrared and photoluminescence spectroscopies have been used to investigate the local environment of the Eu3+ ions in luminescent sol-gel derived materials-di-ureasils-based on a hybrid framework represented by U(600). This host is composed of a siliceous backbone grafted, through urea cross-links, to both ends of polymer segments incorporating 8.5 oxyethylene repeat units. The active centers have been introduced as europium perchlorate, Eu(ClO4)3. Samples with compositions n = 232, 62, 23, 12, and 6 (where n denotes the ratio of (OCH2CH2) moieties per lanthanide ion) have been examined. The combination of the information retrieved from the analysis of characteristic bands of the FTIR spectra-the perchlorate and the Amide I/Amide II features-with that obtained from the photoluminescence data demonstrates that at compositions n = 232 and 62 the anions are free, whereas the Eu3+ ions are complexed by the heteroatoms of the polyether chains. At higher salt concentration, the cations are bonded, not only to the ClO4 - ions, but also to the ether oxygen atoms of the organic segments and to the carbonyl oxygen atoms of the urea linkages. The dual behavior of U(600) with respect to cation coordination has been attributed to the presence in this nanohybrid of strong hydrogen-bonded urea-urea structures, which, at low salt content, cannot be disrupted, thus inhibiting the formation of Eu3+-O=C(urea) contacts and promoting the interaction between the lanthanide ions and the (OCH2CH2) moieties. The present work substantiates the claim that the activation of the coordinating sites of the di-ureasil framework can be tuned by varying either the guest salt concentration at constant chain length or the length of the.organic segments at constant salt concentration. This relevant property opens challenging new prospects in the fields of application of this class of hybrids. © 2001 American Chemical Society.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.