Multiple energy transfers in rare earth complex-doped SiO2 spheres

Silica spheres doped with Eu(TTFA)(3) and/or Sm(TTFA)(3) were synthesized by using the modified Stober method. The transmission electron microscope image reveals that the hybrid spheres have smooth surfaces and an average diameter of about 210 nm. Fluorescence spectrometer was used to analyze the fluorescence properties of hybrid spheres. The results show that multiple energy transfer processes are simultaneously achieved in the same samples co-doped with Eu (TTFA)(3) and Sm(TTFA)(3), namely between the ligand and Eu3+ ion, the ligand and Sm3+ ion, and Sm3+ ion and Eu3+, ion. Energy transfer of Sm3+-> Eu3+, in the hybrid spheres leads to fluorescence enhancement of Eu3+ emission by approximately an order of magnitude. The lifetimes of the hybrid spheres were also measured.

Low temperature preparation of ceria solid solutions doubly doped with rare-earth and alkali-earth and their properties as solid oxide fuel cells

A series of solid electrolytes, (Ce(0.8)Ln(0.2))(1 - x)MxO2 - delta(Ln = La, Nd, Sm, Gd, M:Alkali-earth), were prepared by amorphous citrate gel method. XRD patterns indicate that a pure fluorite phase is formed at 800 degreesC. The electrical conductivity and the AC impedance spectra were measured. XPS spectra show that the oxygen vacancies increase owing to the MO doping, which results in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte is improved. The effects of rare-earth and alkali-earth ions on the electricity were discussed. The open-circuit voltages and maximum power density of planar solid oxide fuel cell using (Ce0.8Sm0.2)(1 - 0.05)Ca0.05O2 - delta as electrolyte are 0.86 V and 33 mW . cm(-2), respectively.

Sol-gel derived silicate oxyapatite phosphor films doped with rare earth ions

Rare-earth (Eu3+, Tb3+)-doped Ca2Y8(SiO4)(6)O-2 luminescent thin films were dip-coated on silicon and quartz glass substrates through a sol-gel route. X-ray diffraction (XRD), scanning electron microscopy (SEM) and luminescence excitation and emission spectra as well as luminescence decays were used to characterize the resultant films. The results of XRD reveal that these films remain amorphous below 700 degreesC, begin to crystallize at 800 degreesC, and crystallize completely around 1000 degreesC with an oxyapatite structure. The grain structure of the film can be seen clearly from SEM micrographs, where particles with various shape and average size of 250 nm can be resolved. The Eu3+ and Tb3+ ions show their characteristic red (D-5(0)-F-7(2)) and green (D-5(4)-F-7(5)) emission in the films with a quenching concentration of 10 and 6 mol% (of Y3+), respectively. The lifetime of Eu-3divided by increases with the heat treatment temperature front 700 to 1100 degreesC.

VUV-UV photoluminescence spectra of strontium orthophosphate doped with rare earth ions

The measurements of VUV-UV photoluminescence emission (PL) and photoluminescence excitation (PLE) spectra of rare earth ions activated strontium orthophosphate [Sr-3(PO4)(2):RE, RE = Ce, Sm, Eu, Tb] are performed. Whenever the samples are excited by VUV or UV light, the typical emission of Ce-3+,Ce- Sm3+, Eu3+, Eu2+ and Tb3+ ions can be observed in PL spectra, respectively. The charge transfer bands (CTBs) of Sm3+ and Eu3+ are found, respectively, peaking at 206 and 230nm. The absorption bands peaking in the region of 150-160 nm are assigned to the host lattice sensitization bands, i.e., the band-to-band transitions of PO43- grouping in Sr-3(PO4)(2). It is speculated that the first f-d transitions of Sm3+ (Eu3+), and the CTB of Tb3+ are, respectively, located around 165 (14 3) and 167 urn by means of VUV-UV PLE spectra and relational empirical formula, these f-d transitions or CT bands are included in the bands with the maxima at 150-160 nm, respectively. The valence change of europium from trivalent to divalent in strontium orthophosphate prepared in air is observe by VUV-UV PL and PLE spectra.

Preparation of borates doped with divalent rare earth ions (RE2+) in air and spectroscopy of divalent rare earth ions (RE2+ = Sm, Eu, Tm, Yb)

The spectroscopic feature of divalent Sm2+, Eu2+, Tm2+ and Yb2+ is discussed in this paper. Especially the spectroscopic properties of some berates containing tetrahedral BO4 group such as SrB4O7, SrB6O10 and BaB8O13 doped with these divalent ions are reported. When the divalent alkaline earth ion in these berates is replaced partially by the above trivalent rare earth ion, the charge carried in the produced defects can be used as reductant to reduce the doped rare earth ion into divalent state at high temperature even in air. Therefore, a convenient and safe method is provided to prepared phosphors doped with these divalent rare earths.

Preparation, characterization and luminescent properties of MCM-41 type materials impregnated with rare earth complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Preparation and luminescent properties of inorganic polymer nano - Structured hybrid films doped with rare earth complexes

The inorganic/polymer hybrid films with good luminescent properties have been obtained by the sol - gel process via incorporating the polymer component doped with rare earth complexes. These films exhibit good toughness and transparency. Their fluorescence spectra and lifetimes indicate that they all have the characteristic luminescence of the central rare earth ions. The lifetimes of these films are longer than those of pure complexes. TEM have showed that the rare earth complexes are dispersed homogeneously in SiO2/PVB interpenetratiny networks, and the dispersed size is between 20 and 30 nn.

Luminescence properties of rare-earth (Eu3+ and Tb3+) complexes with paraaminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method

Ternary complexes of europium and terbium with paraaminobenzoic acid and 1,10-phenanthroline (Eu(p-ABA)(3). phen . 2H(2)O and Tb(p-ABA)(3). phen . 2H(2)O, where p-HABA = paraaminobenzoic acid and phen = 1,10-phenanthroline) were introduced into a silica matrix by sol-gel method. The luminescence behavior of the complexes in silica gels was studied in comparison with the. corresponding solid-state complexes by means of emission, excitation spectra, and Lifetimes. Within the range of effective dopant concentrations, the luminescence intensities of rare-earth complexes in silica gel increase with the increasing of their dopant concentration. The lifetimes of rare-earth ions (Eu3+ and-Tb3+) in silica gel doped with europium and terbium complexes become longer than those in pure complexes. Very small amounts of rare-earth complexes doped in silica gel matrix can exhibit excellent luminescence properties, (C) 1998 Elsevier Science Ltd.

Luminescence properties of the ternary rare earth complexes with beta-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Ternary complexes of rare earth Eu(dbm)(3).phen and Tb(acac)(3).phen (dbm = dibenzoylmethanide, acac = acetylacetone and phen = 1,10-phenanthroline) were introduced into silica gel by the sol-gel method. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than in the pure rare earth complexes. The lifetimes of rare earth ions in silica gel (Eu3+ and Tb3+) doped with Eu(dbm)(3).phen and Tb(acac)(3).phen were longer than those in purl Eu(dbm)(3).phen and Tb(acac)(3).phen. A very small amount of rare earth complexes doped in a silica gel matrix can retain excellent luminescence properties. (C) 1997 Elsevier Science S.A.

LUMINESCENCE AND ENERGY MIGRATION IN THE OXYAPATITE CA2GD8(SIO4)6O2 DOPED WITH SEVERAL RARE-EARTH AND MERCURY-LIKE IONS

Energy transfer phenomena have been observed by activating the oxyapatite host-lattice Ca2Gd8(SiO4)6O2 with Eu3+, Tb3+, Dy3+, Sm3+. This is based on the energy migration in the Gd3+ sublattice and trapping by the activators. The trapping efficiency for G

Rare-earth complexes of ferrocene-containing ligands: Visible-light excitable luminescent materials

The ferrocene-derivatives bis(ferrocenyl-ethynyl)-1,10-phenanthroline (Fc(2)phen) and ferrocenoyltrifluoroacetone (Hfta) have been used to synthesize ferrocene-containing rare-earth beta-diketonate complexes. The complexes [Ln(tta)(3)(Fc(2)phen)] and [Ln(fta)(3)(phen)] (where Ln = La, Nd, Eu, Yb) show structural similarities to the tris(2-thenoyltrifluoroacetonate)(1,10-phenanthroline)lanthanide(III) complexes, [Ln(tta)(3)(phen)]. The coordination number of the lanthanide ion is 8, and the coordination sphere can be described as a distorted dodecahedron. However, the presence of the ferrocene moieties shifts the ligand absorption bands of the rare-earth complexes to longer wavelengths so that the complexes can be excited not only by ultraviolet radiation but also by visible light of wavelengths up to 420 nm. Red photoluminescence is observed for the europium(III) complexes and near-infrared photoluminescence for the neodymium(III) and ytterbium(III) complexes. The presence of the ferrocene groups makes the rare-earth complexes hydrophobic and well-soluble in apolar organic solvents.

Rare-earth quinolinates: Infrared-emitting molecular materials with a rich structural chemistry

Near-infrared-emitting rare-earth chelates based on 8-hydroxyquinoline have appeared frequently in recent literature, because they are promising candidates for active components in near-infrared-luminescent optical devices, such as optical amplifiers, organic light-emitting diodes, .... Unfortunately, the absence of a full structural investigation of these rare-earth quinolinates is hampering the further development of rare-earth quinolinate based materials, because the luminescence output cannot be related to the structural properties. After an elaborate structural elucidation of the rare-earth quinolinate chemistry we can conclude that basically three types of structures can be formed, depending on the reaction conditions: tris complexes, corresponding to a 1:3 metal-to-ligand ratio, tetrakis complexes, corresponding to a 1:4 metal-to-ligand ratio, and trimeric complexes, with a 3:8 metal-to-ligand ratio. The intensity of the emitted near-infrared luminescence of the erbium(Ill) complexes is highest for the tetrakis complexes of the dihalogenated 8-hydroxyquinolinates.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.