Optical characteristics of Er3+-Yb3+ doped SnO2 xerogels

Er3+ doped SnO2 xerogels have been obtained from aqueous colloidal suspensions. Emission and excitation spectra were obtained and allowed the identification of two main families of sites for Er3+. In the first one Er3+ substitutes for Sn4+ in the SnO2 cassiterite structure. In the second Er3+ are found adsorbed at the SnO2 particle surface. For the first family of sites the technological important infrared Er3+ emission about 1.5 mum is efficiently excited through absorption at the SnO2 conduction band at 3.8 eV. on the other hand the emission due to adsorbed ions appears inhomogeneously broadened by the statistical distribution of sites available for Er3+ ions at the surface of the particles. Moreover it is not excited by the host. The emission of this second family of sites could be also excited by an energy transfer mechanism involving Yb3+ ions also adsorbed a posteriori at particles surface. Results are compared with spectra obtained for Eu3+ doped samples. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Enhanced emission from Eu(III) beta-diketone complex combined with ether-type oxygen atoms of di-ureasil organic-inorganic hybrids

Organic-inorganic hybrids, named di-ureasils and described by polyether-based chains grafted to both ends to a siliceous backbone through urea cross linkages, were used as hosts for incorporation of the well-known coordination complex of trivalent europium (Eu3+) ions described by the formula [Eu(TTA)(3)(H2O)(2)] (where TTA stands for thenoyltrifluoroacetone). By comparing with Eu3+-doped di-ureasil without complex form the new materials prepared here enhanced the quantum efficiency for photoemission of Eu3+ ions. The enhancement can be explained by the coordination ability of the organic counterpart of the host structure which is strong enough to displace water molecules in [Eu(TTA)(3)(H2O)(2)] from the rare earth neighbourhood after the incorporation process. High intensity of Eu3+ emission was observed with a low non-radiative decay rate under ultraviolet excitation. The quantum efficiency calculated from the decay of D-5(0) emission was 74%, which in the same range of values previously obtained for the most efficient Eu3+ coordination compounds reported in literature. Luminescence, X-ray absorption and infrared absorption results considered together leads to a picture where the first coordination shell of Eu3+ is composed of the 6 oxygen atoms of the 3 beta-diketonate ligands and 2 ether-like oxygen atoms of the host. (C) 2003 Elsevier B.V. B.V. All rights reserved.

SiO2-GeO2 soot preform as a core for Eu2O3 nanocoating: Synthesis and photophysical study

Nowadays solid state chemists have the possibility of work with low temperature strategies to obtain solid state materials with appropriate physical and chemical properties for useful technological applications. Photonic core shell materials having a core and shell domains composed by a variety of compounds have been synthesized by different methods. In this work we used silica-germania soot prepared by vapor-phase axial deposition as a core where a nanoshell of Eu2O3 was deposited. A new sol-gel like method was used to obtain the Eu2O3 nanoshell coating the SiO2-GeO2 particles, which was prepared by the polymeric precursor method. The photophysical properties of Eu3+ were used to obtain information about the rare earth surrounding in the SiO2-GeO2@Eu2O3 material during the sintering process. The sintering process was followed by the luminescence spectra of Eu3+ and all the samples present the characteristic emission related to the D-5(0) -> F-7(J) (J=0, 1, 2, 3 and 4). The ratios of the D-5(0) -> F-7(2)/D-5(0) -> F-7(1) emission intensity for the SiO2-GeO2@Eu2O3 systems were calculated and it was observed an increase in its values, indicating a low symmetry around the Eu3+ as the temperature increases.

The behavior of dissolved uranium in groundwaters of the Morro do Ferro thorium deposit, Brazil

Groundwater samples were collected for several months in boreholes drilled at Morro do Ferro, a thorium and rare earth deposit located on the Poços de Caldas Plateau, Minas Gerais State, Brazil. An aquifer system has developed in the weathered mantle due to in situ intense alteration. The weathered zone includes a thick argillaceous laterite greater than 100 m thick. The U content and 324U/238U activity ratio were measured in the groundwater samples and in spoil samples of a borehole drilled in the ore body. Some possible mechanisms related to the mobilization of uranium are considered such as complexation with humic substances and adsorption by clays. © 1989.

Lithium-lanthanum double chromates

Synthesis and crystallographic data are reported for low and high temperature forms of LiLa(CrO4)2. The compounds are closely related to lamellar rare earth phosphates and arsenates of sodium and to RbLu(CrO4)2. Lattice parameters of the orthorhombic (low temperature) and monoclinic (high temperature) forms are given. The low temperature form is moisture sensitive and Li+ ions are easily displaced by protons. Thermal decomposition takes place at 250 °C and results in the formation of LiCrO2, LaCrO4, LaCrO3 and Cr2O3. © 1993.

Synthesis, characterization and spectroscopy of the europium doped lanthanum trimetaphosphate

Orthorhombic modification of europium doped lanthanum trimetaphosphate has been prepared. The compound was obtained by precipitation of rare earth chloride solution with trimetaphosphoric acid. The characterizations were made using X-ray diffractometry, chemical analysis and infrared spectroscopy. Excitation and emission spectra were recorded at liquid nitrogen and room temperatures. Assignments of the 5D0→7FJ (J=0, 1, 2, 3, 4, 5) transitions were made and an unusual high 5D0→7F4 transition intensity with six split lines has been observed. Structural distortion of the crystal lattice may be caused by the Eu3+ ion inclusion. The simple overlap model was applied for the calculation of the total splitting of the 5D0→7F1 transition, the 5D0→7F0/5D 0→7F2 transition intensity ratio and the Ωλ (λ=2.4) intensity parameters. Theoretical predictions showed to be in good accordance with the experimental data. © 1988 Elsevier Science S.A.

Absorption and fluorescence of Er3+-doped LiYF4: Measurements and simulation

Er3+:LiYF4 single crystal has been studied by absorption and fluorescence spectroscopy in the IR-visible-UV (0-44000 cm-1) region from 4.2 K to room temperature. Polarized spectra were recorded in order to assign numerous Stark levels of electronic transitions mentioned but not attributed before in the related literature and to discuss the irreducible representations (irreps) of the 4I15/2 sublevels. A parametric hamiltonian, including free ion (Eν, α, β, γ, Tλ, ζ, Mk and Pi) and crystal field parameters (B2 0, B4 0, B4 4, B6 0 and B6 4) in an approximate D2d symmetry for the rare earth site in this scheelite type structure, was used to simulate 109 energy positions of the Er ion with a r.m.s. standard deviation of 14.6 cm-1. A comparison with previously published results for Nd3+ in the same matrix is done. © 1998 Elsevier Science S.A.

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb1-xLaxTiO3 thin films, (X=0.0; 13 and 0.27mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO2/Si(111), Si(100) and glass substrates by spin coating, and annealed in the 200-300°C range in an O2 atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO3. The films deposited on Pt/Ti/SiO2/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration. © 2002 Elsevier Science B.V. All rights reserved.

Thermal studies of solid 2-methoxybenzylidenepyruvate of lighter trivalent lanthanides

Solid-state compounds with a general formula of LnL3· nH2O, where Ln stands for lighter trivalent lanthanides (lanthanum to samarium), L is 2-methoxybenzylidenepyruvate and n=1.5, 2, 2, 1.5 and 2, respectively, have been synthesized. On heating these compounds are decompose in two or three steps. They lose their hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (La to Sm) were: 222.7, 163.6, 497.7, 513.9 and 715.4 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Thermal studies on solid 2-chlorobenzylidenepyruvate of lighter trivalent lanthanides

Solid compounds of general formula LnL3 for La and Ce and LnL3·nH2O for Pr, Nd and Sm where Ln stands for trivalent lanthanides, L is 2-chlorobenzylidenepyruvate and n=2, 3 and 2 respectively, have been synthesized. On heating these compounds decompose in two or five steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (Pr, Nd and Sm) were: 140.1, 148.2 and 221.3 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Tm3+ and Tm3+-Ho3+ doped fluorogermanate glasses for S-band amplifiers

Two series of glasses with composition (mol%) 70PbGeO3- 15PbF2-15CdF2, the first one with different Tm 3+ contents (0.2, 0.4, 0.6 and 0.8 mol%) and the second one with 0.2 mol% Tm3+ and different Ho3+ contents (0.1, 0.5, 1.0 and 1.5 mol%), have been prepared and some of their spectroscopic properties studied. Absorption in the visible-near infrared and emission in the near infrared region of the electromagnetic spectrum have been obtained. Concerning emission at the 1.4-1.5 μm region, optimization of rare earth ions content leads to 0.2 and 0.5 mol% for Tm3+ and Ho3+, respectively. We discuss potential application of these compositions. © 2005 Elsevier B.V. All rights reserved.

Efficient UV-visible upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate vitroceramic

Cooperative energy-transfer upconversion luminescence in Tb 3+/Yb 3+-codoped PbGeO 3-PbF 2-CdF 2 vitroceramic and its precursor glass under resonant and off-resonance infrared excitation, is investigated. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm, identified as due to the 5D 3( 5G 6 → 7F J(J=6,5,4) and 5D 4 → 7F J(J=6,5,4,3) transitions, respectively, were readily observed. The results indicate that cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The comparison of the upconversion process in a vitroceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.

Production and characterization of Tm3+/Yb3+ codoped waveguides based on PbO-GeO2 thin films

Fabrication and optical characterization of Tm3+/Yb3+ codoped PbO-GeO2 (PGO) pedestal-type waveguides are investigated in this work. It is important to mention that, to the best of authors' knowledge, the use of PGO pedestal-type waveguide has not been studied before. PGO thin films codoped with Tm3+ and Yb3+ were obtained through RF magnetron sputtering technique. The pedestal profile was obtained using conventional optical lithography procedures, followed by plasma etching and sputtering deposition. The profile of Tm3+/Yb3+ codoped PGO waveguides was observed by means of Scanning Electron Microscopy (SEM) measurements. Also the infrared and infrared-to-visible frequency upconversion luminescences of Tm3+ ions were measured exciting the samples with a cw 980 nm diode laser. Propagation losses around 11 dB/cm and 9 dB/cm were obtained at 630 and 1050 nm, respectively, for waveguides in the 20-100 μm width range. Single-mode propagation was observed for waveguides width up to 12 μm and 7 μm, at 1050 nm and 630 nm, respectively; larger waveguides width provided multi-mode propagation. The present results corroborate the possibility of using Tm3+/Yb3+ codoped PGO thin films as active waveguide for photonic applications. © 2013 Elsevier B.V. All rights reserved.

Luminescent properties of hybrid materials prepared by the polymeric precursor method

Rare earth complexes (RE) can be incorporated in silica matrixes, originating organic/inorganic hybrid materials with good thermal stability and high rare earth emission lines. In this work, the hybrid material was obtained by the polymeric precursor method and ultrasonic dispersed with spherical silica particles prepared by the Stöber Method. The Raman spectra indicated that the Eu3+ ions are involved in a polymeric structure formed as consequence of the chelation and polyesterification reactions of this ion with citric acid and ethylene glycol. After the ultrasonic stirring, 2-hydroxynicotinic ligand will also compose this polymeric rigid structure. The TGA/DTA analysis showed that this polymeric material was thermal decomposed at 300 °C. Moreover, this process allows the chelating process of the 2-hydroxynicotinic acid ligand to the Eu3+ ions. The 29Si NMR showed that the ultrasonic dispersion of the reactants was not able to promote the functionalization of the silica particles with the 2-hydroxynicotinic acid ligand. Moreover, heat treatment promotes the [Eu(HnicO2)3] complex particles incorporation into silica pores. At this temperature, the TGA curve showed that only the thermal degradation of ethylene glycol and citric acid used during the experimental procedure occurs. The silica and hybrid materials are composed by spherical and aggregated particles with particle size of approximately 450 nm, which can be influenced by the heat treatment. These materials also present an absorption band located at 337 nm. The photoluminescent study showed that when the hybrid samples were excited at 337 nm wavelength, the ligand absorbs the excitation light. Part of this energy is transferred to the Eu3+ ion, which main emission, 5D0→ 7F2, is observed in the emission spectrum at 612 nm. As the heating temperature increases to 300 C, the energy transfer is more favorable. The lifetime values showed that the Eu3+ emission is enhanced due to the energy transfer process in the powders. © 2013 Elsevier B.V. All rights reserved.

Thermoanalytical study of heavier trivalent lanthanides fumarates

Solid-state heavier lanthanides fumarates compounds have been synthesized, and the compounds were characterized by employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), TG coupled to FTIR, elemental analysis, and complexometry. On heating, the dehydration occurs in a single and two consecutive steps and the thermal decomposition of the anhydrous compounds occurs in consecutive and/or overlapping steps, with formation of the respective oxides: Tb4O7 and Ln2O3 (Ln=Dy to Lu). The results also led to information about composition, thermal behavior, and the type of coordination of the isolated compounds. © 2012 Akadémiai Kiadó, Budapest, Hungary.