Rare Earth Doped SnO(2) Nanoscaled Powders and Coatings: Enhanced Photoluminescence in Water and Waveguiding Properties

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

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.

The theory of vibronic transitions in rare earth compounds

The theory of vibronic transitions in rare earth compounds is re-examined in the light of a more reliable representation for the ligand field Hamiltonian than the crude electrostatic model. General expressions that take into account the relevant contributions from the forced electric dipole and dynamic coupling mechanisms are derived for the vibronic intensity parameters. These include additional terms, from charge and polarizability gradients, which have not been considered in previous work. Emphasis is given to the relative signs of these various contributions. Under certain approximations these expressions may be conveniently written in terms of accessible ligand field parameters. A comparison with experimental values for the compounds Cs2NaEuCl6 and LiEuF4 is made and satisfactory agreement between theory and experiment is found. A discussion is given on the sensitivity of the calculated intensities to the values of radial integrals, interconfigurational energy differences and ligand field parameters that may be used. Finally, the problem in which a vibronic and an electronic level are in resonance, or near resonance, is analyzed. Suitable expressions to describe the effects of the even-rank components of the vibronic Hamiltonian are obtained. It is found that, depending on the strength of the vibronic interaction and the resonance conditions, the admixture between these two levels may lead to intensities of nearly equal values. © 1995.

Novel fabrication process of planar waveguides in rare-earth doped fluoroindate glasses

We report the successful fabrication of planar waveguides in rare-earth doped fluoroindate glass substrates. A new procedure for waveguide fabrication using a thermally evaporated AgF nonmetallic film was developed. The refractive index changes of more than 0.03, associated to low propagation losses achieved, open new perspectives and show the potentiality of using this glass family toward further developments in fabrication and design of integrated optical devices for optical communication wavelengths.© 1995 American Institute of Physics.

Influence of Earth's shadow on the rotational motion of an artificial satellite perturbed by solar radiation torque

A semi-analytical approach is proposed to study the rotational motion of an artificial satellite under the influence of the torque due to the solar radiation pressure and taking into account the influence of Earth's shadow. The Earth's shadow is introduced in the equations for the rotational motion as a function depending on the longitude of the Sun, on the ecliptic's obliquity and on the orbital parameters of the satellite. By mapping and computing this function, we can get the periods in which the satellite is not illuminated and the torque due to the solar radiation pressure is zero. When the satellite is illuminated, a known analytical solution is used to predict the satellite's attitude. This analytical solution is expressed in terms of Andoyer's variables and depends on the physical and geometrical properties of the satellite and on the direction of the Sun radiation flux. By simulating a hypothetical circular cylindrical type satellite, an example is exhibited and the results agree quite well when compared with a numerical integration. © 1997 COSPAR. Published by Elsevier Science Ltd.

Synthesis and thermal study of 8-hydroxy-quinoline derivatives of the alkaline Earth metals: I. Strontium complexes

Strontium complexes of 5,7-dibromo-, 5,7-dichloro-, 7-iodo- and 5-chloro-7-iodo-8-hydroxyquinoline were precipitated from an aqueous ammonia and acetone medium. The complexes obtained were Sr[(C9H4ONBr2)2]·2.5H 2O; Sr[(C9H4ONCl2)(OH)]·1.5H2O; Sr[(C9H5ONI)2]·5H2O and Sr[(C9H4ONICl)(OH)]·1.25H2O. The residues of their thermal decomposition were SrBr2; a mixture of SrCl2, SrCO3 and SrO3 SrCO3, and SrCO3, respectively. All were characterized by means of thermogravimetry, differential thermal analysis, complexometry with EDTA, atomic absorption spectroscopy, IR spectroscopy and X-ray diffraction. © 1999 Akadémiai Kiadó.

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho3+, Tm3+ and Nd3+ ions and codoped with Pr3+/Nd3+ and Yb3+/Tb3+ ions. The results for the Ho3+-doped samples show strong evidence of energy transfer (ET) between Ho3+ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm3+-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr3+/Nd3+ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd 3+ and the Pr3+ ions. It was observed that the presence of Nd3+ ions enhanced the Pr3+ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd3+-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd3+ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb3+/ Tb3+-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb3+ emission in the blue is due to ET from a pair of excited Yb3+ ions followed by ESA in the Tb 3+ ions. © 2002 Académie des sciences/Éditions scientifiques et médicales Elsevier SAS.

Rare earth doped HfO2 nanoparticles embedded in SiO2-HfO2 planar waveguides. Preparation, optical, structural and spectroscopic characterization

In this work we present results on the preparation of planar waveguides based on HfO2 and HfO2-SiO2. Stable sols containing europium and erbium doped HfO2 nanoparticles have been prepared and characterized. The nanosized sol was either deposited (spin-coating) on quartz substrates or embedded in (3-glycidoxipropil)trimethoxisilane (GPTS) used as a hybrid host for posterior deposition. The refractive index dispersion and luminescence characteristics were determined for the resulting HfO2 films. The optical parameters of the waveguides such as refractive index, thickness and propagation losses were measured for the hybrid composite. The planar waveguides present thickness of a few micra and support well confined propagating modes.

Discriminating among earth composition models using geo-antineutrinos

It has been estimated that the entire Earth generates heat corresponding to about 40 TW (equivalent to 10,000 nuclear power plants) which is considered to originate mainly from the radioactive decay of elements like U, Th and K, deposited in the crust and mantle of the Earth. Radioactivity of these elements produce not only heat but also antineutrinos (called geo-antineutrinos) which can be observed by terrestrial detectors. We investigate the possibility of discriminating among Earth composition models predicting different total radiogenic heat generation, by observing such geo-antineutrinos at Kamioka and Gran Sasso, assuming KamLAND and Borexino (type) detectors, respectively, at these places. By simulating the future geo-antineutrino data as well as reactor antineutrino background contributions, we try to establish to which extent we can discriminate among Earth composition models for given exposures (in units of kt · yr) at these two sites on our planet. We use also information on neutrino mixing parameters coming from solar neutrino data as well as KamLAND reactor antineutrino data, in order to estimate the number of geo-antineutrino induced events. © SISSA/ISAS 2003.

Infrared-to-visible frequency upconversion in transparent glass ceramics containing trivalent-rare-earth-doped nanocrystals

In this work we report on visible upconversion emission in Er 3+-, and Ho3+-doped PbGeO3-PbF 2-CdF2-based transparent glass ceramics under 980 nm infrared excitation. In erbium-doped vitroceramic samples, blue(410 ran), green(530, and 550 nm) and red(660 nm) emission signals were generated, which were identified as due to the 2H9/2, 2H 11/2, 4S3/2, and 4F9/2 transitions to the 4I15/2 ground-state, respectively. Intense red(650 nm) upconversion emission corresponding to the 5F5 - 5I8 transition and very small blue(490 nm) and green(540 nm) signals assigned to the 5F 2,3 - 5I8 and 4S2, 5F4 - 5I8 transitions, respectively, were observed in the holmium-doped samples. The 540 nm is the dominant upconversion signal in Ho3+-doped vitroceramics under 850 nm excitation. The dependence of the upconversion processes upon pump power and doping concentration are also investigated, and the main routes for the upconversion excitation processes are also identified. The comparison of the upconversion process in transparent glass ceramics and the precursor glass was also examined and the results revealed that the former present higher upconversion efficiencies.

A study of the relative velocities of small particles that are orbiting the earth

The evolution of the velocity of the particles with respect to the circular orbits of satellites that are around the Earth that the particles will cross, suggests a range of possible velocities of impact as a function of the altitude of the satellite. A study made from those results show that the maximum relative velocities occur at the semi-latus rectum, independent of the initial semi-major axis of the particle. Considering both the solar radiation pressure and the oblateness of the Earth, it is visible that a precession in the orbit occurs and there is also a variation in the eccentricity of the particle as a function of its orbital region and its size. This is important information, because the damage caused in a spacecraft depends on the impact velocity.

Study of biosorption of rare earth metals (La, Nd, Eu, Gd) by Sargassum sp. biomass in batch systems: Physicochemical evaluation of kinetics and adsorption models

This work evaluated kinetic and adsorption physicochemical models for the biosorption process of lanthanum, neodymium, europium, and gadolinium by Sargassum sp. in batch systems. The results showed: (a) the pseudo-second order kinetic model was the best approximation for the experimental data with the metal adsorption initial velocity parameter in 0.042-0.055 mmol.g -1.min-1 (La < Nd < Gd < Eu); (b) the Langmuir adsorption model presented adequate correlation with maximum metal uptake at 0.60-0.70 mmol g-1 (Eu < La < Gd < Nd) and the metal-biomass affinity parameter showed distinct values (Gd < Nd < Eu < La: 183.1, 192.5, 678.3, and 837.3 L g-1, respectively); and (c) preliminarily, the kinetics and adsorption evaluation did not reveal a well-defined metal selectivity behavior for the RE biosorption in Sargassum sp., but they indicate a possible partition among RE studied. © (2009) Trans Tech Publications.

Optical and transport properties of rare-earth trivalent ions located at different sites in sol-gel SnO2

Photoluminescence and photo-excited conductivity data as well as structural analysis are presented for sol-gel SnO2 thin films doped with rare earth ions Eu3+ and Er3+, deposited by sol-gel-dip-coating technique. Photoluminescence spectra are obtained under excitation with various types of monochromatic light sources, such as Kr+, Ar+ and Nd:YAG lasers, besides a Xe lamp plus a selective monochromator with UV grating. The luminescence fine structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at the asymmetric grain boundary layer 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 in the capture energy is not so evident in these materials with nanoscocopic crystallites, even though the luminescence spectra are rather distinct. It seems that grain boundary scattering plays a major role in Eu-doped SnO2 films. Structural evaluation helps to interpret the electro-optical data. © 2010 IOP Publishing Ltd.

Study of the influence of the rare earth elements (Ce3+ and Ce4+) concentration on the siloxanes coating applied on the copper surface

This work studied the influence of the rare earth (Ce3+ and Ce4+) elements concentration in polysiloxane flints deposited on copper by dip-coating process, and evaluated their resistance in a 3.5 wt.% NaCl medium. Classical electrochemistry techniques were used as open circuit potential, polarization curves and electrochemical impedance spectroscopy. The results revealed that by adding low concentration of Ce4+ ions, the coating prevents the electrolyte uptake any longer retarding the substrate degradation consequently. ©The Electrochemical Society.

Piezoresponse force microscopy characterization of rare-earth doped BiFeO3 thin films grown by the soft chemical method

The multiferroic behavior with ion modification using rare-earth cations on crystal structures, along with the insulating properties of BiFeO3 (BFO) thin films was investigated using piezoresponse force microscopy. Rare-earth-substituted BFO films with chemical compositions of (Bi 1.00-xRExFe1.00O3 (x=0; 0.15), RE=La and Nd were fabricated on Pt (111)/Ti/SiO2/Si substrates using a chemical solution deposition technique. A crystalline phase of tetragonal BFO was obtained by heat treatment in ambient atmosphere at 500 °C for 2 h. Ion modification using La3+ and Nd3+ cations lowered the leakage current density of the BFO films at room temperature from approximately 10-6 down to 10-8 A/cm2. The observed improved magnetism of the Nd3+ substituted BFO thin films can be related to the plate-like morphology in a nanometer scale. We observed that various types of domain behavior such as 71° and 180° domain switching, and pinned domain formation occurred. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cm Oe. © 2012 Elsevier Ltd and Techna Group S.r.l.