Recent advances in lanthanide spectroscopy in Brazil

This review discusses recent advances in lanthanide spectroscopy involving luminescence applications Q2 carried out in Brazil. The revised topics include glasses, sol–gel, light-emitting diodes, nanoparticles, metal–organic frameworks, coordination polymers, thin films, energy transfer processes, upconversion and development of new theoretical tools. The important role played by Prof. Oscar L. Malta on this subject is evidenced by his many contributions to the broad range of investigations reported here and this review is dedicated to him, on the occasion of his 60th birthday

Preparação e caracterização estrutural, mecânica e anelástica de ligas do sistema Ti-Ta contendo oxigênio intersticial, para uso biomédico

Com o envelhecimentoda população, os problemas de saúde relacionados à idade aumentam, como osteoartrite e a osteoporose, doenças que afetam articulações e ossos, e muitas vezes exigem cirurgia para aliviar a dor e aumentar a mobilidade, requerendo o uso de biomateriais. Além disso, há também uma busca por próteses ortopédicas devido a acidentes no trânsito e una prática de esportes. O titânio e suas ligas têm se destacado entre os biomateriais metálicos por possuir propriedades adequadas para tal fim. Para este trabalho, foram preparadas ligas de titânio com 19 e 23% em peso de tântalo, utilizando um forno a arco voltaico, e posteriormente as amostras passaram por tratamento térmico de homogeneização, laminação, tratamento térmico de alívio de tensões e tratamentos térmicos em atmosfera de oxigênio com o objetivo de que as amostras fossem dopadas, uma vez que a introdução deste elemento pode melhorar diversas propriedades do titânio. Para caracterizar as amostras, foram efetuadas análises da composição química e de gases, medidas de densidade, difração de raios X (DRX), com análise pelo método de Rietveld, microscopias óptica (MO) e eletrônica de varredura (MEV), com microanálises via Espectroscopia de Energia Dispersiva (EDS). Também foram efetuadas medidas de microdureza e módulo de elasticidade, com a finalidade de estudar o efeito de oxigênio em algumas propriedades mecânicas das ligas. Os resultados de composição química e EDS mostram que as ligas possuem boa qualidade. Os difratogramas de Raios X apresentaram estrutura hexagonal compacta para todas as amostras estudadas, corroborando com as micrografias, onde foi possível observar a formação de agulhas, características da fase ?' (matensítica). A liga com 23% em peso de Tântalo apresenta uma dureza maior do que a liga com 19% em peso de tântalo. As variações nos valores da dureza das ligas foram atribuídas ao processamento...With the population aging, health related to increasing age, such as osteoarthritis and osteoporosis, diseases that affect the joints and bones, and often require surgery to relieve pain and increase mobility, requiring the use of biomaterials. In addition, there is also a search for orthopedic prostheses due to traffic accidents and sports. Titanium and its alloys have been highlighted among metallic biomaterials because have suitable properties for the purpose. For this study, were prepared titanium alloys with 19 and 23% in weight of tantalum, using an arc-furnace, and after the samples have undergone by homogenization heat treatment, cold rolling, solubilization heat treatment, and heat in oxygen atmosphere in order to doping the samples, since the introduction of this element can improve various properties of titanium. To chacarcterize the samples, were performed analysis of chemical and gas composition, density, X-ray diffraction (XRD) with Rietveld analysis, optical microscopy (OM) and scanning electron microscopy (SEM), with microanalysis by Energy Dispersive Spectroscopy (EDS) measurements. Microhardness and elastic modulus measurements were also made, in order to study the effect of oxygem on some mechanical properties of the alloys. The results of the chemical composition and EDS showed that the alloys have good quality. The X-ray diffraction showed hexagonal compact structure for all samples, where could be observed the formation of needles, characteristics of phase ?' (martensite). The alloy with 23 wt% of tantalum has higher hardness than the alloy with 19 wt% of tantalum. The variations in hardness values of the alloys were atributed to processing; it is not possible to observe variations in the values due to the addition of oxygen. The values of elastic modulus did not change due to the increase in the concentration of tantalum, oxygen addition and processing, remaining constantCoordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Matrizes semicondutoras GaAs e Sn'X IND. 2' dopado com terras-raras Ce ou Eu: investigação do transporte elétrico

Dióxido de estanho (Sn'X IND. 2') é um semicondutor de bandgap largo com condutividade do tipo-n na forma não dopada, sendo aplicado em dispositivos diversos. Neste trabalho, filmes finos e géis secos de Sn'X IND. 2' dopados com os íons terras-raras 'Ce POT. 3+' e Eu POT 3+' foram sintetizados através do processo sol-gel. Por outro lado, filmes finos de GaAs têm também sido amplamente utilizados, devido a alta mobilidade eletrônica e transição direta. Neste trabalho, também foram produzidos filmes finos de GaAs através da técnica de evaporação resistiva. Serão mostrados e discutidos aqui resultados referentes a filmes finos de Sn'X IND. 2' dopado com íons terras-raras, filmes finos de GaAs e resultados referentes ao crescimento de filmes finos de GaAs sobre filmes finos de SnO2 dopados com terras-raras. Medidas de absorção óptica permitiram avaliar a qualidade óptica dos filmes e estimar a energia do bandgap. Dados de difração de raios-X mostraram estrutura do tipo rutilo e fase cassiterita dos filmes de Sn'X IND. 2' e também as direções principais dos filmes de GaAs. A microscopia eletrônica de varredura permitiu a espessura e a qualidade morfológica da heterojunção, tanto com relação à interface Sn'X IND. 2'/GaAs como da superfície. A investigação das propriedades elétricas em Sn'X IND. 2' mostra a alta resistividade do material devido ao caráter aceitador de íons terras-raras na matriz. Foi investigada também a captura de elétrons fotoexcitados por centros de 'Ce POT 3+' termicamente ativados. Do modelo proposto, foram obtidos parâmetros importantes, como a barreira de captura devido aos defeitos dominantes. Resistividade em função da temperatura na heterojunção Sn'X IND. 2'/GaAs mostrou a diminuição da resistência do conjunto.Tin dioxide (Sn'X IND. 2') is a wide bandgap semiconductor material whith n-type conductivity the undoped form. This compound has been applied for several kinds of devices. In this work, thin films and xeogels of Sn'X IND. 2' doped with the rare-earth ions 'Ce POT. 3+' and Eu POT 3+' have been produced by the sol-gel process. On the other band, GaAs thin films have also been widely used, due to high electronic mobility and direct bandgap transition. In this work, GaAs thin films have been deposited by the resistive evaporation technique. It is shown and discussed here results concerning rare-earth doped Sn'X IND. 2' thin films. GaAs thin films and the growing of GaAs on the top of rare-earth doped Sn'X IND. 2'. Through the optical absorption spectra it has been possible to evaluate the films optical quality and to estimate the optical bandgap. X-ray diffraction data show the rutile like structure and cassiterie phase of Sn'X IND. 2' thin films and also show the main directions of GaAs films. Scanning electron microscopy allowed evaluating the thickness and morphological quality of the heterojunction, concerning the infarce as well as the surface. Investigation of electrical properties of Sn'X IND. 2' shows high resistivity of this material due to the acceptor-lide character of rare-earth ions in the matrix. It has also been investigated the trapping of photo-induced electrons by the thermally activated Ce centers. From a proposed model, it has been obtained some relevant parameters, such as the capture barrier due to the dominant defects. Data of resistivity as function of temperature for the Sn'X IND. 2'/GaAs heterojunction show the decrease of overall resistance.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Interface Formation and Electrical Transport in SnO2:Eu3+/GaAs Heterojunction Deposited by Sol-Gel Dip-Coating and Resistive Evaporation

The natural n-type conduction of tin dioxide (SnO2) may be compensated by trivalent rare-earth doping. In this work, SnO2 thin films doped with Eu3+ have been deposited by the sol-gel dip-coating (SGDC) process, topped by a GaAs layer deposited by the resistive evaporation technique. The goal is the combination of a very efficient rare-earth emitting matrix with a high-mobility semiconductor. The x-ray diffraction pattern of SnO2:Eu/GaAs heterojunctions showed simultaneously the crystallographic plane characteristics of GaAs as well as cassiterite SnO2 structure. The electric resistance of the heterojunction device is much lower than the resistance of the SnO2:2 at.%Eu and GaAs films considered separately. Micrographs obtained by scanning electron microscopy (SEM) of the cross-section showed that the interface is clearly identified, exhibiting good adherence and uniformity. A possible explanation for the low resistivity of the SnO2:2 at.%Eu/GaAs heterojunction is the formation of small channels with two-dimensional electron gas (2DEG) behavior.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Photo-Induced conductivity of heterojunction GaAs/Rare-Earth doped SnO2

Rare-earth doped (Eu3+ or Ce3+) thin layers of tin dioxide (SnO2) are deposited by the sol-gel-dip-coating technique, along with gallium arsenide (GaAs) films, deposited by the resistive evaporation technique. The as-built heterojunction has potential application in optoelectronic devices, because it may combine the emission from the rare-earth-doped transparent oxide, with a high mobility semiconductor. Trivalent rare-earth-doped SnO2 presents very efficient emission in a wide wavelength range, including red (in the case of Eu3+) or blue (Ce3+). The advantage of this structure is the possibility of separation of the rare-earth emission centers, from the electron scattering, leading to an indicated combination for electroluminescence. Electrical characterization of the heterojunction SnO2:Eu/GaAs shows a significant conductivity increase when compared to the conductivity of the individual films. Monochromatic light excitation shows up the role of the most external layer, which may act as a shield (top GaAs), or an ultraviolet light absorber sink (top RE-doped SnO2). The observed improvement on the electrical transport properties is probably related to the formation of short conduction channels in the semiconductors junction with two-dimensional electron gas (2DEG) behavior, which are evaluated by excitation with distinct monochromatic light sources, where the samples are deposited by varying the order of layer deposition

Resistividade do filme depositado via sol-gel e estado de oxidação do dopante Ce na matriz SnO2

Incorporação de Ce3+ ou Ce4+ em filmes finos de SnO2 depositados via sol-gel-dip-coating aumenta drasticamente a resistividade elétrica. No primeiro caso, temos comportamento aceitador do dopante, levando a matriz à alta compensação de carga. Por outro lado, para Ce4+, verifica-se aumento na largura da região de depleção do contorno de grão, resultando em maior espalhamento de elétrons. Medidas de caracterização elétrica sob pressão ambiente levam à barreiras de potencial mais altas do que as medidas sob vácuo, devido a adsorção de oxigênio na superfície das partículas. A presença de Ce3+ aumenta a transmitância no infravermelho, o que significa menor quantidade de elétrons livres. Dados de XANES confirmam que o tratamento térmico a 550 ºC dos filmes, ainda que promova oxidação parcial para Ce4+, preserva uma quantidade significativa (em torno de 60%) no estado Ce3+. Espectroscopia Raman mostra a evolução dos modos de vibração intra-grãos de SnO2 com o aumento da temperatura de tratamento térmico.Incorporation of Ce3+ or Ce4+ in sol-gel dip-coating SnO2 thin films increases drastically its electrical resistivity. In the first case, it is due the acceptor-like nature of the doping ion, leading the matrix to high charge compensation. on the other hand, for Ce4+ doped samples, it is verified a broadening of the grain boundary depletion layer. Measurements under room pressure leads to higher intergrain potential barriers when compared to measurements carried out under vacuum conditions, due to oxygen adsorption at particles surface. The presence of Ce3+ increases the infrared transmittance, which means a lower free electron concentration. XANES data confirms that the thermal annealing at 550 ºC of thin films, although promotes oxidation to Ce4+, still keeps a significantly amount (about 60%) of ions in the oxidation state Ce3+. Raman spectroscopy data show the evolution of the SnO2 bulk vibration modes with increasing thermal annealing temperature.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES

Schottky emission in nanoscopically crystallized Ce-doped SnO2 thin films deposited by sol-gel-dip-coating

This paper reports the electrical effects of the incorporation of Ce(III) or Ce(IV) in SnO2 thin films, prepared by the sol-gel-dip-coating technique. This doping has drastically increased the resistivity compared to undoped thin films. Nanoscopic dimension of crystallites, in the range 5-10 nm, contributes to this increase. The high number of crystallites decreases the mobility due to the increase of the density of potential barrier between grains per unit of volume. High doping leads to low conductivity when Ce(III) salt is used as precursor, which assures the acceptor-like nature of this ion in the matrix. Current as function of voltage, measured for several temperatures, leads to the predominance of Schottky conduction mechanism, even though a tunneling process seems to be a good approximation for the observed deviations at lower applied electric fields. The potential barrier for Schottky emission is in the range 0.6-0.8 eV. For Ce(IV) doping, an increase of the grain boundary depletion layer seems to be responsible for the observed high resistivity, because it leads to higher electron scattering at grain boundary. Measurements done under room atmosphere lead to a higher barrier height than measurement done under vacuum conditions, due to oxygen adsorption at particles surface. For temperatures higher than 150 degrees C, under vacuum conditions, the elimination of O-2(-) species becomes probable, increasing considerably the current density. (C) 2008 Elsevier B.V. All rights reserved.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP