O emprego de TiO2, na qualidade de semicondutor mais comumente utilizado em fotocatálise heterogênea adquire relevância, devido à sua eficiência na decomposição de poluentes da água, do ar, bactérias, células cancerígenas e na degradação de compostos orgânicos tóxicos. Este trabalho investigou a correlação entre as propriedades fotocrômicas e fotocatalíticas de fibras e dos filmes de TiO2, e de TiO2 dopados com H2WO4 e Na2WO4.2H2O. Para a síntese de fibras por electrospinning os reagentes utilizados foram: ácido acético glacial, propóxido de titânio, polivinilpirrolidona 10%, ácido túngstico e tungstato de sódio di hidratado. As fibras obtidas foram tratadas termicamente entre 650 ºC e 800 ºC, com patamar de 1 hora e taxa de aquecimento de 1,4 °C/min. Para obtenção dos filmes por spin-coater foram peparadas soluções contendo: 0,25 g de fibras tratadas entre 650 ºC e 800 ºC, etanol anidro, acetilacetona, Triton X-100 e polivinilbitiral. As amostras foram caracterizadas por difração de raios X (DRX), microscopia eletrônica de varredura (MEV) e de transmissão (MET), análise termogravimétrica (TGA) e termo-diferencial (ATD), espectroscopia de reflectância difusa (ERD), perfilometria, teoria Brunnauer Emmet e Teller (BET), ensaios de degradação de 125 mL de uma solução 20 ppm do corante alaranjado de metila e colorimetria através do sistema CIELa*b*. Os melhores resultados foram obtidos com as amostras deTiO2∕Na2WO4.2H2O. Estas amostras foram mais eficientes na mineralização do corante alaranjado de metila, pois 3 das 4 amostras sintetizadas degradaram aproximadamente 100% do corante e simultaneamente expressaram os maiores valores de reflectância, possivelmente devido a existência de uma sincronização entre as características químicas e físicas destes óxidos e a formação de defeitos pontuais (vacâncias) que ocupam posições atômicas de rede. / The use of TiO2 as the most commonly used semiconductor in heterogeneous photocatalysis becomes relevant because of its efficiency in the decomposition of pollutants from water, air, bacteria, cancer cells and the degradation of toxic organic compounds. This work investigated the correlation between the photocatalytic and photocatalytic properties of TiO2 and TiO2 fibers and TiO2 doped with H2WO4 and Na2WO4.2H2O. For the synthesis of fibers by electrospinning the reagents used were: glacial acetic acid, titanium propoxide, 10% polyvinylpyrrolidone, tungstic acid and sodium tungstate dihydrate. The obtained fibers were heat treated between 650 °C and 800 °C, with a 1 hour threshold and a heating rate of 1.4 °C/min. To obtain the films by spin-coater were prepared solutions containing: 0.25 g of treated fibers between 650 ºC and 800 ºC, anhydrous ethanol, acetylacetone, Triton X-100 and polyvinylbutyral. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission (TEM), thermogravimetric (TGA) and thermo-differential analysis (DTA), diffuse reflectance spectroscopy (ERD), profilometry, Brunnauer Emmet and Teller (BET) theory, 125 ml degradation assays of a 20 ppm solution of methyl orange dye and colorimetry through the system CIELa*b*. The best results were obtained with TiO2/Na2WO4.2H2O samples. These samples were more efficient in the methyl orange dye mineralization, since 3 of the 4 synthesized samples degraded approximately 100% of the dye and simultaneously expressed the highest values of reflectance, possibly due to the existence of a synchronization between the chemical and physical characteristics of these oxides and the formation of point defects (vacancies) that occupy atomic network positions.

O presente trabalho teve como objetivo utilizar a técnica nuclear de Correlação Angular γ-γ Perturbada (CAP) para a medida de interações hiperfinas em filmes finos e amostras em pó de óxidos semicondutores SnO2 e TiO2 puros e dopados com metais de transição para uma investigação sistemática de defeitos estruturais e do magnetismo sob o ponto de vista atômico tendo como principal motivação a candidatura à aplicação desses óxidos em spintrônica. O trabalho também teve como foco a preparação e caracterização das amostras por meio de técnicas convencionais, como difração de raios X, microscopia eletrônica de varredura, espectroscopia de energia dispersiva e medidas de magnetização. Amostras puras dos filmes foram medidas mediante a variação sistemática da temperatura de tratamento térmico e do campo magnético aplicado. Tais medidas foram realizadas no HISKP, na Universidade de Bonn (Rheinische Friedrich-Wilhelms-Universität Bonn), através de implantação de íons de 111In(111Cd) ou 181Hf(181Ta); no IPEN, por sua vez, essas medidas foram realizadas após a difusão dos mesmos núcleos de prova. Outra parte das medidas CAP foram feitas através de implantação de íons de 111mCd(111Cd) e 117Cd(117In) no Isotope Mass Separator On-Line (ISOLDE) do Centre Européen Recherche Nucléaire (CERN). As medidas foram realizadas nos intervalos de temperatura de 8 K a 1173 K. Para análise de ferromagnetismo, medidas foram feitas à temperatura ambiente com e sem aplicação de campo magnético externo. Após a comparação dos resultados das medidas macroscópicas e atômicas das amostras, foi possível concluir que há uma correlação entre os defeitos, o magnetismo e a mobilidade dos portadores de carga nos semicondutores aqui estudados. Um passo adiante na busca de semicondutores, cujo ordenamento magnético possibilite o seu uso na eletrônica baseada em spin. Alguns resultados já foram publicados, incluindo resultados obtidos na Universidade de Bonn durante o período de doutorado sanduíche [1-7]. / This study aimed the use of nuclear technique Perturbed γ-γ Angular Correlation Spectroccopy (PAC) to measure the hyperfine interactions in thin films and powder samples of SnO2 and TiO2 pure and doped with transition metals to obtain a systematic investigation of defects and magnetism from an atomic point of view with the main motivation the application in spintronics. The work also focused on the preparation and characterization of samples by conventional techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and magnetization measurements. Pure samples of the films were measured by the systematic variation of thermal treatment and applied magnetic field. These measurements were performed in HISKP at the University of Bonn (Rheinische Friedrich-Wilhelms-Universität Bonn) using 111In(111Cd) or 181Hf (181Ta); at IPEN, in turn, these measurements were performed after the diffusion of the same probe nuclei. Another part of PAC measurements were carried out using 111mCd(111Cd) and 117Cd (117In) in Isotope Mass Separator On-Line (ISOLDE) at Centre Européen Recherche Nucléaire (CERN). The measurements were performed from 8 K to 1173 K. After comparing results from macroscopic techniques with those from PAC, it was concluded that there is a correlation between the defects, magnetism and the mobility of charge carriers in semiconductors studied here. A step forward in the search for semiconductors, whose magnetic ordering allows its use in electronics based on spin. Some results have been published, including results obtained at the University of Bonn for the sandwich doctorate period [1-7].

Neste trabalho foram estudadas diferentes modificações superficiais do titânio (Ti) como método de preparação de superfícies de eletrodos para baterias de íons lítio (Li+) Inicialmente, as modificações foram produzidas pelas micro-indentações, com posterior corrosão eletroquímica por pites em soluções de brometo. As superfícies polidas, tratadas termicamente e modificadas através de micro-indentações foram avaliadas em diferentes parâmetros, tais como o potencial aplicado, concentração dos íons agressivos no eletrólito, temperatura, tempo dos testes e principalmente, sobre o impacto das deformações causadas pela força indentações para localização de orifícios produzidos por pites. Filmes porosos de titânia (TiO2) crescidos sobre o Ti puro, foram produzidos por anodização a plasma (anodização por centelhamento ou sparking) em 1M H3PO4 e em 1M Na2SO4 e por anodização nanotubular em 1M H3PO4 + 1M NaOH + 0,4 %(peso) HF. Os resultados mostraram, em óxidos tipo “esponja” formados na anodização a plasma em 1M H3PO4 e 1M Na2SO4, a incorporação de elementos do eletrólito contendo, respectivamente, P e S, numa relação de P/O > S/O e em óxidos nanotulares, a predominante incorporação de elemento de F. Posteriormente, as superfícies corroídas por pites e as superfícies de óxidos crescidos por anodização a plasma foram convertidas por sulfetação em diferentes materiais micro e nanoestruturados compostos por sulfetos e oxisulfetos de titânio, ajustando-se as condições de processo. O desenvolvimento proposto mostrou que é possível modificar a composição química do óxido formado por anodização a plasma para nanocristais de TiS2, nanofitas de TiS3 e TiOxSy, sem danificar a morfologia original dos nanoporos de TiO2. Os compostos formados podem ser usados como eletrodos nanoarquiteturados tridimensionais (3D) para microbaterias de íons lítio (Li+) com alta densidade de potência. A síntese desses compostos é realmente promissora, porque eles têm a capacidade de inserir mais íons lítio do que TiO2 puro, resultando em uma melhoria na capacidade das microbaterias. / In this study, different surface modifications of titanium (Ti) were studied as a method of surface preparation of electrodes for ion lithium batteries (Li+). Initially, the modifications were produced by micro-indentation with subsequent electrochemical pitting corrosion in solutions of bromide. The polished surfaces, heat treated and modified through micro indentations were evaluated for different values of parameters, such as applied potential, concentration of aggressive ions in the electrolyte, temperature, polarization time, and mainly intensity of the deformation caused by indentations for localizing holes produced by pitting. It was expected the adjust of location of these parameter settings promotes nucleation of pits, according to the pattern of indentations and growth of pitting depth for increased surface area. Porous films of titania (TiO2) were produced on pure Ti by plasma anodization (or sparking) in 1M H3PO4 and 1M Na2SO4. Nanotubes were synthesized by porous anodization in 1M NaOH + 1M H3PO4 + 0.4 (wt%) HF. The results showed oxide "sponge" like formed by plasma anodization, incorporating elements of the electrolyte containing respectively, P and S in a ratio P/O> S/O and, in nanotubular oxides, with predominant incorporation of F. Subsequently, the pitted surfaces and the surfaces of oxides grown by plasma anodization were converted by sulfidation into different micro and nanostructured materials consisting of titanium sulfide and oxisulfides by adjusting the process conditions. The proposed development has shown that it is possible to modify the chemical composition of the oxide formed by plasma anodizing to nanocrystals of TiS2 and nanobelts of TiS3 and TiOxSy without damaging the original morphology of the nanoporous TiO2. The formed compounds can be used as three-dimensional (3D) nanoarchitectured electrodes for ion lithium batteries (Li+) with high power density. The synthesis of these compounds is promising due to a higher ability to intercalate more ions lithium than pure TiO2, resulting in an improvement in the capacity of microbatteries.

O presente trabalho teve como objetivo utilizar a técnica nuclear de Correlação Angular γ-γ Perturbada (CAP) para a medida de interações hiperfinas em filmes finos e amostras em pó de óxidos semicondutores SnO2 e TiO2 puros e dopados com metais de transição para uma investigação sistemática de defeitos estruturais e do magnetismo sob o ponto de vista atômico tendo como principal motivação a candidatura à aplicação desses óxidos em spintrônica. O trabalho também teve como foco a preparação e caracterização das amostras por meio de técnicas convencionais, como difração de raios X, microscopia eletrônica de varredura, espectroscopia de energia dispersiva e medidas de magnetização. Amostras puras dos filmes foram medidas mediante a variação sistemática da temperatura de tratamento térmico e do campo magnético aplicado. Tais medidas foram realizadas no HISKP, na Universidade de Bonn (Rheinische Friedrich-Wilhelms-Universität Bonn), através de implantação de íons de 111In(111Cd) ou 181Hf(181Ta); no IPEN, por sua vez, essas medidas foram realizadas após a difusão dos mesmos núcleos de prova. Outra parte das medidas CAP foram feitas através de implantação de íons de 111mCd(111Cd) e 117Cd(117In) no Isotope Mass Separator On-Line (ISOLDE) do Centre Européen Recherche Nucléaire (CERN). As medidas foram realizadas nos intervalos de temperatura de 8 K a 1173 K. Para análise de ferromagnetismo, medidas foram feitas à temperatura ambiente com e sem aplicação de campo magnético externo. Após a comparação dos resultados das medidas macroscópicas e atômicas das amostras, foi possível concluir que há uma correlação entre os defeitos, o magnetismo e a mobilidade dos portadores de carga nos semicondutores aqui estudados. Um passo adiante na busca de semicondutores, cujo ordenamento magnético possibilite o seu uso na eletrônica baseada em spin. Alguns resultados já foram publicados, incluindo resultados obtidos na Universidade de Bonn durante o período de doutorado sanduíche [1-7]. / This study aimed the use of nuclear technique Perturbed γ-γ Angular Correlation Spectroccopy (PAC) to measure the hyperfine interactions in thin films and powder samples of SnO2 and TiO2 pure and doped with transition metals to obtain a systematic investigation of defects and magnetism from an atomic point of view with the main motivation the application in spintronics. The work also focused on the preparation and characterization of samples by conventional techniques such as X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy and magnetization measurements. Pure samples of the films were measured by the systematic variation of thermal treatment and applied magnetic field. These measurements were performed in HISKP at the University of Bonn (Rheinische Friedrich-Wilhelms-Universität Bonn) using 111In(111Cd) or 181Hf (181Ta); at IPEN, in turn, these measurements were performed after the diffusion of the same probe nuclei. Another part of PAC measurements were carried out using 111mCd(111Cd) and 117Cd (117In) in Isotope Mass Separator On-Line (ISOLDE) at Centre Européen Recherche Nucléaire (CERN). The measurements were performed from 8 K to 1173 K. After comparing results from macroscopic techniques with those from PAC, it was concluded that there is a correlation between the defects, magnetism and the mobility of charge carriers in semiconductors studied here. A step forward in the search for semiconductors, whose magnetic ordering allows its use in electronics based on spin. Some results have been published, including results obtained at the University of Bonn for the sandwich doctorate period [1-7].

Energy traps at the silicon surface originating from discontinuities in the lattice is detrimental to the performance of solar cells. Acting as recombination centers, they offer a location where the charge carriers may easily return to their original energy band after excitation. Surface passivation is an effective method to combat this and can be done either by suppressing traps (lowering trap density) or by forming an electric field, preventing the carriers from reaching the defect states. Silicon oxide, SiO2, and aluminum oxide, Al2O3, are two materials which have previously been shown to provide good passivating qualities. In this thesis, SiO2 and Al2O3 have been used both as single layers and in a stack configuration to passivate the surface of crystalline silicon (c-Si). Using a response surface methodology approach, temperature optimization with respect to deposition and annealing temperature has been conducted for SiO2/Al2O3 stacks deposited with plasma-enhanced atomic layer deposition, PEALD. It was shown that the same deposition temperature (Tdeposition = 140 °C, Tanneal = 395 °C) could be used for both materials and provide good passivation with an effective surface recombination velocity, Seff, of 5.3 cm/s (1Ωcm n-type Si wafers). From FTIR measurements, an increase in hydroxyl groups was seen as the SiO2 deposition temperature increased while the opposite was observed for Al2O3 which also showed fewer carbon related impurities with increasing temperature. Increasing the SiO2 temperature strongly affected the fixed charge density, causing it to decrease and even switch polarity. The fixed charge density could also be controlled by varying the thickness of the intermediate SiO2 layer. At a thickness of 1-2 nm, a minimum in the effective lifetime was observed and was correlated to Si close to flat-band conditions. N-type wafers showed a larger negative fixed charge density than p-type wafers which results in stronger field-effect passivation. For phosphorous doped emitters (200 Ω/sq on 10 Ωcm p-type wafer), it was seen that SiO2/Al2O3 stacks with a SiNx anti-reflection coating performed better than SiO2 or Al2O3 single layers. By depositing SiO2 at 130 °C in SiO2/Al2O3 stacks and annealing at 450 °C, an implied open circuit voltage (iVoc) of 710 mV was measured (AM1.5G) together with an implied fill factor (iFF) of 84.1% and a recombination parameter (J0) of 19.2 fA/cm2. Al2O3 single layer showed an extremely low J0 of 10 fA/cm2 but suffered from a decreased iFF and strong injection dependent lifetimes which originates from an inversion layer. ALD ozone processes were successfully developed for SiO2 and Al2O3.  The deposition rate per cycle for SiO2 was found to be only ~0.175 Ǻ/cycle (PEALD ~1.1 Ǻ/cycle), making it rather unpractical for use outside of research. Single layer SiO2 deposited with ozone showed, similarly to a plasma process, almost no surface passivation. Al2O3 however proved to be highly passivating on its own with a τeff = 3.8 ms, Seff = 1.2 cm/s (1 Ωcm n-type) after depositing at 250 °C. Studies on the effect of annealing showed that an annealing temperature of 450 °C is necessary to completely activate the passivation. The low Seff values were attributed to a very high negative fixed charge density ~1013 cm-2 together with strong chemical passivation.

L'ajustement adéquat de formulations sol-gel et de leurs compositions en TiO2 et SiO2 a conduit à des revêtements composites TiO2-SiO2 naturellement super-hydrophiles et présentant une persistance optimale de leur super-hydrophilie en l'absence de rayonnement UV. Cette persistance optimale est également corrélée à une facilité accrue de photo-régénération de la super-hydrophilie, par une courte exposition UV, lorsque cette propriété finit par disparaître au cours d'un vieillissement prolongé. Des adaptations spécifiques des protocoles expérimentaux montrent également qu'il est possible d'extrapoler ces performances de mouillage à toutes sortes de supports, non seulement des supports en acier inoxydable, mais aussi des supports à faible tenue thermique (par exemple des polymères ou textiles peuvent être envisagés). Des études physico-chimiques et morphologiques indiquent que, si des effets de porosité et rugosité de surface ne sont pas à exclure, les performances de mouillage des revêtements composites découlent probablement avant tout d'effets d'interfaces granulaires TiO2-SiO2. Cette hypothèse semble en partie confirmée par des premières mesures de forces superficielles par AFM en milieu aqueux et de mouillabilité à pH variable. Les travaux mettent également en évidence un parallèle entre la lipophilie et l'hydrophilie de surface de différents films sol-gel. Bien que de façon générale ce parallèle ne plaide pas en faveur d'une nettoyabilité accrue de la surface revêtue, des tests de nettoyabilité statique et dynamique montrent finalement que, du fait de leur forte composante polaire d'énergie de surface, les revêtements composites super-hydrophiles favorisent un dégraissage aisé des surfaces polluées à l'huile minérale ou végétale, ce qui valide définitivement le concept de surfaces à nettoyabilité accrue. Des approches théoriques ont également été régulièrement proposées et permettent de justifier en grande partie les comportements de mouillage à l'eau ou à l'huile observés sur les revêtements faisant l'objet de ce travail.

L'étude des premiers instants de la croissance par dépôt chimique en phase vapeur à partir d'un précurseur métalorganique (MOCVD) de films de TiO2 sur Si(100) a été réalisée in situ par analyse de surfaces (XPS, ARXPS, AES). Un dispositif expérimental original a été conçu à cet effet et mis au point. Des caractérisations ex situ (HRTEM, SIMS, GIXRD...) ont complété les informations obtenues in situ.<br />La formation d'une couche interfaciale de SiOy<2, par interaction du précurseur Ti(OCH(CH3)2)4 avec le substrat, précède la formation de TiO2 et conduit à la présence de carbone à l'interface. La diffusion de silicium au sein de la couche superficielle de TiO2 a été constatée à la température de dépôt de 675 °C. Dès les premiers instants de la croissance, des cristallites de structure anatase et rutile se forment au sein de la couche de TiO2 amorphe. La croissance des grains de rutile s'arrête en cours de dépôt. Celle des grains d'anatase se poursuit sous forme de colonnes monocristallines.

Ce travail de thèse porte sur l'élaboration et la caractérisation optique et structurale de films de silice ou de titane mésostructurés porteurs de nanoparticules d'argent. Il s'intéresse également aux propriétés photochromiques des films à base de titane. Pour ce travail, des films mésoporeux de SiO2, et de TiO2, amorphe ou anatase, ont été synthétisés par voie sol-gel et caractérisés. Après leur imprégnation par des ions métalliques, trois protocoles de réduction ont été utilisés. La croissance thermique favorise la coalescence des nanoparticules; des bâtonnets d'argent sont obtenus dans les films de silice hexagonaux 2D alors que des agglomérats se forment en surface et dans l'épaisseur des films de TiO2 présentant des pores sphériques. La réduction chimique permet une croissance rapide des nanoparticules d'argent dans les pores; des bâtonnets et sphères de taille et forme contrôlées sont obtenus dans les films de SiO2 et de TiO2, respectivement. La croissance optique des nanoparticules d'argent par photoréduction est aussi un procédé rapide; des nanoparticules avec une plus large distribution de taille que leurs similaires chimiques sont obtenues dans les films de TiO2, mais seulement quelques nanoparticules dans la matrice SiO2 en raison de sa faible réponse à l'UV. L'étude du comportement photochromique des nanoparticules d'argent déposées dans des films de TiO2 a démontré l'influence de la répartition initiale des nanoparticules et de l'intensité incidente sur la couleur du film. Un blanchiment du film optique ou chimique est observé après insolation avec une lumière monochromatique puissante, et un comportement multiphotochromique pour de faibles intensités lumineuses.

Les procédés de couplage d'un plasma à pression atmosphérique et d'un catalyseur représentent une solution prometteuse pour la dépollution atmosphérique, ou plus spécifiquement pour le traitement des Composés Organiques Volatils. En particulier, le faible coût énergétique de cette technique la rend très intéressante pour les petites concentrations (traitement d'odeurs), difficiles à traiter avec les techniques habituelles. Parmi les catalyseurs qui peuvent être employés, le TiO2 (photocatalyseur) est avantageux pour son faible coût, sa non toxicité, et surtout son excellente sélectivité en CO2. Le couplage avec un plasma pourrait améliorer la vitesse de traitement qui est très lente en photocatalyse seule. La synergie plasma/TiO2 est étudiée depuis 2000 seulement. Le but de ce travail est d'identifier les mécanismes responsables de cette synergie en séparant les contributions de la décharge, de la porosité et de l'activité photocatalytique du TiO2. Pour y parvenir, une approche originale à été utilisée en étudiant à la fois une décharge à pression atmosphérique (DBD) et une décharge à basse pression (DC pulsée) autorisant l'utilisation de diagnostics lasers infra-rouge pour effectuer des mesures in situ résolues en temps.

<p>Adsorption of organic molecules at a surface of titanium dioxide (101) anatase is studied using quantum-chemical density functional theory. Anatase can be used in solar cells. For the clean anatase surface the band gap is so large that only UV-light can excite electrons. Different groups with conjugated systems are attached to obtain a more suitable band gap. </p><p>Phenol was attached in different positions to a cluster of anatase and geometry optimized using the B3LYP-functional. The geometry that was energetically most favorable was used to put in phenylmethanol, phenylethanol, naphthol, 2-phenanthrol, 1-pyrol and 2-perylol. To give a more realistic model of phenol at anatase, a study of a two- dimensional periodic anatase surface was also made. </p><p>Molecular orbitals were calculated to study the overlap between HOMO and LUMO orbitals. The calculation shows that phenol will remain as a molecule and will not dissociate. The band gap gets smaller when molecules are attached at the cluster and with 2-perylol it reaches the energy of visible light. </p><p>The molecular orbitals for HOMO, LUMO and LUMO of the adsorbed molecule were investigated. HOMO was localized at the molecule, LUMO at the cluster and LUMO of the adsorbed molecule move closer to the energy of LUMO when the number of rings increases.</p>