Synthesis and characterization of nanoperforated metal oxide thin films

For advanced devices in the application fields of data storage, solar cell and biosensing, one of the major challenges to achieve high efficiency is the fabrication of nanopatterned metal oxide surfaces. Such surfaces often require both precise structure at the nanometer scale and controllable patterned structure at the macro scale. Nowadays, the dominating candidates to fabricate nanopatterned surfaces are the lithographic technique and block-copolymer masks, most of which are unfortunately costly and inefficient. An alternative bottom-up approach, which involves organic/inorganic self-assembly and dip-coating deposition, has been studied intensively in recent years and has proven to be an effective technique for the fabrication of nanoperforated metal oxide thin films. The overall objective of this work was to optimize the synthesis conditions of nanoperforated TiO2 (NP-TiO2) thin films, especially to be compatible with mixed metal oxide systems. Another goal was to develop fabrication and processing of NP-TiO2 thin films towards largescale production and seek new applications for solar cells and biosensing. Besides the traditional dip-coating and drop-casting methods, inkjet printing was used to prepare thin films of metal oxides, with the advantage of depositing the ink onto target areas, further enabling cost-effective fabrication of micro-patterned nanoperforated metal oxide thin films. The films were characterized by water contact angle determination, Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Grazing Incidence XRay Diffraction. In this study, well-ordered zinc titanate nanoperforated thin films with different Zn/Ti ratios were produced successfully with zinc precursor content up to 50 mol%, and the dominating phase was Zn2Ti3O8. NP-TiO2 structures were also obtained by a cost-efficient means, namely inkjet printing, at both ambient temperature and 60 °C. To further explore new biosensing applications of nanoperforated oxide thin films, inkjet printing was used for the fabrication of both continuous and patterned polymeric films onto NP-TiO2 and perfluorinated phosphate functionalized NP-TiO2 substrates, respectively. The NP-TiO2 films can be also functionalized with a fluoroalkylsilane, resulting in hydrophobic surfaces on both titania and silica. The surface energy contrast in the nanoperforations can be tuned by irradiating the films with UV light, which provides ideal model systems for wettability studies.

Hydrogen Sensor Application of Anodic Titanium Oxide Nanostructures

Hydrogen (H2) fuel cells have been considered a promising renewable energy source. The recent growth of H2 economy has required highly sensitive, micro-sized and cost-effective H2 sensor for monitoring concentrations and alerting to leakages due to the flammability and explosiveness of H2 Titanium dioxide (TiO2) made by electrochemical anodic oxidation has shown great potential as a H2 sensing material. The aim of this thesis is to develop highly sensitive H2 sensor using anodized TiO2. The sensor enables mass production and integration with microelectronics by preparing the oxide layer on suitable substrate. Morphology, elemental composition, crystal phase, electrical properties and H2 sensing properties of TiO2 nanostructures prepared on Ti foil, Si and SiO2/Si substrates were characterized. Initially, vertically oriented TiO2 nanotubes as the sensing material were obtained by anodizing Ti foil. The morphological properties of tubes could be tailored by varying the applied voltages of the anodization. The transparent oxide layer creates an interference color phenomena with white light illumination on the oxide surface. This coloration effect can be used to predict the morphological properties of the TiO2 nanostructures. The crystal phase transition from amorphous to anatase or rutile, or the mixture of anatase and rutile was observed with varying heat treatment temperatures. However, the H2 sensing properties of TiO2 nanotubes at room temperature were insufficient. H2 sensors using TiO2 nanostructures formed on Si and SiO2/Si substrates were demonstrated. In both cases, a Ti layer deposited on the substrates by a DC magnetron sputtering method was successfully anodized. A mesoporous TiO2 layer obtained on Si by anodization in an aqueous electrolyte at 5°C showed diode behavior, which was influenced by the work function difference of Pt metal electrodes and the oxide layer. The sensor enabled the detection of H2 (20-1000 ppm) at low operating temperatures (50–140°C) in ambient air. A Pd decorated tubular TiO2 layer was prepared on metal electrodes patterned SiO2/Si wafer by anodization in an organic electrolyte at 5°C. The sensor showed significantly enhanced H2 sensing properties, and detected hydrogen in the range of a few ppm with fast response/recovery time. The metal electrodes placed under the oxide layer also enhanced the mechanical tolerance of the sensor. The concept of TiO2 nanostructures on alternative substrates could be a prospect for microelectronic applications and mass production of gas sensors. The gas sensor properties can be further improved by modifying material morphologies and decorating it with catalytic materials.

Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.

Étude par dynamique moléculaire de l'ablation par impulsions laser ultrabrèves de cibles nanocristallines

L’ablation de cibles d’Al nanocristallines (taille moyenne des cristallites d = 3,1 et 6,2 nm) par impulsions laser ultrabrèves (200 fs) a été étudiée par l’entremise de si- mulations combinant la dynamique moléculaire et le modèle à deux températures (two- temperature model, TTM) pour des fluences absorbées allant de 100 à 1300 J/m2. Nos simulations emploient un potentiel d’interaction de type EAM et les propriétés électro- niques des cibles en lien avec le TTM sont représentées par un modèle réaliste possédant une forme distincte dans le solide monocristallin, le solide nanocristallin et le liquide. Nous avons considéré l’effet de la taille moyenne des cristallites de même que celui de la porosité et nous avons procédé à une comparaison directe avec des cibles mono- cristallines. Nous avons pu montrer que le seuil d’ablation des métaux nanocristallins est significativement plus bas, se situant à 400 J/m2 plutôt qu’à 600 J/m2 dans le cas des cibles monocristallines, l’écart étant principalement dû à l’onde mécanique plus im- portante présente lors de l’ablation. Leur seuil de spallation de la face arrière est aussi significativement plus bas de par la résistance à la tension plus faible (5,40 GPa contre 7,24 GPa) des cibles nanocristallines. Il est aussi apparu que les contraintes résiduelles accompagnant généralement l’ablation laser sont absentes lors de l’ablation de cibles d’aluminium nanocristallines puisque la croissance cristalline leur permet d’abaisser leur volume spécifique. Nos résultats indiquent aussi que le seuil de fusion des cibles nano- cristallines est réduit de façon marquée dans ces cibles ce qui s’explique par la plus faible énergie de cohésion inhérente à ces matériaux. Nos simulations permettent de montrer que les propriétés structurelles et électroniques propres aux métaux nanocristallins ont toutes deux un impact important sur l’ablation.

Étude de la voie de signalisation de l’insuline chez la drosophile par une approche phosphoprotéomique

La phosphorylation est une modification post-traductionnelle modulant l’activité, la conformation ou la localisation d’une protéine et régulant divers processus. Les kinases et phosphatases sont responsables de la dynamique de phosphorylation et agissent de manière coordonnée. L’activation anormale ou la dérégulation de kinases peuvent conduire au développement de cancers ou de désordres métaboliques. Les récepteurs tyrosine kinase (RTKs) sont souvent impliqués dans des maladies et la compréhension des mécanismes régissant leur régulation permet de déterminer les effets anticipés sur leurs substrats. Dans ce contexte, le but de cette thèse est d’identifier les évènements de phosphorylation intervenant dans la voie de l’insuline chez la drosophile impliquant un RTK : le récepteur de l’insuline (InR). La cascade de phosphorylation déclenchée suite à l’activation du récepteur est conservée chez le mammifère. Afin d’étudier le phosphoprotéome de cellules S2 de drosophile, nous avons utilisé une étape d’enrichissement de phosphopeptides sur dioxyde de titane suivie de leur séparation par chromatographie liquide (LC) et mobilité ionique (FAIMS). Les phosphopeptides sont analysés par spectrométrie de masse en tandem à haute résolution. Nous avons d’abord démontré les bénéfices de l’utilisation du FAIMS comparativement à une étude conventionnelle en rapportant une augmentation de 50 % dans le nombre de phosphopeptides identifiés avec FAIMS. Cette technique permet de séparer des phosphoisomères difficilement distinguables par LC et l’acquisition de spectres MS/MS distincts où la localisation précise du phosphate est déterminée. Nous avons appliqué cette approche pour l’étude des phosphoprotéomes de cellules S2 contrôles ou traitées à l’insuline et avons identifié 32 phosphopeptides (sur 2 660 quantifiés) pour lesquels la phosphorylation est modulée. Étonnamment, 50 % des cibles régulées possèdent un site consensus pour la kinase CK2. Une stratégie d’inhibition par RNAi a été implémentée afin d’investiguer le rôle de CK2 dans la voie de l’insuline. Nous avons identifié 6 phosphoprotéines (CG30085, su(var)205, scny, protein CDV3 homolog, D1 et mu2) positivement régulées suite à l’insuline et négativement modulées après le traitement par RNAi CK2. Par essai kinase in vitro, nous avons identifié 29 cibles directes de CK2 dont 15 corrélaient avec les résultats obtenus par RNAi. Nous avons démontré que la phosphorylation de su(var)205 (S15) était modulée par l’insuline en plus d’être une cible directe de CK2 suite à l’expérience RNAi et à l’essai kinase. L’analyse des données phosphoprotéomiques a mis en évidence des phosphopeptides isomériques dont certains étaient séparables par FAIMS. Nous avons déterminé leur fréquence lors d’études à grande échelle grâce à deux algorithmes. Le script basé sur les différences de temps de rétention entre isomères a identifié 64 phosphoisomères séparés par LC chez la souris et le rat (moins de 1 % des peptides identifiés). Chez la drosophile, 117 ont été répertoriés en combinaison avec une approche ciblée impliquant des listes d’inclusion. Le second algorithme basé sur la présence d’ions caractéristiques suite à la fragmentation de formes qui co-éluent a rapporté 23 paires isomériques. L’importance de pouvoir distinguer des phosphoisomères est capitale dans le but d’associer une fonction biologique à un site de phosphorylation précis qui doit être identifié avec confiance.

Effets des nanoparticules manufacturées sur les cellules pulmonaires humaines

La détection et la caractérisation des nanoparticules manufacturées (NPM) est l’une des premières étapes pour contrôler et diminuer leurs risques potentiels sur la santé humaine et l’environnement. Différents systèmes d’échantillonnage dans l’air existent pour l’évaluation d’une exposition aux NPM. Cependant, ils ne mesurent pas le risque potentiel de cette exposition à la santé humaine ni les mécanismes cellulaires qui en seraient responsables. Nos objectifs de recherche sont 1) Évaluer les effets de différents types de nanoparticules sur des cellules pulmonaires humaines et 2) Identifier de nouveaux mécanismes intracellulaires activés lors de l’exposition à divers types de NPM. Méthodologie: La lignée de cellules A549 a été utilisée. Trois types de NPM ont été étudiés (différentes concentrations et temps d’exposition): les nanoparticules de dioxyde de titane de type anatase (TiO2), les nanotubes de carbone simple paroi (NTCSP) et les nanoparticules de noir de carbone (NC). La viabilité cellulaire a été mesurée par le test MTS, le test PrestoBlue et le test d’exclusion du bleu de Trypan (uniquement pour les NTCSP). La mesure du stress oxydatif a été déterminée par la mesure des dérivés réactifs de l’oxygène (ROS) en utilisant l’essai DCFH-DA. L’activation d’une réponse anti-oxydative a été déterminée par la mesure de la forme réduite (GSH) et oxydée (GSSG) du glutathion, ainsi que du ratio GSH/GSSG (seulement avec NTCSP et TiO2). Résultats: Les trois nanoparticules ne semblent pas être toxiques pour les cellules A549 car il y a une diminution significative mais minime de la viabilité cellulaire. Cependant, elles induisent une augmentation du contenu intracellulaire en ROS qui est à la fois dépendante du temps et de la concentration. Aucun changement dans les concentrations de GSH et GSSG n’a été observé. En conclusion, nos données indiquent que la mesure de la viabilité n’est pas un critère suffisant pour conclure à la toxicité des NPM. La production de ROS est un critère intéressant, cependant il faudra démontrer l’activation de systèmes anti-oxydatifs pour expliquer l’absence de mortalité cellulaire suite à l’exposition aux NPM.

Investigations on Some Titania Supported Catalysts

Titania is a versatile metal oxide with multiple applications. Titania supported catalysts are reported to be much more active compared to conventional silica or alumina supported ones in some reactions. TiO2 (anatase) having high surface area, with better crystallinity and high onset temperature of rutilation can be prepared by thermal hydrolysis of titanyl sulfate solution under controlled conditions. Calcinations at 350oC for 6 hrs were necessary to crystallize anatase. Method of preparation and percentage of the loaded metal oxides have greater influence on surface area. Drastic decrease in surface area was observed upon rutilation. Rutilation started at different temperatures depending on the metal oxide and the method of preparation. TiO2 should be characterized with high surface area, phase purity and high onset temperature of rutilation.Which should be well above the optimum temperature of a designated reaction in which it is employed as a catalyst. Variation in physical properties, depending upon the method of preparation is greater in TiO2 supported catalysts. Methanation activity was found to be highly dependent on nickel concentration present on the surface of the pellets. The methanation activity is strongly influenced by support material. The rate and turn over frequency of methanation and toluene oxidation activity of these catalysts are also equally important from an industrial point of view.

(1−x)MgAl2O4-xTiO2 dielectrics for microwave and millimeter wave applications

The MgAl2O4 ceramics were prepared by the conventional solid-state ceramic route and the dielectric properties studied in the microwave frequency region (3–13 GHz). The phase purity and crystal structure were identified using the X-ray diffraction technique. The MgAl2O4 spinel ceramics show interesting microwave dielectric properties (εr = 8.75, Qux f = 68 900 GHz (loss tangent = 0.00017 at 12.3 GHz), τf =−75 ppm/◦C). The MgAl2O4 has high negative τf, which precludes its immediate use in practical applications. Hence the microwave dielectric properties of MgAl2O4 spinels were tailored by adding different mole fractions of TiO2. The εr and Q factor of the mixed phases were increased with the molar addition of TiO2 into the spinel to form mixtures based on (1−x)MgAl2O4-xTiO2 (x = 0.0−1.0). For x = 0.25 in (1−x)MgAl2O4-xTiO2, the microwave quality factor reaches a maximum value of Qux f = 105 400 GHz (loss tangent = 0.00007 at 7.5 GHz) where εr and τf are 11.035 and −12 ppm/◦C, respectively. The microwave dielectric properties of the newly developed 0.75MgAl2O4-0.25TiO2 dielectric is superior to several commercially available low loss dielectric substrates.

Ship-in-a-bottle synthesis of 2,4,6-triphenylthiapyrylium cations encapsulated in zeolites Y and beta: a novel robust photocatalyst

The 2,4,6-triphenylthiapyrylium ion has been obtained imprisoned inside the supercages of the tridirectional, large pore zeolites Y and beta via ship-in-a-bottle synthesis from chalcone and acetophenone in the presence of hydrogen sulfide. The resulting solids are efficient and robust photocatalysts that are able to degrade phenol and aniline in water with a higher efficiency than the P-25 TiO2 standard. Preliminary tests have shown that these encapsulated dye materials are also efficient photocatalysts for the oxidative degradation of malodorous sulfurcontaining molecules.

Tailoring the microwave dielectric properties of BaRE2Ti4O12 and BaRE2Ti5O14 ceramics bycompositional variations

Ceramic dielectric resonators in the BaO-RE2O3-TiO2 (RE=rare earth) system have been prepared by the conventional solid state ceramic route. The dielectric properties have been tailored by substitution of different rare earth oxides and by bismuth oxide addition. The dielectric constants increased with Bi addition whereas the Q decreased. The temperature coeffecient of the resonant frequency improved with bismuth addition.

Tailoring the Microwave Dielectric Properties of BaRE2Ti4012 and BaRE2Ti5014 Ceramics by Compositional Variations

Ceramic dielectric resonators in the BaO-RE2O3-TiO2 (RE = rare earth) system have been prepared by the conventional solid state ceramic route. The dielectric properties have been tailored by substitution of different rare earth oxides and by bismuth oxide addition. The dielectric constants increased with Bi addition whereas the 0 decreased. The temperature coefficient of the resonant frequency improved with bismuth addition

Luminescence tuning and enhanced nonlinear optical properties of nanocomposites of ZnO–TiO2

In this article we present the spectral and nonlinear optical properties of ZnO–TiO2 nanocomposites prepared by colloidal chemical synthesis. Emission peaks of ZnO–TiO2 nanocomposites change from 340 nm to 385 nm almost in proportion to changes in Eg. The nanocomposites show self-defocusing nonlinearity and good nonlinear absorption behaviour. The nonlinear refractive index and the nonlinear absorption increase with increasing TiO2 volume fraction at 532 nm and can be attributed to the enhancement of exciton oscillator strength. ZnO–TiO2 is a potential nanocomposite material for the tunable light emission and for the development of nonlinear optical devices with a relatively small limiting threshold

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity.

Spectral Characterization of Laser Induced Plasma from Titanium Dioxide

Optical emission from TiO2 plasma, generated by a nanosecond laser is spectroscopically analysed. The main chemical species are identified and the spatio-temporal distribution of the plasma parameters such as electron temperature and density are characterized based on the study of spectral distribution of the line intensities and their broadening characteristics. The parameters of laser induced plasma vary quickly owing to its expansion at low background pressure and the possible deviations from local thermodynamic equilibrium conditions are tested to show its validity