A oxidação anódica local utilizando o Microscópio de Força Atômica (AFM - Atomic Force Microscopy) foi investigada aplicando-se uma tensão negativa entre sonda de nitreto de silício e superfícies de Si. Todas as amostras foram limpas em uma solução de 1 NH4OH (30%): 1H2O2 (38%): 4H2O(DI) a 80ºC conhecida na literatura como SC1 (Standard Cleaning 1) ou, alternativamente, uma imersão em solução diluída de ácido hidrofluorídrico seguido de SC1 ou fervura em álcool isopropílico. As nano-oxidações consistiram de padrões quadrados localizados de óxido com área de 0,25 µm² e foram obtidos através do crescimento de linhas paralelas com espaço e comprimento interlinear constante (<2 nm) e várias varreduras dos quadrados em uma mesma área. Das análises de AFM, foram obtidos perfis transversais e 3D, os quais foram empregados na obtenção da espessura do óxido como função da tensão aplicada, número de varreduras e intervalo de tempo após a limpeza SC1. Foi observado que a espessura aumenta com a tensão negativa aplicada e com o número de varreduras. Também foram realizadas simulações para levantar as distribuições de tensão e de campo elétrico no sistema sonda-ar-silício ou sonda-ar-óxido-silício(substrato). Observou-se uma oxidação local assistida por um alto campo elétrico capaz de induzir difusão iônica local finita na extremidade da sonda. Foi simulado também o efeito das diferentes terminações de sonda do AFM, circular ou pontiaguda, no campo elétrico e na queda de tensão. Foram também realizadas oxidações com sondas recobertas com ouro em superfícies de Si precedidas de imersão simples em solução de ácido hidrofluorídrico seguido ou não do procedimento de limpeza SC1. Por fim, análises de absorção por infravermelho (FTIR) foram realizadas em superfícies de Si oxidadas por AFM para analisar a estrutura dos óxidos anódicos obtidos. A oxidação anódica utilizando sondas de nitreto de silício ocorre apenas após pré-limpeza terminada com SC1, sendo catalisada pelos altos campos elétricos (_ 106 V/cm), tendo como elementos reagentes, as espécies H2O adsorvidas e o óxido nativo hidrolisado na superfície após a etapa de limpeza SC1. / Local anodic oxidation of silicon using Atomic Force Microscopy (AFM) was investigated by applying a negative voltage between silicon nitride tip and Si surfaces. All samples were cleaned with an ammonium-based solution known in literature as standard cleaning 1 (SC1) or a dip in a diluted hydrofluoric acid solution followed by SC1 or, also, boiling in isopropyl alcohol. Localized squares patterns of oxide, 0.25 µm² in area, were formed by growing parallel lines with constant interlinear spacing and length and several scans in the same area. From AFM analysis with non-biased tip, it was obtained 3D and section profiles, which were used to obtain the oxide thickness as a function of the applied voltage, number of scans and interval of time after SC1 cleaning. It was noteworthy that thickness increases with the applied negative voltage and with the number of scans. Simulations were performed in order to model voltage and electric field distributions of the system tip-air-silicon or tip-air-oxide-silicon(substrate) indicating a local oxidation assisted by high electrical field and local ionic diffusion of species. It was simulated the effect of tip termination, circular or sharpen, on the electric field and voltage distributions. In addition, oxidations were performed using Au coated tips onto Si surfaces previously dipped in diluted hydrofluoric acid solution followed or not by SC1 cleaning process. Finally, infrared absorption analysis (FTIR) were performed in order to analise the structure of the obtained anodic oxides. The anodic oxidation using silicon nitride tips has occurred only after SC1 precleaning step, being catalized by high electric field (_ 106 V/cm), having as reagents, the adsorbed water species and hydrolized native oxide on the surface after the SC1 cleaning step.

[pt] Nesta dissertação de mestrado, nós desenvolvemos um processo de litografia baseado na técnica de microscopia de força atômica. O estudo do processo de litografia aqui utilizado inicia-se com a deposição e caracterização de filmes finos de sulfeto de arsênio amorfo (a-As2S3) em substratos de silício e a deposição de uma camada metálica de alumínio, utilizada como máscara, sobre a superfície do a-As2S3. O microscópio de força atômica é utilizado para escrever os padrões de forma controlada na camada metálica, e para tal, a influencia dos parâmetros de controle do microscópio na realização da litografia foi analisada. Para a transferência do padrão litografado realiza-se um posterior processo de fotossensibilização e dissolução química do a-As2S3 com uma solução de K2CO3. Após a dissolução, uma camada de ouro foi depositada por erosão catódica DC, seguido de uma nova dissolução, desta vez com NaOH resultando na transferência de nanoestruturas de Au para o substrato de silício. / [en] In this dissertation, we have developed a lithography process based on the atomic force microscopy of technique. The study of the lithography process starts with the deposition and characterization of amorphous arsenic sulfide thin films (a-As2S3) in silicon substrates and the deposition of a metallic aluminum layer, used as mask, on the surface of the a-As2S3. An atomic force microscope was used to write patterns in a controlled way on the metallic layer. Therefore, the influence of microscope feedback system on the accomplishment of the lithography was analyzed. In order to transfer the lithographed pattern to a silicon substrate, the a- As2S3 was exposed to a UV light source and was dissolved with a K2CO3 solution. Then, a thin gold layer was deposited by sputtering DC, and a new dissolution, now with NaOH was performed, leading to the deposition of Au nanostructures onto the silicon substrate.

[pt] Neste trabalho, foram estudadas blendas formadas pelo polímero Policloreto de Vinila (PVC) e pelo polímero biodegradável Poli Hidroxibutirato (PHB), com diferentes concentrações relativas de cada polímero. As blendas foram preparadas em forma de membrana, com concentrações de PHB variando de 2 a 40%. A técnica utilizada para o preparo das amostras foi a evaporação do solvente, sendo dicloroetano o solvente utilizado. A composição química das superfícies das blendas foi caracterizada utilizando a técnica de espectroscopia de fotoelétrons induzida por raios-X (XPS). A morfologia e as propriedades mecânicas das amostras foram estudadas com o auxílio da microscopia de força atômica (AFM). Medidas de calorimetria diferencial exploratória foram realizadas a fim de conhecermos a miscibilidade das blendas formadas. Nas blendas formadas observou-se uma segregação de PHB para a superfície, sendo o percentual de PHB na superfície na faixa de 18±2%, mesmo para blendas com mais baixa concentração relativa de PHB. Entretanto o grau de cristalização do PHB em cada blenda aumenta com a incorporação do polímero na blenda. Foi observado um aumento na dureza conforme aumentamos a concentração de PHB na blenda. As blendas foram caracterizadas como parcialmente miscíveis. / [en] In this work, the study of polymer blends surfaces formed by a biodegradable polymer (poly3-hydroxybutyrate, PHB) and PVC (polyvinyl chloride) with different molar percentages of PHB is presented. The blends samples were prepared as membranes with PHB molar concentrations from 2 to 40%. The technique used to prepare the membranes was the solvent-casting technique, using dichloroethene as solvent. The chemical composition of the blends samples surfaces were characterized by X-ray photoelectron spectroscopy (XPS). Their morphologies and mechanical properties were studied by atomic force microscopy (AFM). Differential scanning calorimeter measures were obtained in order to know the blends miscibility. A PHB surface segregation of 18±2% was observed, even for the blends with lower PHB concentrations. However, the degree of the PHB crystallization in each blend increases with the increasing incorporation of PHB in the blend volume. An increase in the blends hardness was observed while the PHB blends concentration increases. The blends were founded to be partially miscible.

[pt] Neste trabalho, foram estudadas filmes poliméricos densos formadas por acetato de celulose (AcC) e polihidroxialkanoato de cadeia média PHAmcl, com diferentes concentrações relativas de cada polímero. Os filmes de PHAmcl/DAC foram preparadas a partir de soluções poliméricas, diluídas em dimetil cetona, na qual se realiza uma mistura com agitação contínua. Foram preparadas as amostras: AcC puro, PHAmcl puro e seis misturas com concentrações variando de 2 porcento a 12 porcento (m/v) de PHAmcl em AcC. Medidas de calorimetria diferencial exploratória e análise dinâmica mecânica foram realizadas a fim de se conhecer a miscibilidade das blendas formadas A composição química das superfícies desses filmes foi caracterizada utilizando a técnica de espectroscopia de fotoelétrons induzida por raios-X (XPS). A morfologia e as propriedades mecânicas das amostras foram estudadas com o auxílio da microscopia de força atômica (AFM). Observou-se nas misturas um enriquecimento na superfície de PHAmcl e uma alteração da morfologia para toda a superfície com a incorporação de PHAmcl. Foi observada uma diminuição na dureza com o aumento a concentração de PHAmcl no filmes. Os filmes apresentaram miscibilidade até 10 porcento PHAmcl/90porcentoAcC em volume. / [en] In this work, the study of thick films formed by cellulose acetate and medium chain length polyhydroxyalkanotes with different molar concentration of PHB is presented. The films were prepared by polymeric solutions diluted in dimethil ketone with continued agitation. The solvent evaporation occurs on a glass plate in controlled atmosphere of 300 C. Eight samples were prepared: pure AcC and PHAmcl and mixtures with PHAmcl bulk concentrations in the range of 2 to 12 percent (w/v). Differential scanning calorimetry and dynamic mechanical analysis measurements were performed in order to know the samples miscibility. The surface chemical composition of the samples was characterized by X- ray photoelectron spectroscopy (XPS). The morphology and mechanical properties were studied by atomic force microscopy (AFM). PHAmcl surface enrichment and morphology modification of the films were observed on the whole surface with the increasing of PHAmcl. A decrease in the films hardness was observed for increasing PHAmcl bulk concentration. The films were found to be miscible until 10percentPHAmcl/90percentAcC bulk concentration.

Le récepteur low-density lipoprotein receptor-related protein 1 (LRP-1) est capable d’internaliser des protéases impliquées dans la progression du cancer, et constitue donc une cible thérapeutique prometteuse. Cependant, LRP-1 peut également réguler certaines protéines membranaires. Son ciblage dans une stratégie de modulation de la protéolyse pourrait donc affecter l’adhésion et la dynamique du cytosquelette. Dans ce travail, nous avons étudié l’influence de l’invalidation de LRP-1 sur des paramètres originaux corrélés au potentiel invasif de cellules cancéreuses par microscopie à force atomique (AFM). Cette invalidation induit des changements dans la dynamique d’adhérence des cellules et dans la morphologie, tels qu’un renforcement des fibres de stress et un étalement plus prononcé, causant une augmentation de la surface et de la circularité cellulaires. L’analyse des propriétés mécaniques par AFM a montré que ces différences sont acccompagnées par une augmentation du module d’Young. De plus, les mesures montrent une diminution globale de la motilité cellulaire et une perturbation de la persistance directionnelle. Une augmentation de la force d’adhésion entre cellules invalidées pour LRP-1 et une bille fonctionnalisée à la gélatine a également été observée. Enfin, nos données de spectroscopie de force enregistrées à l’aide d’une pointe fonctionnalisée par un anticorps anti-sous-unité d’intégrine β1 montrent que l’invalidation de LRP-1 modifie la dynamique des intégrines. Dans leur ensemble, nos résultats montrent que des techniques classiquement utilisées dans l’investigation de cellules cancéreuses peuvent être couplées à l’AFM pour ouvrir l’accès à des paramètres complémentaires, pouvant faciliter la discrimination entre différents degrés de potentiel invasif. / The low-density lipoprotein receptor-related protein 1 (LRP-1) can internalize proteases involved in cancer progression and is thus considered a promising therapeutic target. However, it has been demonstrated that LRP-1 is also able to regulate membrane-anchored proteins. Thus, strategies that target LRP-1 to modulate proteolysis could also affect adhesion and cytoskeleton dynamics. Here, we investigated the effect of LRP-1 silencing on parameters reflecting cancer cells’ invasiveness by atomic force microscopy (AFM). The results show that LRP-1 silencing induces changes in the cells’ adhesion behavior, particularly the dynamics of cell attachment. Clear alterations in morphology, such as more pronounced stress fibers and increased spreading, leading to increased area and circularity, were also observed. The determination of the cells’ mechanical properties by AFM showed that these differences are correlated with an increase in Young’s modulus. Moreover, the measurements show an overall decrease in cell motility and modifications of directional persistence. An overall increase in the adhesion force between the LRP-1-silenced cells and a gelatin-coated bead was also observed. Ultimately, our AFM-based force spectroscopy data, recorded using an antibody directed against the β1 integrin subunit, provide evidence that LRP-1 silencing modifies integrin dynamics. Together, our results show that techniques traditionally used for the investigation of cancer cells can be coupled with AFM to gain access to complementary phenotypic parameters that can help discriminate between specific phenotypes associated with different degrees of invasiveness.

Les vésicules extracellulaires (VEs) sont des nanovésicules circulantes (30 à 100nm de diamètre) libérées dans l'espace extracellulaire par la plupart des cellules humaines, suite à leur activation ou à leur apoptose. Les VEs se divisent en 3 grandes catégories ; les exosomes (Exo), les microparticules (MPs) et les corps apoptotiques (cAPO). Les VEs sont présentes à l'état physiologique dans les différents fluides biologiques du corps humain et jouent un rôle majeur dans différents processus physio-pathologiques. De nos jours, plusieurs techniques, certaines en routine, sont utilisées pour étudier les VEs. Cependant, aucune d'entre elles ne permet de déterminer à la fois leur concentration, leur taille et leurs caractéristiques biochimiques. Un consensus existe sur la nécessité de combiner des techniques pour disposer enfin d'une caractérisation fine et complète des VEs. Il est d'un intérêt majeur de développer des plateformes analytiques dédiées à ces VEs en vue d'améliorer la qualification des échantillons biologiques et de découvrir de nouveaux biomarqueurs de pathologies humaines ou de bio-indicateurs de suivi thérapeutique.Notre projet consiste à développer une plateforme NanoBioAnalytique (NBA) combinant trois techniques : l'imagerie par Résonance des Plasmons de Surface (SPRi), la Microscopie à Force Atomique (AFM) et la Spectrométrie de Masse (MS). L'enjeu est de développer une interface biopuce-instruments qui permettra d'effectuer des investigations multiphysiques et multiéchelles apportant, en une stratégie globale, les informations plus complètes sur les différentes populations de VEs.[...]Ces travaux ont montré la capacité de notre plateforme à détecter sélectivement, et simultanément, différentes sous-populations des VEs co-existantes dans un échantillon complexe tel que du plasma, en s'appuyant sur l'expression différentielle des marqueurs protéiques membranaires. Les taux de capture se sont avérés être directement corrélés à la concentration des vésicules dans l'échantillon injecté. L'analyse AFM a permis de déterminer la distribution en taille de différentes sous-populations de VEs et permettre une analyse différentielle de la distribution en taille sur la gamme 20 nm - 1000 nm. Enfin, des études protéomiques "sur-puce" ont été également engagées afin de caractériser la composition en protéines des VEs libérées sous différentes conditions. Cette analyse a permis d'établir des premiers profils protéomiques différentiels des VEs dans les échantillons étudiés.La plateforme NBA est une méthode efficace pour caractériser et quantifier les VEs, sans marquage et avec une grande sensibilité, sur une large gamme dynamique (environ 10(7) à 10(12) particules/mL) cohérente avec celle existante en fluide physiologique et sur une plage de taille couvrant 2 décades. Elle s'inscrit parmi les approches les plus prometteuses pour l'investigation des VEs en complément de la cytométrie en flux. La grande adaptabilité de cette méthode d'analyse des VEs ouvre de larges perspectives de déploiement dans les secteurs de la Santé, de l'Environnement et de l'Agro-alimentaire. / Extracellular vesicles (EVs) are small vesicles (30 to 1000 nm) released from different cell types, upon activation or apoptosis, and present in most body fluids (Blood, Urine….). Based on the current state of knowledge of their biogenesis and biochemical properties, EVs can be devided into three distinct populations: exosomes (EXO), microparticles (MPs) and apoptotic bodies (APOb). EVs have been found to play important biological roles and are also biomarkers of different pathologies. […] The first step consists of the injection of the samples containing EVs onto the biochip surface. This step is accomplished by SPR technique that allows label-free monitoring of EVs immunocapture onto the surface of a biochip presenting different specific bioreceptors. Following the capture of EVs, a nanometrological investigation of the biochip surface by AFM is engaged to characterize the physical properties of captured vesicles (size, morphology, etc..). Owning a nanometrical resolution, AFM can discriminate between individual EVs and vesicles or protein aggregates, leading to an accurate characterization of individual vesicles. The coupling of SPR technique with AFM was adapted to offer a representative global view of each array of bioreceptors and to measure the size of thousands of individual EVs. A proteomic investigation was also engaged to characterize the proteomic compositions of the different subpopulations of EVs. Such an investigation could contribute to the understanding of EVs biogenesis, biology and pathophysiology. To evaluate the potential of our platform to detect, quantify and characterize nanoparticles, two calibration particles, which cover the lower and upper size range of EVs, were chosen: (i) virus-like particles of 50 nm of diameter, also called CP50, and (ii) protein-functionnalized synthetic beads of 920 nm of diameter, called CP920. The capture tests in SPR showed a specific capture of these two calibration particles with their specific bioreceptors, immobilized onto the biochip surface, regardless the complexity of the media in which they were diluted. Also, a positive correlation was obtained between the capture level, measured by SPR, and the particle 9

In the past two decades much effort has been put in the characterization of the mechanical<p>and surface properties at the nano-scale in order to conceive reliable N/MEMS<p>(Nano and Micro ElectroMechanical Systems) applications. Techniques like nanoindentation,<p>nanoscratching, atomic force microscopy have become widely used to measure<p>the mechanical and surface properties of materials at sub-micro or nano scale. Nevertheless,<p>many phenomena such us pile-up and pop-in as well as surface anomalies<p>and roughness play an important role in the accurate determination of the materials<p>properties. The first goal of this report is to study the infulence of these sources of data<p>distortion on the experimental data. The results are discussed in the first experimental<p>chapter.<p>On the other hand, conceptors would like to adapt/tune the mechanical and surface<p>properties as a function of the required application so as to adapt them to the industrial<p>need. Coatings are usually applied to materials to enhance performances and reliability<p>such as better hardness and elastic modulus, chemical resistance and wear resistance.<p>In this work, the magnetron sputtering technique is used to deposit biocompatible thin<p>layers of different compositions (titanium carbide, titanium nitride and amorphous<p>carbon) over a titanium substrate. The goal of this second experimental part is the<p>study of the deposition parameters influence on the resulting mechanical and surface<p>properties.<p>New materials such as nanocrystal superlattices have recently received considerable<p>attention due to their versatile electronic and optical properties. However, this new<p>class of material requires robust mechanical properties to be useful for technological<p>applications. In the third and last experimental chapter, nanoindentation and atomic<p>force microscopy are used to characterize the mechanical behavior of well ordered lead<p>sulfide (PbS) nanocrystal superlattices. The goal of this last chapter is the understanding<p>of the deformation process in order to conceive more reliable nanocrystal<p>superlattices. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

This thesis studies a scheme to fabricate small-scaled metal structures by electrochemical metal deposition and lift off. The key point is the use of self-assembled monolayers (SAMs) to control both interfacial charge transfer in electrodeposition and adhesion of the deposit to the substrate. Patterned SAMs exhibiting blocking and non-blocking areas are applied as templates in electrochemical deposition of Cu or Au. Thiol SAMs on Au substrates are used, namely alkane thiols and thiols combining an aliphatic chain with a biphenyl or biphenyl analogous pyridine-phenyl moieties. The patterning of SAMs is realised with microcontact printing (μCP) and electron beam lithography. Electrochemical deposition based on defects in the SAMs is optimised towards generating small nanostructures and depending on the system single or stepped potential procedures are applied. Generated metal structures are transferred to an insulator by lift off. Au microstructures (~10 μm) have been made with microcontact printing and transferred onto epoxy glue, which can potentially be used as microelectrodes in electroanalytical chemistry. Sub-100 nm Cu features and sub-40 nm Au features have been created with electron beam lithography respectively. Lift off process has successfully transferred Cu nanostructures onto epoxy glue with high precision. In contrast to the deposition mediated by defects, Cu deposition mediated by discharging Pd²⁺ coordinated to a pyridine terminated SAM directly through the SAM molecules has been explored as a new approach. This new approach has potential to decrease the size of the metal structure further and the preliminary results show possibility of sub-10 nm features. SAMs prepared with a newly synthesised molecule, 3-(4'-(methylthio)-[1,1'-biphenyl]-4-yl)propane-1-thiol, are characterised by STM, XPS and NEXAFS. The metal structures are investigated by SEM, AFM and STM.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Abstract This thesis presents a novel method for fabricating quantum dot light-emitting devices (QDLEDs) based on colloidal inorganic light-emitting nanoparticles incorporated into an organic semiconductor matrix. CdSe core/ZnS shell nanoparticles were inkjet-printed in air and sandwiched between organic hole and electron transport layers to produce efficient photon-emissive media. The light-emitting devices fabricated here were tested as individual devices and integrated into a display setting, thus endorsing the capability of this method as a manufacturing approach for full-colour high-definition displays. By choosing inkjet printing as a deposition method for quantum dots, several problems currently inevitable with alternative methods are addressed. First, inkjet printing promises simple patterning due to its drop-on-demand concept, thus overruling a need for complicated and laborious patterning methods. Secondly, manufacturing costs can be reduced significantly by introducing this prudent fabrication step for very expensive nanoparticles. Since there are no prior demonstrations of inkjet printing of electroluminescent quantum dot devices in the literature, this work dives into the basics of inkjet printing of low-viscosity, relatively highly volatile quantum dot inks: piezo driver requirements, jetting parameters, fluid dynamics in the cartridge and on the surface, nanoparticle assembly in a wet droplet and packing of dots on the surface are main concerns in the experimental part. Device performance is likewise discussed and plays an important role in this thesis. Several compositional QDLED structures are described. In addition, different pixel geometries are discussed. The last part of this dissertation deals with the principles of QDLED displays and their basic components: RGB pixels and organic thin-film transistor (OTFT) drivers. Work related to transistors is intertwined with QDLED work; ideas for surface treatments that enhance nanoparticle packing are carried over from self-assembled monolayer (SAM) studies in the OTFT field. Moreover, all the work done in this thesis project was consolidated by one method, atomic force microscopy (AFM), which is discussed throughout the entire thesis.