O objetivo principal deste trabalho foi desenvolver um dispositivo de filme fino com anisotropia de resistividade elétrica. A idéia foi usar um efeito quântico presente em filmes muito finos de materiais condutores ou semicondutores com morfologia anisotrópica na superfície. A morfologia foi um perfil unidirecional quase-senoidal. As resistividades foram determinadas medindo-se as resistências elétricas destes materiais em direções ortogonais, levando-se em conta a geometria da amostra e suas dimensões. O material condutor usado foi Polimetilmetacrilato (PMMA) com ouro implantado na superfície. A profundidade média de implantação foi 2,7 nm. Na fabricação do dispositivo foi utilizada micro e nanolitografia, caracterização por Microscopia Eletrônica de Varredura e Microscopia de Força Atômica e implantação de ouro por MePIIID (Metal Plasma Immersion Ion Implantation and Deposition). / The main purpose of this work was to develop a thin film device with electrical anisotropic resistivity. The idea was to use a quantum effect which is present in very thin films of conductor or semiconductor materials with anisotropic morphology on the surface. The morphology was a sinusoidal-like unidirectional profile. The resistivities were determined measuring the electrical resistances of theses materials in orthogonal directions, taking in account the sample geometry and dimensions. The conductive material used was Polymethylmethacrylate (PMMA) with gold implanted on the surface. The average implanted depth was 2.7 nm. In the device fabrication were used micro and nanolithography, characterization by Scanning Electron Microscopy and Atomic Force Microscopy and gold implantation by MePIIID (Metal Plasma Immersion Ion Implantation and Deposition).

Dans son ensemble, les techniques de pointe actuelles procurent l'information nécessaire à une analyse approfondie de la cellule, ce qui nécessite cependant l’utilisation d’instruments et de plateformes analytiques différentes. Les biopuces à cellule permettent l’analyse des cellules vivantes en temps réel et constituent donc un outil important pour de nombreuses applications dans la recherche biomédicale telles que la toxicologie et la pharmaceutique.En effet, le suivi en temps réel de la réponse non-seulement physique mais aussi chimique des cellules, obtenue suite à des stimuli externes spécifiques et en utilisant un système d'imagerie cellulaire, peut fournir une meilleure compréhension des mécanismes et des voies de signalisation impliquées dans la réaction toxicologique.Le développement de tels dispositifs multianalytiques pour l'analyse biologique repose essentiellement sur la capacité de produire des surfaces fonctionnelles de pointe permettant une interaction et organisation contrôlée des cellules et d'autres entités telles que par exemple des anticorps ou des nanoparticules. Par conséquent, un grand effort technologique repose sur le développement des techniques permettant la création de motifs fonctionnels sur une surface de nature souvent inerte. Dans cette thèse, nous proposons deux techniques de micro- et nanofabrication permettant la création de motifs de cellules et d’anticorps sur un revêtement non-adhésif composé de poly (oxyde d'éthylène) (« PEO-like ») déposé par plasma. La première approche consiste à immobiliser par physisorption un micro-réseau de molécules adhésives de la matrice extracellulaire (par exemple la fibronectine) en utilisant des techniques d’impression par microcontact et par non-contact. La deuxième approche permet la création de motifs adhésifs sur la surface constitués de nanoparticules d'or (Au NPs) en utilisant des techniques d’impression similaire. L'immobilisation des Au NPs sur le revêtement « PEO-like » ne nécessite pas de modifications chimiques et est réalisé par une technique d'autoassemblage simple et irréversible. Ces surfaces d'or nanostructurées ont été testées pour l’analyse du phénomène de reconnaissance biomoléculaire et en tant que plateforme de culture cellulaire. Finalement, cette plateforme a été intégrée à un microscope plasmonique qui a permis, de façon préliminaire, la surveillance et la visualisation de la motilité d’une cellule unique, cela en temps réel et sans marquage, ainsi que la détection spécifique et sensible de protéines tests / State of the art techniques give as a whole the required information needed for the complete cell analysis but require different instruments and different types of platforms. The concept of cells on-a-chip allowing real-time analysis of living cells is, therefore, an important tool for many biomedical research applications such as toxicology and drug discovery. Monitoring in real-time the physical but also chemical response of live cells to specific external stimuli using live-cell imaging can provide a better understanding of the mechanisms and pathways involved in the toxicological reaction. The development of such multianalytical devices for biological analysis relies essentially on the ability to design advanced functional surfaces enabling a controlled interaction and organisation of cells and other nanostructures (e.g antibodies and nanoparticles). Therefore, a large technological effort is related on the development of advanced patterning techniques. In this thesis, we propose two simple and direct micro- and nano-fabrication techniques enabling the creation of cellular and sensing patterns on a non-adhesive and cell repellent plasma-deposited poly (ethyleneoxide) (PEO-like) coating. The first approach consists in immobilising a microarray of ECM molecules (cell-adhesive proteins, e.g fibronectin) on the cell repellent PEO-like surface by physisorption using microspotting or microcontact printing techniques. The second approach enables the creation of Gold nanoparticles (Au NPs) adhesive patterns on the surface using similar spotting techniques. The immobilization of Au NPs on PEO-like coatings does not require any prior chemical modifications and is achieved by a straightforward and irreversible self-assembly technique. These gold nanostructured surfaces have been tested for protein bio-recognition analysis and as a cell culture platform. Ultimately, this platform was integrated to a novel plasmonic microscope which enabled, preliminarily, the label-free monitoring and visualisation of a single cell attachment and detachment in real time, as well as the specific and sensitive detection of test proteins in a cell-free environment

Ce travail s'inscrit dans le cadre du développement de matériaux composites nanostructurés à propriétés électriques et magnétiques inédites. Afin de répondre à des besoins technologiques pour, l'électronique de puissance intégrée : le stockage ou la transmission de l'énergie, les télécommunications (antenne intégrée...), le stockage de l'information par enregistrement magnétique et le marquage biologique, le composite doit présenter globalement une polarisation magnétique élevée ainsi qu'un comportement isolant permettant de pousser les limites fréquentielles, minimiser les pertes dynamiques et découpler les grains entre eux. Les matériaux composites élaborés sont constitués d'une matrice d'accueil - magnétique (ferrite spinelle) ou non-magnétique (diélectrique = silice) - dans laquelle sont dispersées des particules métalliques (Fer-Nickel ou Cobalt). Ces matériaux sont novateurs dans la mesure où le matériau final peut bénéficier d'un couplage des propriétés magnétiques des deux phases constitutives. L'holographie électronique en transmission a mis en évidence une ocnfiguration de spins de type « vortex » dans les nanoparticules de Fe30Ni70. Les mesures holographiques ont été comparées au profil de l'aimantation, dans un vortex, modélisé par une approche micromagnétique. Des analyses physico-chimiques approfondies nous ont permis de confirmer les topologies visées : pour le composite métal-diélectrique, l'épaisseur de la couche d'enrobage a pu être contrôlée à l'échelle nanonométrique. Pour le composite métal-oxyde obtenu par croissance directe du ferrite sur la phase métallique, on a démontré une bonne dispersion des particules métalliques. Les propriétés magnétiques et structurales des différents composites, en poudre ou compactés par SPS (compactage-frittage flash), ont été caractérisées et discutées. Les propriétés fonctionnelles ont été aussi étudiées et sont très prometteuses pour les applications visées. L'enrobage des nanoparticules par la silice a permis la préparation de leur surface dans la perspective d'une fonctionnalisation par des entités biologiques.

Ces travaux de thèse portent sur la conception, la fabrication et la caractérisation de résonateurs nano-optomécaniques sous forme de disques en arséniure de Gallium (GaAs). Ces disques sont à la fois des résonateurs mécaniques oscillant au GHz, et des résonateurs optiques à mode de galerie à haut facteur de qualité (>10^5). En confinant l'énergie mécanique et optique sur un volume sub-µm^3, ils permettent d'atteindre un couplage optomécanique extrêmement large (g0 >1 MHz). Nous présentons les développements technologiques ayant permis l'intégration de ces résonateurs avec des guides de couplage optique directement sur échantillon semi-conducteur, tout en maintenant des performances à l'état de l'art. Nous discutons les différents mécanismes de couplage optomécanique (pression de radiation, photoélasticité) dans les disques GaAs, ainsi que les sources de dissipation optique et mécanique dans ces résonateurs. Nous présentons également des expériences d'optomécanique à l'air libre et en cryostat à basse température, allant de la mesure du mouvement brownien et l'observation de rétroaction dynamique, jusqu'à des premières tentatives d'approche du régime quantique du mouvement. Enfin, nous présentons un développement nano-optomécanique complémentaire mené sur le matériau nitrure de silicium (SiN), aboutissant à la fabrication de résonateurs à mode de galerie sur puce à haut facteur de qualité. Après l'étude des instabilités optiques et de la dynamique d'auto-pulsation de ces résonateurs, nous présentons des premières signatures de couplage optomécanique dissipatif dans ces systèmes.

Today, the growing and aging population, and the rise of new global threats on human health puts an increasing demand on the healthcare system and calls for preventive actions. To make existing medical treatments more efficient and widely accessible and to prevent the emergence of new threats such as drug-resistant bacteria, improved diagnostic technologies are needed. Potential solutions to address these medical challenges could come from the development of novel lab-on-chip (LoC) for point-of-care (PoC) diagnostics. At the same time, the increasing demand for sustainable energy calls for the development of novel approaches for energy conversion and storage systems (ECS), to which micro- and nanotechnologies could also contribute. This thesis has for objective to contribute to these developments and presents the results of interdisciplinary research at the crossing of three disciplines of physics and engineering: electrokinetic transport in fluids, manufacturing of micro- and nanofluidic systems, and surface control and modification. By combining knowledge from each of these disciplines, novel solutions and functionalities were developed at the macro-, micro- and nanoscale, towards applications in PoC diagnostics and ECS systems. At the macroscale, electrokinetic transport was applied to the development of a novel PoC sampler for the efficient capture of exhaled breath aerosol onto a microfluidic platform. At the microscale, several methods for polymer micromanufacturing and surface modification were developed. Using direct photolithography in off-stoichiometry thiol-ene (OSTE) polymers, a novel manufacturing method for mold-free rapid prototyping of microfluidic devices was developed. An investigation of the photolithography of OSTE polymers revealed that a novel photopatterning mechanism arises from the off-stoichiometric polymer formulation. Using photografting on OSTE surfaces, a novel surface modification method was developed for the photopatterning of the surface energy. Finally, a novel method was developed for single-step microstructuring and micropatterning of surface energy, using a molecular self-alignment process resulting in spontaneous mimicking, in the replica, of the surface energy of the mold. At the nanoscale, several solutions for the study of electrokinetic transport toward selective biofiltration and energy conversion were developed. A novel, comprehensive model was developed for electrostatic gating of the electrokinetic transport in nanofluidics. A novel method for the manufacturing of electrostatically-gated nanofluidic membranes was developed, using atomic layer deposition (ALD) in deep anodic alumina oxide (AAO) nanopores. Finally, a preliminary investigation of the nanopatterning of OSTE polymers was performed for the manufacturing of polymer nanofluidic devices. / <p>QC 20140509</p> / Rappid / NanoGate / Norosensor

O objetivo principal deste trabalho foi desenvolver um dispositivo de filme fino com anisotropia de resistividade elétrica. A idéia foi usar um efeito quântico presente em filmes muito finos de materiais condutores ou semicondutores com morfologia anisotrópica na superfície. A morfologia foi um perfil unidirecional quase-senoidal. As resistividades foram determinadas medindo-se as resistências elétricas destes materiais em direções ortogonais, levando-se em conta a geometria da amostra e suas dimensões. O material condutor usado foi Polimetilmetacrilato (PMMA) com ouro implantado na superfície. A profundidade média de implantação foi 2,7 nm. Na fabricação do dispositivo foi utilizada micro e nanolitografia, caracterização por Microscopia Eletrônica de Varredura e Microscopia de Força Atômica e implantação de ouro por MePIIID (Metal Plasma Immersion Ion Implantation and Deposition). / The main purpose of this work was to develop a thin film device with electrical anisotropic resistivity. The idea was to use a quantum effect which is present in very thin films of conductor or semiconductor materials with anisotropic morphology on the surface. The morphology was a sinusoidal-like unidirectional profile. The resistivities were determined measuring the electrical resistances of theses materials in orthogonal directions, taking in account the sample geometry and dimensions. The conductive material used was Polymethylmethacrylate (PMMA) with gold implanted on the surface. The average implanted depth was 2.7 nm. In the device fabrication were used micro and nanolithography, characterization by Scanning Electron Microscopy and Atomic Force Microscopy and gold implantation by MePIIID (Metal Plasma Immersion Ion Implantation and Deposition).

Les nano-antennes optiques constituent un élément clé pour le contrôle et l’intéraction lumière/matière à l’échelle nanométrique. Ces systèmes opèrent dans le domaine de l’optique visible et proche infrarouge. Les propriétés de ces composants sont contrôlées en modifiant la taille, la forme et le matériau utilisé. Ces paramètres sont ajustés par les processus de fabrication de l’antenne. Dans le domaine des radio-fréquences, le tuner permet d’ajuster la fréquence de résonance de l’antenne de façon dynamique. Nous avons dans le cadre de cette thèse voulu adapter ce concept de tuner au domaine de l’optique. Le principe employé consiste à changer la résistance de charge de l’antenne, c’est-à-dire l’indice du milieu électrique environnant. Pour cela, nous avons utilisé un matériau anisotrope constitué de molécules de cristaux liquides. L’indice optique est alors modifié par l ’application d’un champ électrique statique. Le changement des propriétés spectrales ainsi que de diffusion d’une antenne de type dimère sont ici démontrées.Toujours en analogie avec les antennes radio-fréquences, nous avons étudié la propriété de transduction électron-photon dans le cas des antennes optiques. Dans ce but, nous avons considéré deux configurations. La première concerne l’utilisation de nanotubes de carbone placés dans une configuration de transistor à effet de champ. Ces objets émettent de la lumière par une recombinaison de paires électrons-trous dans le domaine des longueurs d’ondes Télécom. La seconde configuration emploie des jonctions tunnels fabriquées par électro-migration. Dans ce cas là, la jonction est assimilée à une antenne à interstice. A cause des faibles dimensions des jonctions (autour de 1 nm), nous nous sommes intéressés à la réponse en optique non linéaire de ses objets. Cette technique permet de localiser la jonction tunnel grâce à une forte exaltation du signal. L’etude des différentes caractérisques de ses jonctions sont ici présentées. Une fois la transduction du signal réalisée par l’antenne radiofréquence, celui-ci est acheminé via une ligne de transmission. A l’ échelle nanométrique, les guides plasmoniques s’avèrent être un type de structure approprié. Dans ce cas, les guides peuvent à la fois servir d’´electrode mais aussi de guide. Dans le cadre de cette thèse, nous avons étudié par microscopie à fuites radiatives, dans l’espace direct et réciproque, la plus simple des géométries : le guide ruban métallique. Nous avons cherché à comprendre, pourquoi ce type de structure présente une largeur de coupure. / Optical nano-antennae are the new class of components to control light/matterinteraction at the nanoscale. These devices are operating in the visible to near infraredpart of the spectrum. The properties of these nano objects are controlled by theform, the size and the material.In the radio frequency domain, the tuner changes dynamically the operatingwavelength of the antenna. In this thesis work, we search to transfer this conceptto the nanoscale. The principle is to change the load impedance of the antenna, i.e.changing the optical index of the dielectric medium around the nano-object. Forthat we used anisotropic liquid cristal molecules. The value of the optical index iscontrolled by applying an external electrical static field. The effects on the spectraland scattering properties are demonstrated on a single dimer nano-antenna.However with the microwave antennae, we were interesting to the electronsphotonstransduction with an optical antenna. In this mind, we studied two differentsconfigurations. The first one concerns the use of carbon nanotubes placedin a field effect transistor configuration. These nano-objects emit light in the Telecomwavelength range by a radiative combination of electrons and holes. the secondconfiguration used planar tunnel junctions made by electromigration. In this case,the junctions are view as an optical gap antenna. Because the gap are very small(around 1 nm), we have studied the nonlinear optical response of these objects. Thisnonlinear optical characterization allows to determined the location of the tunneljunctions by an enhancement of the optical signal. The results about the properties(electrical and optical) of these tunnel junctions are presented.Once the transduction by the radio frequency antenna is achieved, this signalis transporting by a transmission line. By transposition at the nanoscale, the plasmonicswaveguides prove to be the most appropriate structure. In this case, theycould be used as an electrode or a waveguide. In this thesis work, we have studiedby leakage radiation microscopy, in the direct and reciprocal space, the simplestgeometry : plasmonic metal strips. We search to understand why these structureshave a cut-off width.

The aim of this work is to create a process which allows the tailored growth of Ge nanocrystals for use in photovoltic applications. The multilayer systems used here provide a reliable method to control the Ge nanocrystal size after phase separation. In this thesis, the deposition of GeOx/SiO2 and Ge:SiOx~ 2/SiO2 multilayers via reactive dc magnetron sputtering and the self-ordered Ge nanocrystal formation within the GeOx and Ge:SiOx~ 2 sublayers during subsequent annealing is investigated. Mostly the focus of this work is on the determination of the proper deposition conditions for tuning the composition of the systems investigated. For the GeOx/SiO2 multilayers this involves changing the GeOx composition between elemental Ge (x = 0) and GeO2 (x = 2), whereas for the Ge:SiOx~ 2/SiO2 multilayers this involves changing the stoichiometry of the Ge:SiOx~ 2 sublayers in the vicinity of stochiometric silica (x = 2). The deposition conditions are controlled by the variation of the deposition rate, the deposition temperature and the oxygen partial pressure. A convenient process window has been found which allows the sequential deposition of GeOx/SiO2 or Ge:SiOx ~2/SiO2 without changing the oxygen partial pressure during deposition. For stoichiometry determination Rutherford back-scattering spectrometry has been applied extensively. The phase separation in the spatially confined GeOx and Ge:SiOx ~2 sublayers was investigated by X-ray absorption spectroscopy at the Ge K-edge. The Ge sub-oxides content of the as-deposited multilayers diminishes with increasing annealing temperature, showing complete phase separation at approximately 450° C for both systems (using inert N2 at ambient pressure). With the use of chemical reducing H2 in the annealing atmosphere, the temperature regime where the GeOx phase separation occurs is lowered by approximately 100 °C. At temperatures above 400° C the sublayer composition, and thus the density of the Ge nanocrystals, can be altered by making use of the reduction of GeO2 by H2. The Ge nanocrystal formation after subsequent annealing was investigated with X-ray scattering, Raman spectroscopy and electron microscopy. By these methods the existence of 2 - 5 nm Ge nanocrystals at annealing temperatures of 550 (GeOx) - 700° C (Ge:SiOx ~2) has been confirmed which is within the multilayer stability range. The technique used allows the production of extended multilayer stacks (50 periods ~ 300 nm) with very smooth interfaces (roughness ~ 0.5 nm). Thus it was possible to produce Ge nanocrystal layers with ultra-thin SiO2 separation layers (thickness ~ 1 nm) which offers interesting possibilities for charge transport via direct tunneling.

The aim of this work is to create a process which allows the tailored growth of Ge nanocrystals for use in photovoltic applications. The multilayer systems used here provide a reliable method to control the Ge nanocrystal size after phase separation. In this thesis, the deposition of GeOx/SiO2 and Ge:SiOx~ 2/SiO2 multilayers via reactive dc magnetron sputtering and the self-ordered Ge nanocrystal formation within the GeOx and Ge:SiOx~ 2 sublayers during subsequent annealing is investigated. Mostly the focus of this work is on the determination of the proper deposition conditions for tuning the composition of the systems investigated. For the GeOx/SiO2 multilayers this involves changing the GeOx composition between elemental Ge (x = 0) and GeO2 (x = 2), whereas for the Ge:SiOx~ 2/SiO2 multilayers this involves changing the stoichiometry of the Ge:SiOx~ 2 sublayers in the vicinity of stochiometric silica (x = 2). The deposition conditions are controlled by the variation of the deposition rate, the deposition temperature and the oxygen partial pressure. A convenient process window has been found which allows the sequential deposition of GeOx/SiO2 or Ge:SiOx ~2/SiO2 without changing the oxygen partial pressure during deposition. For stoichiometry determination Rutherford back-scattering spectrometry has been applied extensively. The phase separation in the spatially confined GeOx and Ge:SiOx ~2 sublayers was investigated by X-ray absorption spectroscopy at the Ge K-edge. The Ge sub-oxides content of the as-deposited multilayers diminishes with increasing annealing temperature, showing complete phase separation at approximately 450° C for both systems (using inert N2 at ambient pressure). With the use of chemical reducing H2 in the annealing atmosphere, the temperature regime where the GeOx phase separation occurs is lowered by approximately 100 °C. At temperatures above 400° C the sublayer composition, and thus the density of the Ge nanocrystals, can be altered by making use of the reduction of GeO2 by H2. The Ge nanocrystal formation after subsequent annealing was investigated with X-ray scattering, Raman spectroscopy and electron microscopy. By these methods the existence of 2 - 5 nm Ge nanocrystals at annealing temperatures of 550 (GeOx) - 700° C (Ge:SiOx ~2) has been confirmed which is within the multilayer stability range. The technique used allows the production of extended multilayer stacks (50 periods ~ 300 nm) with very smooth interfaces (roughness ~ 0.5 nm). Thus it was possible to produce Ge nanocrystal layers with ultra-thin SiO2 separation layers (thickness ~ 1 nm) which offers interesting possibilities for charge transport via direct tunneling.:Contents 1 Introduction and motivation 1 2 Basic aspects 6 2.1 Microstructure of sub-stoichiometric oxides (SiOx, GeOx) 6 2.2 Phase transformations 9 2.3 Quantum confinement effect in nanocrystals 12 2.4 Applications of nanostructures in 3rd generation photovoltaics 17 3 Experimental setup 21 3.1 The magnetron deposition chamber 21 3.2 (Reactive) dc sputtering 22 3.3 Annealing processing 26 3.4 X-ray facilities 26 4 Analytical methods 30 4.1 Rutherford backscattering spectrometry (RBS) 30 4.2 Raman scattering 33 4.3 (Grazing incidence) X-ray diffraction (GIXRD) 35 4.4 X-ray reflectivity (XRR) 39 4.5 X-ray absorption near edge structure (XANES) 41 4.6 Transmission electron microscopy (TEM) 42 5 Properties of reactive dc magnetron sputtered Si-Ge-O (multi)layers 44 5.1 Deposition rate and film stoichiometry investigations 44 5.2 Stoichiometry dependent properties of GeOx/SiO2 multilayers 47 5.3 Lateral intercluster distance of the Ge nanocrystals in multilayers 51 6 Confined Ge nanocrystal growth in GeOx/SiO2 multilayers 54 6.1 Phase separation in GeOx single layers and GeOx/SiO2 multilayers 54 6.2 Crystallization in GeOx single layers and GeOx/SiO2 multilayers 58 6.3 Multilayer stability and smallest possible Ge nanocrystal size 60 6.4 Stacked Ge NC films with ultra thin SiO2 separation layers 66 7 Confined Ge nanocrystal growth in Ge:SiOx/SiO2 multilayers 71 7.1 Phase separation in Ge:SiOx/SiO2 multilayers 72 7.2 Crystallisation in Ge:SiOx/SiO2 multilayers 76 8 Summary and conclusions 79 List of Figures 83 List of Tables 85 Bibliography 86