Vertically aligned nanocomposite (VAN) thin films have recently stimulated significant research interest to achieve better material functionality or multifunctionalities. In VAN thin films, both phases grow epitaxially in parallel on given substrates and form a unique nano-checkerboard structure. Multiple strains, including the vertical strain which along the vertical interface and the substrate induced strain which along the film and substrate interface, exist in VAN thin films. The competition of these strains gives a promise to tune the material lattice structure and future more the nanocomposite film physical properties. Those two phases in the VAN thin films are selected based on their growth kinetics, thermodynamic stability and epitaxial growth ability on given substrates. In the present work, we investigated unique epitaxial two-phase VAN (BiFeO3)x:(Sm2O3)1-x and (La0.7Sr0.3MnO3)x:(Mn3O4)1-x thin film systems by pulsed laser deposition. These VAN thin films exhibit a highly ordered vertical columnar structure with good epitaxial quality. The strain of the two phases can be tuned by deposition parameters, e.g. deposition frequency and film composition. Their strain tunability is found to be related directly to the systematic variation of the column widths and domain structures. Their physical properties, such as dielectric loss and ferromagnetisms can be tuned systematically by this variation. The growth morphology, microstructure and material functionalities of VAN thin films can be varied by modifying the phase ratio, substrate orientation or deposition conditions. Systematic study has been done on growing (SrTiO3)0.5:(MgO)0.5 VAN thin films on SrTiO3 and MgO substrates, respectively. The variation of column width demonstrates the substrate induced strain plays another important role in the VAN thin film growth. The VAN thin films also hold promise in achieving porous thin films with ordered nanopores by thermal treatment. We selected (BiFeO3)0.5:(Sm2O3)0.5 VAN thin films as a template and get uniformly distributed bi-layered nanopores. Controllable porosity can be achieved by adjusting the microstructure of VAN (BiFeO3):(Sm2O3) thin films and the annealing parameters. In situ heating experiments within a transmission electron microscope column provide direct observations into the phases transformation, evaporation and structure reconstruction during the annealing. Systematic study in this dissertation demonstrate that the vertically aligned nanocomposite microstructure is a brand new architecture in thin films and an exciting approach that promises tunable material functionalities as well as novel nanostructures.

Vertically aligned nanocomposite (VAN) oxide thin films are unique nanostructures with two-phase self-assembled, heteroepitaxially grown on single-crystal substrates. Both phases tend to grow vertically and simultaneously on a given substrate with lattice matching in the system. The nanostructured thin film system could form different in-plane morphologies including nano-checkerboard, nanopillar in matrix and nanomaze structures. The VAN thin films with tunable vertical lattice strain and novel microstructures provide fascinating approaches to achieve enhanced functionalities. In this dissertation, the microstructure and vertical strain effect on low-field magnetoresistance (LFMR) have been investigated in heteroepitaxial La0.7Sr0.3MnO3 (LSMO):CeO2 and LSMO:ZnO VAN thin films with a vertical strain of 0.13 % and 0.5 %, respectively. We demonstrate that LFMR can be tuned by column width and vertical strain in these VAN systems, i.e., smaller column width and larger vertical strain could result in a larger LFMR in the vertical nanocomposite heteroepitaxial thin films. The physical mechanism of enhanced LFMR in LSMO-based VAN has been explored. Single-phase LSMO and LSMO-based VANs have been grown on different substrates with different secondary phase compositions. Substrate effect in single-phase LSMO films shows that LFMR tends to increase with grain misorientation factor because the cross-section of electron conduction paths reduces as grain misorientation factor increases. (LSMO)1-x:(ZnO)x VAN heteroepitaxial films without large angle grain boundary (GB) have been used to study the pure phase boundary (PB) effect on the LFMR. It shows that increased PBs tends to reduce the cross-section of the conducting path and thus favor the spin-dependent tunneling in nanomaze structures with ferromagnetic/insulating/ferromagnetic vertical sandwiches. Tilted aligned LSMO nanostructured films with artificial GBs have been designed to investigate pure GBs influence on LFMR. The results indicate that decoupling of neighboring ferromagnetic (FM) domains by artificial GBs is necessary to achieve enhanced LFMR properties; and the strength of the GBs can be controlled by post-annealing to tune the LFMR effect. The VAN heteroepitaxial films display excellent microstructure compatibility and strain tuning. Perovskite oxides can be combined with many other oxide materials to form VAN architectures. The microstructure and lattice strain in the unique heteroepitaxial VANs can be used to engineer and tune the existing/new functionalities.

<p>Functional oxide-based thin films have attracted much attention owing to their broad applications in modern society. The multifunction tuning in oxide thin films is critical for obtaining enhanced properties. In this dissertation, four new nanocomposite thin film systems with highly textured growth have been fabricated by pulsed laser deposition technique. The functionalities including ferromagnetism, ferroelectricity, multiferroism, magnetoelectric coupling, low-field magnetoresistance, transmittance, optical bandgap and dielectric constants have been demonstrated. Besides, the tunability of the functionalities have been studied via different approaches.</p> <p>First, varies deposition frequencies have been used in vertically aligned nanocomposite BaTiO₃:YMnO₃ (BTO:YMO) and BaTiO₃:La_0.7Sr_0.3Mn₃(BTO:LSMO) thin films. In both systems, the strain coupling effect between the phases are affected by the density of grain boundaries. Increasing deposition frequency generates thinner columns in BTO:YMO thin films, which enhances the anisotropic ferromagnetic response in the thin films. In contrast, the columns in BTO:LSMO thin films become discontinuous as the deposition frequency increases, leading to the diminished anisotropic ferromagnetic response. Coupling with the ferroelectricity in BTO, the room temperature multiferroic properties have been obtained in these two systems.</p> <p> Second, the impact of the film composition has been demonstrated in La_0.7Ca_0.3MnO₃ (LCMO):CeO₂thin film system, which has an insulating CeO₂in ferromagnetic conducting LCMO matrix structure. As the atomic percentage of the CeO₂increases, enhanced low-field magnetoresistance and increased metal-to-insulator transition temperature are observed. The thin films also show enhanced anisotropic ferromagnetic response comparing with the pure LCMO film.</p> <p> Third, the transition metal element in Bi₃MoM_TO₉(M_T, transition metals of Mn, Fe, Co and Ni) thin films have been varied. The thin films have a multilayered structure with M_T-rich pillar-like domains embedded in Mo-rich matrix structure. The anisotropic magnetic easy axis and optical properties have been demonstrated. By the element variation, the optical bandgaps, dielectric constants as well as anisotropic ferromagnetic properties have been achieved. </p> <p> The studies in this dissertation demonstrate several examples of tuning the multifunctionalities in oxide-based nanocomposite thin films. These enhanced properties can broaden the applications of functional oxides for advanced nanoscale devices.</p><br>

Le développement de procédé évoluant à la pression atmosphérique représente un enjeu majeur dans le dépôt de couches minces nanocomposites. Parmi ces procédés, les Décharges à Barrières Diélectriques présentent l'avantage d'être un procédé vert sans effluent gazeux, pouvant facilement être intégrées dans une chaine de production industrielle. L'approche choisie pour la réalisation de couches minces nanocomposites repose sur l'injection sous forme d'aérosol d'une suspension colloïdale dans la DBD. Les nanoparticules semi-conductrices de TiO2 sont choisies et mise en suspension dans un alcool polymérisable tel que l'isopropanol. L’objectif de ce travail est de contrôler le transport des nanoparticules et la croissance de la matrice dans la DBD en vue de réaliser une couche mince nanocomposite.Différentes méthodes de formation de l'aérosol et de filtration sont évaluées, ainsi que différents gaz vecteur (Ar, N2). Dans tous les cas considérés, la décharge est filamentaire.L'estimation des valeurs des différentes forces s'exerçant sur une nanoparticule dans une DBD confortée par un modèle numérique à permis d'orienter les expérimentations. Il est ainsi possible, à partir des paramètres permettant de générer le plasma, d'influencer le dépôt des nanoparticules et la croissance de la matrice. Les dépôts obtenus sont analysés ex situ par microscopie électronique à balayage, spectroscopie infrarouge, Raman et à rayon X et in situ avec la diffusion laser.Dans le régime filamentaire considéré, nous montrons que le flux de gaz et la fréquence de la tension joue des rôles prépondérants sur le dépôt des couches minces nanocomposites. Cette étude a permis de mettre en évidence qu’une simple fréquence n’est pas suffisante pour déposer la couche mince nanocomposite. Cependant l’utilisation d’une double fréquence semble être la meilleure approche pour séparer le transport des nanoparticules de celui de la croissance de la matrice. / Development of an atmospheric pressure process presents a major concern in the deposition of nanocomposites thin films. Among these processes, Dielectrics Barrier Discharges takes advantages to be green processes without gas effluent, which can be easily integrate in an industrial line production. The chosen approach for the nanocomposite thin film deposition is based on the injection of an aerosol of a colloidal suspension in the DBD. Semi-conductive TiO2 nanoparticles are chosen and put in suspension in a polymerizable alcohol as isopropanol. The objective of the present work is to control the transport of the nanoparticles as well as the matrix growth in the DBD in order to realize the nanocomposites thin film Different methods of the aerosol formation and filtration are evaluated, as well as the carrier gas (Ar, N2). In each case considered, the discharge works in filamentary. Estimating values of the different forces acting on the nanoparticles in a DBD comforted by a numerical model allowed to guide the experimentations. Thanks to the parameter which generated the plasma, it is possible to influence the nanoparticles deposition and the matrix growth. Depositions are ex situ analyzed by scanning electron microscopy, Infra-red, Raman, and X-ray spectroscopy and in situ by laser scattering. In the filamentary regime considered, we show that the gas flow rate and the frequency of the voltage play a dominant role on the deposition of nanocomposites thin films. This study allowed to highlight that a simple frequency is not enough to deposit the nanocomposite thin film. However, the use of a double frequencies seems to be the best way to separate the nanoparticles transport to the surface from that of the matrix growth.

Les nanoparticules (NPs) d'Ag sont très utilisées dans le secteur de la santé, dans l'industrie alimentaire et dans les produits de consommation pour leurs propriétés antimicrobiennes. Le grand rapport surface sur volume des NPs d'Ag permet une augmentation importante du relargage d'Ag comparé au matériau massif et donc une toxicité accrue vis à vis des micro-organismes sensibles à cet élément. Ce travail de thèse présente une évaluation des propriétés antimicrobiennes de petites NPs d'Ag (<20 nm) enrobées dans des matrices de silice sur la photosynthèse d'algues vertes. Deux techniques d'élaboration par voie physique ont été utilisées pour fabriquer ces nanocomposites: (i) l'implantation ionique à basse énergie et (ii) la pulvérisation d'Ag couplée avec la polymérisation plasma. Les propriétés structurales et optiques de ces nanostructures ont été étudiées par microscopie électronique à transmission, réflectivité et ellipsométrie. Cette dernière technique, couplée à un modèle basé sur l'approximation quasi-statique de type Maxwell-Garnett, a permis la détection de petites variations dans la taille et la densité des NPs d'Ag. Le relargage d'argent de ces NPs d'Ag enrobées dans des diélectriques a été mesuré par spectrométrie de masse après immersion dans de l'eau tamponnée. La toxicité à court terme de l'Ag sur la photosynthèse d'algues vertes, Chlamydomonas reinhardtii, a été évaluée par fluorométrie. L'enrobage des nanoparticules dans un diélectrique réduit leur interaction avec l'environnement, et les protège d'une oxydation rapide. La libération d'Ag bio-disponible (impactant sur la photosynthèse des algues) est contrôlée par la profondeur à laquelle se trouvent les NPs d'Ag dans la matrice hôte de silice. Cette étude permet d'envisager le design de revêtements à effet biocide contrôlé. En couplant les propriétés antimicrobiennes de ces NPs d'Ag enrobées à leur qualité d'antenne plasmonique, ces nanocomposites peuvent être utilisés pour détecter et prévenir les premières étapes de la formation de biofilms sur des surfaces. Ainsi, une dernière partie de ce travail est dédiée à l'étude de la stabilité et de l'adsorption de protéines fluorescentes Discosoma rouges recombinantes (DsRed) sur ces surfaces diélectriques avec la perspective du développement de dispositifs SERS. / Silver nanoparticles (AgNPs) because of their strong biocide activity are widely used in health-care sector, food industry and various consumer products. Their huge surface-volume ratio enhances the silver release compared to the bulk material, leading to an increased toxicity for microorganisms sensitive to this element. This work presents an assessment of the biocide properties on algal photosynthesis of small (<20 nm) AgNPs embedded in silica layers. Two physical approaches were used to elaborate these nanocomposites: (i) low energy ion beam synthesis and (ii) combined silver sputtering and plasma polymerization. These techniques allow elaboration of a single layer of AgNPs embedded in silica films at defined nanometer distances (from 0 to 7 nm) beneath the free surface. The structural and optical properties of the nanocomposites were studied by transmission electron microscopy, reflectance spectroscopy and ellipsometry. This last technique, coupled to modelling based on the quasi-static approximation of the classical Maxwell-Garnett formalism, allowed detection of small variations over the size and density of the embedded AgNPs. The silver release from the nanostructures after immersion in buffered water was measured by inductively coupled plasma mass spectrometry. The short-term toxicity of Ag to the photosynthesis of green algae, Chlamydomonas reinhardtii, was assessed by fluorometry. Embedding AgNPs reduces their interactions with the buffered water, protecting the AgNPs from fast oxidation. The release of bio-available silver (impacting on the algal photosynthesis) is controlled by the depth at which AgNPs are located for the given host silica matrix. This provides a procedure to tailor the biocide effect of nanocomposites containing AgNPs. By coupling the controlled antimicrobial properties of the embedded AgNPs and their quality as plasmonic antenna, these coatings can be used to detect and prevent the first stages of biofilm formation. Hence, the last part of this work is dedicated to a study of the structural stability and adsorption properties of Discosoma recombinant red (DsRed) fluorescent proteins deposited on these dielectric surfaces with perspectives of development of SERS devices.

Ce travail de thèse porte sur la déformation bi-axiale contrôlée de nano-composites W/Cu en couches minces déposées sur des substrats polyimides. La nano-structuration est obtenue par stratification de deux matériaux immiscibles (W et Cu) par pulvérisation ionique avec contrôle de la taille des grains au sein du film mince par contrôle de l'épaisseur selon la direction decroissance du film. Nous avons développé une procédure permettant de caractériser le comportement mécanique des échantillons à deux échelles différentes. L'essai de traction biaxial est couplé à la diffraction des rayons X (déformation microscopique) et à la corrélation d'images numériques (déformation macroscopique). Nous avons utilisé une machine de tractionbi-axiale développée dans le cadre d’un projet ANR sur la ligne de lumière DiffAbs du synchrotron SOLEIL. Elle permet de contrôler les contraintes dans des films minces supportés par des substrats polyimides. La confrontation des résultats obtenus par ces deux techniques dans le domaine d'élasticité a montré que la déformation est intégralement transmise via l’interfacefilm - substrat. La seconde étape de notre travail a consisté à étudier les déformations du nanocomposite W/Cu au-delà du domaine d’élasticité. Nous avons mis en évidence trois domaines de déformation associés à différents mécanismes de déformation. La limite d'élasticité du nanocomposite W/Cu a été déterminée en comparant la déformation élastique du film mince à la déformation macroscopique du substrat. Enfin, l'étude de la limite d'élasticité du nanocomposite W/Cu pour différents ratios de force a révélé un comportement fragile du nanocomposite W/Cu. / This thesis focuses on the biaxial deformation of W/Cu nanocomposite thin films deposited on polyimide substrates. The grain size in the thin film is controlled by stratification of two immiscible materials (W and Cu) employing sputtering techniques. We developed a procedure to characterize the mechanical behavior of samples at two different scales. A biaxial tensile test is coupled to X-ray diffraction (microscopic deformation) and digital image correlation (macroscopic deformation) techniques. We used a biaxial tensile setup developed in the framework of an ANR project on the DiffAbs beamline at synchrotron SOLEIL allowing forthe control of stresses in thin films supported by polyimide substrates. By comparing the strains obtained by these two techniques, the applied strain is determined to be transmitted unchanged in the elastic domain through the film - substrate interface. The second part of our work was to study the deformation of W/Cu nanocomposite beyond the elastic range. We have highlighted three domains of deformation associated with different deformation mechanisms. The elastic limit of the W/Cu nanocomposite was determined by comparing the elastic deformation of the thin film to the macroscopic deformation of the substrate. Finally, the elastic limit of W/Cu nanocomposite was studied for different load ratios. The overall results emphasized the brittle behavior of these nanocomposites.