Les oxydes sont des matériaux complexes possédant une physique riche et toujours au centre de nombreuses recherches. Parmi ces oxydes, les manganites ont retenu notre attention car ils présentent une transition métal-isolant abrupte en température, générant un très fort coefficient en température en conditions d’environnement standards. L’objectif de ce travail est de démontrer que ce fort coefficient peut être exploité pour l’amélioration des performances des jauges de pression de type Pirani qui subissent un certain essoufflement dans leur développement. La voie menant à l’aboutissement d’une telle jauge à base d’oxydes pose en revanche un certain nombre de limites technologiques à lever et auxquelles nous avons répondu. La première de ces limites concerne l’intégration des oxydes monocristallins sur silicium, que nous avons reproduite et étendue au cas des substrats de type SOI et GaAs. Nos procédés proposent de passer par deux techniques, l’épitaxie par jets moléculaire et l’ablation laser, pour assurer une croissance optimale de nos films sur ces substrats et d’assurer la reproductibilité de leur réponse en température, notamment la position de leur température de transition en accord avec l’état de l’art. L’épitaxie de ces oxydes génère un niveau de contrainte non négligeable qui n’a jamais été mesuré. En concevant divers dispositifs autosupportés, et en s’appuyant sur les considérations théoriques et des modélisations par éléments finis, nous avons pu quantifier la relaxation de cette contrainte importante et assurer près de 100% de reproductibilité des systèmes suspendus. Ces mêmes systèmes nous permettent de caractériser pour la première fois le facteur de jauge des manganites monocristallines par l’application d’une contrainte contrôlée par nanoindentation. Il est également démontré qu’ils constituent des jauges de pression Pirani à la sensibilité accrue de deux ordres de grandeur pour une consommation en puissance réduite. Des solutions permettant d’améliorer l’ensemble des aspects de ces jauges sont étudiées. / Functional perovskite oxides are of great interest for fundamental and applied research thanks to the numerous physical properties and inherent mechanisms they display. With the maturation of thin film deposition techniques, research teams are able to reproduce oxide films and nanostructures of great crystalline quality with some of the most remarkable properties found in physics, a state leading now to upper-level thoughts like their ability to fulfill industrial needs. This thesis work is an answer to some of the problematics that arise when considering the oxide transition from the research to the industrial world, by focusing on their integration for micromechanical devices (MEMS) such as sensors. In order to ease the access to MEMS manufacturing, it is of importance to allow the deposition of thin oxide films on semiconductor substrates. A first study show that these access bridges can be crossed when using appropriate buffer layers such as SrTiO3 deposited on Silicon or gallium arsenide – produced in close collaboration with INL by Molecular Beam Epitaxy - and yttria-stabilized zirconia directly grown on silicon by pulsed laser deposition, which adapts the surface properties of the substrate to perovksite-based materials. Formation of thin epitaxial and monocristalline films of functional oxides is thus allowed on such buffer layers. As an example, characterization of two mixed-valence manganites La0.80Ba0.20MnO3 and La0.67Sr0.33MnO3 demonstrates that both materials are of excellent crystalline quality on these semiconducting substrates and that their physical characteristics match the one found on classical oxide substrates like SrTiO3. Stress evolution in thin films, which has a major effect in epitaxial materials, is then addressed to quantify its impact on oxide microstructure viability. This work gives an identification of the most significant factors favoring stress generation in the case of the films we produced. Then, based on the deformation measurement of free-standing cantilevers made of manganites on pseudo-substrates, and with the support of appropriate analytical models, a new state of equilibrium is established, giving new information about the evolution of static stress from deposition to MEMS device manufacturing. Solutions to manage their reproducibility is then studied. From another perspective, free-standing microstructures made of monocristaline manganites were used to display the effect of dynamical strain on their electrical resistivity (piezoresistivity) and their inherent structures.Finally, a specific example of the capabilities of reproducible free-standing microbridges made of manganites is presented through the conception of a pressure gauge based on Pirani effect. Indeed, it is shown that the abrupt resistivity change this material exhibits near their metal-to-insulating transition creates high temperature coefficients in standard application environments that can be taken as an advantage to improve the sensibility and power consumption of such gauges whose development had significantly slowed down over the past years. A set of improvements on their sensitivity range and their signal acquisition is also presented. Combined to a specific and innovative package, it is also demonstrated that Pirani gauge capabilities can be enhanced and that the complete devices fulfill embedded application requirements.

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg-1). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg-1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg-1 at 0.17C and cycling stability of 130 mAhg-1 up to 50 cycles at 1.7C.

This dissertation reports the synthesis and characterization of semi-fluorinated polymers derived from the polymerization of bisphenols with fluoroalkenes. A series of diverse bisphenols were chosen from popular commercial bisphenols and new polycyclic aromatic hydrocarbon (PAH) derived bisphenols requiring synthesis. Step-growth condensation polymerization of bisphenols with three different fluoroalkene types was performed while probing polymerization conditions and the structure/properties relationship of the resulting fluoropolymers. The fluoroalkene monomers were chosen from bis(trifluorovinyloxy)biphenyl (TFVE), perfluorocyclohexene (PFCH), and perfluoro acyclic monomers, namely, perfluoro(4-methyl-2-pentene) and 1-perfluoroheptene to undergo this chemistry. This work is divided into four parts based on the polymerization methodology. The first section focuses on the development of a new class of fluorinated arylene vinylene ether (FAVE) and their chain extended polymers prepared via base-catalyzed step-growth polymerization of PAH bisphenols with the TFVE monomer. These reactions afforded polymers containing controlled terminal and enchained fluoroalkenylenes for latent reactivity such as post polymerization functionalization, chain extension, and/or crosslinking. In general, these PAH cores resulted in polymers with improved thermal properties The second portion describes the investigation of step-growth addition/elimination polymerizations of PAH bisphenols and PFCH to prepare a new class of fluoropolymers containing alternating rigid PAH linkages and enchained PFCH vinylene ether moieties in the backbone. The third section covers the preparation and characterization of semi-fluorinated poly(aryl ether sulfone)s by nucleophilic addition/elimination reactions of PFCH with sulfone bisphenols. From commercially bisphenols combined with PAH bisphenols, we introduced the industrially valuable and property enhancing diaryl sulfone unit in a series of semi-fluorinated copolymers. This modular approach greatly expands access to partially fluorinated aryl ether sulfone polymers intended for high performance applications in optoelectronics, separation/purification membranes, and composites. Finally, in the fourth section, a new class of semifluorinated polymers was synthesized via nucleophilic addition/elimination reactions of acyclic perfluoroalkenes with bisphenols. In particular, environmental concerns for biopersistent and highly regulated perfluorooctanoic acid (PFOA) is the driver for using perfluoroheptene, which is derived cleanly by the decarboxylation of these pollutants in one step. This provided a new class of semi-fluorinated materials with promising properties including thermal stable, processability, and transparent film formation.