Eletrônica utilizando polímero em substituição ao silício é uma área de pesquisa recente com perspectivas econômicas promissoras. Compósitos de polímeros com partículas metálicas apresentam interessantes propriedades elétricas, magnéticas e ópticas e têm sido produzidos por uma grande variedade de técnicas. Implantação iônica de metais utilizando plasma é um dos métodos utilizados para obtenção desses compósitos condutores. Neste trabalho é realizada implantação de íons de ouro de baixa energia em PMMA utilizando plasma. O PMMA tem grande importância tecnológica sendo largamente utilizado como resiste em litografias por feixe de elétrons, raios-X, íons e deep-UV. Como resultado da implantação iônica de baixa energia em PMMA há formação de uma camada nanométrica de material condutor. Esse novo material, denominado compósito isolante-condutor, permite criar micro e nanodispositivos através de técnicas largamente utilizadas em microeletrônica. Medidas elétricas são realizadas in situ em função da dose de íons metálicos implantada, o que permite um estudo das propriedades de transporte desses novos materiais, que podem ser modeladas pela teoria da percolação. Simulações utilizando o programa TRIDYN permitem obter a profundidade e o perfil da implantação dos íons. São mostradas caracterizações importantes tais como Microscopia Eletrônica de Transmissão, Microscopia de Varredura por Tunelamento, Espalhamento de Raios-X a Baixos Ângulos, Difração de Raios-X e Espectroscopia UV-vis. Essas técnicas permitem visualizar e investigar o caráter nanoestruturado do compósito metal-polímero. Ainda como parte deste projeto, as camadas condutoras formadas no polímero são caracterizadas quanto à manutenção das suas características de elétron resiste. / Electronics using polymers instead of silicon is a recent research area with promising economic perspectives. Polymer with metallic particles composites presents interesting electrical, magnetic and optical properties and they have been produced by a broad variety of techniques. Metal ion implantation using plasma is one of the used methods to obtain conductor composites. In this work it is performed low energy gold ion implantation in PMMA by using plasma. PMMA has great technological importance once it is broadly used as resist in electron-beam, X-ray, ion and deep UV lithography. As a result of low energy ion implantation in PMMA, a nanometric conducting layer is formed. This new material, named insulator-conductor composite, can allow the creation of micro and nanodevices through well known microelectronics techniques. Electrical measurements are performed in situ as a function of metal ions implanted dose, which allows the investigation of electrical transport of these new materials, which can be modeled by the percolation theory. Simulations using TRIDYN computer code provide the prediction of depth profile of implanted ions. Important characterizations are showed such as Transmission Electron Microscopy, Scanning Tunneling Microscopy, Small Angle X-Ray Scattering, X-Ray Diffraction and UV-vis Spectroscopy. These techniques allow to visualize and to investigate the nanostructured character of the metal-polymer composite. Still as a part of this project, the conducting layers formed are characterized in relation to the maintenance of their characteristics as electron-beam resist.

When azobenzene-modified photosensitive polymer films are irradiated with light interference patterns, topographic variations in the film develop that follow the electric field vector distribution resulting in the formation of surface relief grating (SRG). The exact correspondence of the electric field vector orientation in interference pattern in relation to the presence of local topographic minima or maxima of SRG is in general difficult to determine. In my thesis, we have established a systematic procedure to accomplish the correlation between different interference patterns and the topography of SRG. For this, we devise a new setup combining an atomic force microscope and a two-beam interferometer (IIAFM). With this set-up, it is possible to track the topography change in-situ, while at the same time changing polarization and phase of the impinging interference pattern. To validate our results, we have compared two photosensitive materials named in short as PAZO and trimer. This is the first time that an absolute correspondence between the local distribution of electric field vectors of interference pattern and the local topography of the relief grating could be established exhaustively. In addition, using our IIAFM we found that for a certain polarization combination of two orthogonally polarized interfering beams namely SP (↕, ↔) interference pattern, the topography forms SRG with only half the period of the interference patterns. Exploiting this phenomenon we are able to fabricate surface relief structures below diffraction limit with characteristic features measuring only 140 nm, by using far field optics with a wavelength of 491 nm. We have also probed for the stresses induced during the polymer mass transport by placing an ultra-thin gold film on top (5–30 nm). During irradiation, the metal film not only deforms along with the SRG formation, but ruptures in regular and complex manner. The morphology of the cracks differs strongly depending on the electric field distribution in the interference pattern even when the magnitude and the kinetic of the strain are kept constant. This implies a complex local distribution of the opto-mechanical stress along the topography grating. The neutron reflectivity measurements of the metal/polymer interface indicate the penetration of metal layer within the polymer resulting in the formation of bonding layer that confirms the transduction of light induced stresses in the polymer layer to a metal film. / Azobenzolhaltige Polymere gehören zu einer Klasse funktionaler Materialien, bei denen durch ein äußeres Strahlungsfeld eine starke mechanische Reaktion ausgelöst werden kann. Durch die Bindung an das Polymerrückgrat können die Azobenzole, die unter UV-Belichtung eine Photoisomerisierung ausführen, was zum Teil drastische Effekte zur Folge hat. Unter Belichtung mit Intensitätsmustern, d.h. mit räumlich variierender Verteilung der Polarisation oder der Intensität des einfallenden Lichts verändert sich die Topographie der azobenzolhaltigen Filme, was zur Bildung von Oberflächengittern (engl. Surface Relief Gratings, SRG) führt. In dieser Arbeit wurde eine neue Methode vorgeschlagen, bei der das Verhalten elastischer/morphologischer Eigenschaften unter verschiedenen Belichtungsbedingungen, d.h. mit unterschiedlicher Verteilung der Polarisation und der Intensität in situ lokal als Funktion der Position entlang der SRG aufgenommen werden kann. Außerdem wurde hier vorgeschlagen, opto-mechanische Spannungen, die innerhalb der photosensitiven Polymerfilme während der Belichtung entstehen, mit Hilfe dünner aufgebrachter metallischen Schichten abzubilden und zu analysieren.

Aujourd’hui, la recherche sur les technologies de stockage d’énergie connaît un essor important dû au fort développement de l’électronique portable et des modes de transport écologiques. La plupart des batteries commercialisées utilisent des électrolytes liquides ou à base de liquides qui limitent leur stabilité thermique, la densité d’énergie et la sécurité. Ces limitations pourraient être considérablement diminuées par l’utilisation d’électrolytes polymères solides (SPE) et la technologie lithium métal polymère (LMP). L’objectif des SPE est de combiner au sein du même matériau une conductivité ionique élevée et une tenue mécanique suffisante pour éviter la formation de dentrites de lithium. Dans ce contexte, les copolymères triblocs PS-b-POE-b-PS, avec le POE comme bloc conducteur et le bloc PS apportant la résistance mécanique, sont d’excellents candidats. Afin d’établir des corrélations composition/morphologie/performance, le but de mes travaux de thèse est d’obtenir une caractérisation détaillée des copolymères à blocs synthétisés. Ainsi, les PS-b-POE-b-PS synthétisés (NMP) ont été analysés par chromatographie liquide aux conditions limites de désorption LC LCD. De plus, les analyses de la nano structuration (AFM, TEM et SAXS), des propriétés thermiques (DSC) et mécaniques (DMA) sont discutées. Enfin, des mesures d’impédance ont été effectuées via des cellules symétriques Lithium/ Electrolyte/ Lithium. / The research on electrochemical storage of energy is today in a stage of fast and profound evolution owing to the strong development of portable electronics requesting power energy as well as the requirement of greener transport modes. Most commercial batteries use liquid or liquid-based electrolytes, which limits their thermal stability, energy density and safety. These limitations could be considerably offset by the use of solid polymer electrolytes (SPE) and lithium metal polymer technology (LMP). However, the main drawback of the SPE is the decrease of the ionic conductivity with increasing mechanical strength, necessary to avoid the formation of lithium dendrites during the recharge of the battery. In this context, triblock copolymers PS-b-PEO-b-PS with a PEO block as ionic conductor and PS block providing mechanical strength was a promising candidate as SPE. In order to build composition/morphology/performance relationships, the aim of my PhD is to characterize carefully the block copolymer. For that purpose, the PS-b-PEO-b-PS synthesized (NMP) were characterized using Liquid Chromatography under Limiting Conditions of Desorption (LC LCD). Furthermore, analyses of morphologies and nano-structure by Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM) and Small Angle X-ray Scattering (SAXS) techniques, analyses of thermal (DSC) and mechanical (DSC) properties will be also discussed. Finally, measures of impedance were made via symmetric cells Lithium / Electrolyte / Lithium.