O método de decoração metálica com ouro, desenvolvido por Bassett, em 1958, é de muito interesse no estudo de cristais por microscopia eletrônica de transmissão. Desde aquela época, o método vem sendo aplicado ao estudo de vários fenômenos físicos relacionados à nucleação e epitaxia de filmes finos, bem como em estudos de crescimento e evaporação de cristais. Neste trabalho o método de réplica de decoração foi utilizado para investigar a microtopografia superficial de cristais inorgânicos, de interesse tecnológico e industrial. Nos vários experimentos de decoração, obtivemos adsorção bem localizada dos núcleos de ouro, ao longo de orientações definidas. Nos argilominerais caulinita e diquita, foram marcadas figuras poligonais que seguem os contemos pseudo-hexagonais da própria partícula cristalina. Nos cristais iônicos usados, brometo de potássio e cloreto de sódio, observaram-se degraus monoatômicos em formas variadas, inclusive em espirais originadas por discordâncias em parafuso. Outros sítios da superfície com diferentes energias de adsorção puderam ser identificados em todas as amostras estudadas, através desta metodologia. Nos cristais de calcita não logramos obter figuras de decoração bem definidas, mas sim áreas alternadas com ouro condensado e áreas de interdição, causadas provavelmente pela hidratação natural do mineral. Defeitos pontuais como vacâncias, ilhas ou depressões monoatômicas foram reconhecidos nas figuras de decoração, assim como degraus lineares causados por clivagem. / The gold decoration method originally developed by Bassett in 1958, still is of great interest for unraveling microtopographic details of crystal surfaces in the transmission electron microscope. It is of interest also for studies relating to nucleation and epitaxial growth of thin films, as well as in the study of crystal growth and evaporation itself. The present study was intended to investigate the surface morphologies and defects of some selected inorganic crystals, having technological applications. Ali the different samples prepared by this replica method, presented a clear localization of the gold clusters, along very specific sites. The clay minerais kaolinite and dickite exhibited polygonal figures with a pseudo hexagonal arrangement, parallel to the crystal\'s edges. Growth steps having two different spacings were seen to interlace at 120°. Bromine and sodium halides have monoatomic steps aligned along linear or curved paths; these gold decorated steps could be followed for ample extents in the replicas; among them, other less usual patterns of gold decorated imperfections forming loops, waves and circles were located. The only exception was represented by calcite, in which the decoration was at random. Despite this, some images of deep steps caused by cleavage of the crystals could be clearly recognized. Control images obtained by scanning electron microscopy of cleaved crystals and direct transmission electron microscopy of clay mineral particles, were helpful in the interpretation of the results.

En vue d'applications futures dans le domaine de la récupération d'énergie à basse température à partir de microsystèmes, la connaissance des transferts thermiques aux parois est d'une grande importance. Ces mesures sont réalisées à l'aide de capteurs spécifiques qui permettent de connaître le flux thermique total échangé entre la paroi sur laquelle ils sont installés et le milieu environnant. Cette étude se situe dans le cadre du développement de fluxmètres thermiques a gradient répondant aux contraintes liées aux machines thermiques de type micro-moteur Stirling. Six types de fluxmètres thermiques à sondes à résistance ont été développés à partir de différents matériaux, géométries et formes de capteurs. Une étude électrothermique, prenant en compte l'effet d'auto-échauffement, a été menée et validée expérimentalement. Les techniques de fabrication et de caractérisation, opérés majoritairement en salle blanche, ont permis de réaliser de nombreux capteurs à couches minces. Des supports spécifiques pour ces capteurs ont été développés. Ces capteurs de flux thermique, dont les résistances ont été étalonnées par rapport à une sonde de référence de haute précision, permettent également la mesure de la température. Pour mesurer la densité de flux thermique, deux méthodes ont été testées. La première méthode est indirecte : elle consiste à mesurer le gradient de température à l'aide de deux sondes à résistance en platine. La deuxième méthode est directe : elle repose sur un étalonnage en flux. Enfin, l'influence de l'intrusion des capteurs sur le répartition des flux thermiques dans la pièce à mesurer, avec ou sans support spécifique, a été étudiée. / For future applications in the field of low-temperature energy have sting in microsystems, knowledge of wall heat transfer is of great importance. These measurements are carried out using specific sensors which makes possible to know the total heat flux exchanged between walls and the surrounding environment. This study concerns the development of a gradient heat flux sensor compliant with their requirements associated with thermal machines such as micrometric Stirling engines. Six types of heat flux sensor with resistance temperature detector have been developed from different materials, with various geometries and shapes of sensing elements. An electro thermal study, taking into account the self-heating effect, was carried out and experimentally validated. The fabrication and characterization techniques, mainly carried out in clean rooms, allowed to produce numerous thin-film sensors. Specific housings for these sensors have been developed. These heat flux sensors, whose resistances have been calibrated with a highly accurate reference probe, also allow measuring the temperature. To measure the heat flux density, two methods were tested. The first method is indirect : it consists in measuring the temperature gradient using two platinum resistance probes. The second method is direct : it is based on heat flux calibration. The calibration and measurement benches have been modeled. Then, the experimental and numerical results have been compared. Finally, the influence of the sensor intrusion on the thermal fluxes distribution in the investigated sample, with or without a specific housing, has been studied.

A range of small molecules of interest for use in organic semiconductor devices were studied computationally. Trends in geometry, absorption spectra, molecular orbitals, electrostatic potentials, reorganisation energies were studied. Results suggest that, as with acenes, the performance of non-linear cata-condensed polyaromatic hydrocarbons improves as number of fused benzene rings increases. The torsion in these molecules did not appear to have a large impact on the conjugation across the core and little effect on the absorption spectra, although it did affect the reorganisation energies on which charge mobilities depend. Computational studies of mobilities of anthradithiophene molecules were broadly able to reproduce trends seen experimentally and emphasised the importance of crystal morphology. Experimental work was also carried out to search for cocrystals between anthradithiophene derivatives. Many examples were found with some mixtures forming different cocrystals at different mixture ratios. These results were rationalised by a computational study that showed molecules which had a similar binding energy were more likely to be able to form cocrystals. Cocrystal devices were fabricated and 3 out of 7 showed a larger mobility than devices made out of its constituent materials alone. The best of these had a mobility 65% higher than a device made out of the constituent material with the largest mobility. An energy decomposition analysis was carried out on a novel thallophilic system, a complex of thallium with a neutral β-triketimine ligand which was found to form dimers with close Tl-Tl interactions. Calculations show the electrostatic interaction to be repulsive for the dimer with no counter ions, but attractive when 3,5-bistrifluoromethylphenyl borate counter ions are included. This suggests the metallophilic interaction is counter ion-mediated, requiring the anions to provide favourable electrostatics, even in the case of spatially diffuse and distant counter ions such used here. To enable the studies described here software was written for simulating absorption spectra. An implementation into the Gaussian Suite of programs of an energy decomposition scheme and its extension to include an empirical dispersion correction was also carried out.

Uma vasta gama de sensores são aplicados no mercado atual na busca pela melhoria de processos e produtos. Há um grande crescimento em novos sistemas que possam apresentar recursos que técnicas convencionais não apresentam. A busca por uma nova plataforma de sensoriamento surge a partir do interesse em identificar e controlar parâmetros ambientais isolados. Esta pesquisa em área incipiente no Brasil mostra o desenvolvimento de um sensor a partir de um material inteligente (smart material), que por definição, possui uma ou mais propriedades que podem sofrer mudanças significativas a partir de um estímulo externo. O presente trabalho é baseado na investigação de uma fita de material magnético amorfo, que ao exibir propriedades magnéticas e elásticas pelo efeito da magnetostricção, permite o monitoramento remoto de fenômenos físico-químicos do ambiente em que estiver exposta. O desenvolvimento deste sensor tem finalidade no monitoramento sem fio de solicitação mecânica, e alteração do tipo de fluido presente em um dado ambiente. O estudo e avaliação do sensor contou com técnicas de caracterização experimentais e de simulação. São apresentados sistemas e ensaios capazes verificar as ressonâncias do modo de vibração puro da amostra a partir de medidas ópticas e elétricas, quando submetidos a variação de fenômenos físicos. Os resultados indicam a dependência do efeito direto ao estímulo na ação externa do campo magnético em decorrências das características do material. Os resultados quantificados e qualificados na correlação entre os métodos utilizados, justificam a aplicação do smart material no sensoriamento de viscosidade e carregamento aplicado em ambientes isolados. Em consequência das discussões apresentadas para as curvas comportamentais na variação dos parâmetros físico-químico a plataforma de sensoriamento é validada. / New amorphous magnetic materials have magnetic and elastic properties which allows the identification and control of environmental parameters remotely. This work was based in the investigation of a magnetoelastic thin strip, widely used as anti-theft device. In this study it was discussed the employment of this material as a sensor capable identify an environmental change through magnetoelasticity. In order to characterize the strips it was employed several techniques, namely: finite element modeling of the vibrational modes, electromagnetic impedance and laser interferometry. It was presented an analysis of the displacement of the longitudinal modes. The knowledge of the vibration mode allowed the sensor electric characterization when subjected to environmental changes. According to the sample dimensions under magnetic field, test systems were developed in order to perform optic and electric measurements. A proper parameter adjustment of the power supply allowed the determination of the fundamental and higher order resonance frequencies. The magnetostrictive behaviour of the anti-theft strips is related to the Young modulus where the vibration frequency is inversely proportional to the length of the strip. Studies showed that the strip performance is also related to many other parameters, such as the mechanical and electromagnetic properties and the environment to which it is exposed. The strips here presented are largely employed as sensor for temperature, pressure, density, mas variation, viscosity and flux velocity mainly because their wireless capabilities. The data from the polarization field are a section of the knowledge required to better investigate the best performance of the sensor. The sensor characterization through several techniques applied in viscous media and under pressure raise some issues. However, the construction of some devices allowed the application of different values of viscosity and pressure upon the magnetized strip. This made the results interpretation less complex. The resonances were observed in the experimental data and mathematical modellin. Calibration curves were defined to make the results interpretation easier.Previously applied and studied techniques which cover the characterization and behaviour of the material provide valid justifications for the implementation of remote sensors made of amorphous metallic strips. The results presented here justify the application of the analysed amorphous strip as a viscosity and pressure sensor in isolated enviroments.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2018-03-15T11:39:35Z No. of bitstreams: 2 Dissertação - Diéricon Sousa Cordeiro - 2018.pdf: 6920771 bytes, checksum: 83ec23012a03b4c1207c2f24818766a5 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-03-15T11:39:57Z (GMT) No. of bitstreams: 2 Dissertação - Diéricon Sousa Cordeiro - 2018.pdf: 6920771 bytes, checksum: 83ec23012a03b4c1207c2f24818766a5 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-03-15T11:39:57Z (GMT). No. of bitstreams: 2 Dissertação - Diéricon Sousa Cordeiro - 2018.pdf: 6920771 bytes, checksum: 83ec23012a03b4c1207c2f24818766a5 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-01-31 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Photoluminescent, electroluminescent and photoconductive materials find a wide range of scientific and technological applications, therefore, the accurate photophysics properties description is indispensable. To apply carbazole derivatives as active layers in photovoltaic devices, the steady-state and time-resolved fluorescence spectroscopy of 9-vinylcarbazole (9VCz) and its respective polymer, Poly (N-vinylcarbazole) (PVCz) in solution and thin films prepared by distinct techniques were carried out in this work. Layer-by-Layer by self-assembling and by spin-coating thin films were prepared in order to compare the effects of the distinct techniques on the final photophysics. They also had their morphology characterized by distinct techniques of microscopy. The spectroscopic fluorescence showed that the ideal solutions for producing the thin films were those at concentrations of 10-4 mol L-1 and 10-5 g L-1 for molecule and polymer, respectively. Thin films of the molecule prepared by the self-assembling technique showed structured bands, however, for the polymer, we observed that the spin-coating technique resulted in a film with less aggregation and structured spectra, thus, well defined vibrational bands could be observed. In addition, it was observed that the fluorescence intensity decreases as the number of layer deposition increases in the 9VCz thin films, however, in the self-assembling tri-layer PVCz film, spectra with higher intensity were recorded. Microscopy indicates the formation of thin films; however, it is possible to observe the formation of aggregates on the surface of the thin films, which are also evidenced by steady-state fluorescence. / Materiais com propriedades fotoluminescentes, eletroluminescentes e fotocondutoras encontram aplicações científicas e tecnológicas bastante diversas, para isso, é indispensável executar o estudo detalhado da fotofísica dos materiais de interesse. Com o objetivo de aplicar derivados de carbazol como camada ativa em dispositivos fotovoltaicos, o estudo de espectroscopia de fluorescência fotoestacionária e com resolução temporal do 9-vinilcarbazol (9VCz) e seu respectivo polímero o Poli(N-vinilcarbazol) (PVCz) foi realizado nesse trabalho, quando em solução e quando na forma de filmes finos produzidos por métodos distintos: Layer-by-Layer por automontagem e por spin-coating, afim de comparar o efeito na fotofísica das técnicas de confecção de filmes finos, que também tiveram sua morfologia caracterizada por distintas técnicas de microscopia. Os resultados espectroscópicos das soluções evidenciaram as soluções 10-4 mol L-1 e 10-5 g L-1 para a molécula e para o polímero, respectivamente, como as soluções ideais para produção dos filmes finos. Os filmes finos preparados pela técnica de automontagem apresentaram bandas estruturadas para a molécula, no entanto para o polímero, observou-se que a técnica por spin-coating apresenta menor agregação e espectros mais estruturados, com isso, bandas vibracionais melhor definidas foram visualizadas. Além disso, notou-se que a intensidade de fluorescência apresentou uma diminuição à medida que se aumenta o número de camadas depositadas umas sobre as outras na produção dos filmes finos do 9VCz, no entanto, no filme de PVCz em tricamada, obtido por automontagem a fluorescência tem maior intensidade. A morfologia registrada indica a formação de filmes finos, porém, é possível observar a formação de agregados na superfície dos filmes finos, agregação essa que também é evidenciada pelos dados de espectroscopia de fluorescência fotoestacionária e resolvida no tempo.

A importância da pesquisa em eletrônica orgânica, se comparada à microeletrônica convencional baseada principalmente em silício, surge pela presença de inúmeros semicondutores e técnicas de deposição de baixo custo e em grande superfície. Os Transistores de Filmes Finos Orgânicos (OTFTs, do inglês Organic Thin-Film Transistors) são a unidade fundamental em circuitos eletrônicos e, geralmente, apresentam a estrutura de um transistor de efeito de campo. Podem ser fabricados sobre substratos plásticos e oferecem grande número de aplicações como: mostradores, etiquetas de identificação por rádio frequência e eletrônica têxtil. Além disso, há demanda por componentes eletrônicos portáteis e baratos, principalmente como sensores em diagnósticos médicos e veterinários in-situ. A geometria de OTFT mais utilizada em sensores na atualidade é a bottom gate sobre substratos de silício altamente dopado e com óxido de porta inorgânico. Polímeros como poli(3-hexiltiofeno) (P3HT) vêm sendo amplamente utilizados pela comunidade científica, atestando o potencial comercial deste semicondutor em sensores. Neste contexto, esta tese apresenta o desenvolvimento de transistores à base de P3HT como sensores na detecção de analitos em fase vapor. O estudo é composto por uma etapa inicial de caracterização da mobilidade dos portadores de carga por técnicas de transiente de corrente, seguida pela otimização do desempenho de parâmetros elétricos do transistor através de alterações no processamento dos filmes dielétrico e semicondutor. Enfim, conclui-se a investigação através do entendimento dos fatores ligados à degradação do OTFT após exposição à atmosfera e sob estresse elétrico, além do detalhamento da sensibilidade e especificidade do sensor. Sensores de P3HT oferecem enorme potencial de detecção de amônia, cetonas e compostos organoclorados. Outros semicondutores poliméricos são provavelmente necessários para maior especificidade em relação a vapor dágua e álcoois. / Research on organic electronics, compared to conventional silicon-based microelectronics, is necessary as it offers plenty of semiconductors and low-cost deposition techniques that can be performed over wide surfaces. Organic Thin-Film Transistors (OTFTs) are the fundamental unity in electronic circuits and, usually, display the metal insulator semiconductor field-effect transistor (MISFET) structure. OTFTs can be processed over cheap plastic substrates and integrate a high number of applications as: flexible displays, radio frequency identification tags, textile electronics and sensors (e.g. chemical and biological compounds). Nowadays, consumers demand portable and low-cost electronic devices, mainly as sensors for in-situ medical and veterinarian diagnosis. The most widely used OTFT structure in sensing is the bottom-gate/bottom-contact FET over highly-doped silicon substrates and inorganic dielectrics. Polymers as poly(3-hexylthiophene) (P3HT) have found increasing acceptance by the scientific community, attesting their potential as semiconductors for commercial applications. In this context, the thesis lies in the development of organic transistors based in P3HT polymer for the detection of vapor-phase compounds. This study begins with transistor performance optimization through changes in dielectric and semiconductor processing. Thin-film thickness and P3HT cast solution drying time are the main studied parameters. It involves also the understanding of device performance degradation when exposed to atmosphere and under bias stress, before finally mapping sensitivity and specificity against gaseous analytes. P3HT-based sensors are potentially interesting for ammonia, ketones and organochlorides detection. Other polymeric semiconductors may be necessary to increase specificity against water steam and alcohol analytes.

This thesis investigates the possibility of enhancing the efficiency of thin film solar cells by including periodic material nonhomogeneities in combination with periodically corrugated back reflectors. Two different types of solar cell are investigated; p-i-n junctions solar cells made from alloys of hydrogenated amorphous silicon (a-Si:H) (containing either carbon or germanium), and Schottky barrier junction solar cells made from alloys of indium gallium nitride (InξGa1-ξN). Material nonhomogeneities are produced by varying the fractions of the constituent elements of the alloys. For example, by varying the content of carbon or germanium in the a-Si:H alloys, semiconductors with bandgaps ranging from 1:3 eV to 1:95 eV can be produced. Changing the bandgap alters both the optical and electrical properties of the material so this necessitates the use of coupled optical and electrical models. To date, the majority of solar cell simulations either prioritise the electrical portion of the simulation or they prioritise the optical portion of the simulation. In this thesis, a coupled optoelectronic model, developed using COMSOL Multiphysics®, was used to simulate solar cells: a two-dimensional finite-element optical model, which solved Maxwell's equations throughout the solar cells, was used to calculate the absorption of incident sunlight; and a finite-element electrical drift-diffusion transport model, either one- or two-dimensional depending on the symmetries of the problem, was used to calculate the steady state current densities throughout the solar cells under external voltage biases. It is shown that a periodically corrugated back reflector made from silver can increase efficiency of an a-Si:H alloy single p-i-n junction solar cell by 9:9% compared to a baseline design, while for a triple junction the improvement is a relatively meagre 1:8%. It is subsequently shown that the efficiency of these single p-i-n junction solar cells with a back reflector can be further increased by the inclusion of material nonhomogeneities, and that increasing the nonhomogeneity progressively increases efficiency, especially in thicker solar cells. In the case of InξGa1-ξN Schottky barrier junction solar cells, the gains are shown to be even greater. An overall increase in efficiency of up to 26:8% over a baseline design is reported.

Le besoin croissant d'intégration de nouvelles fonctions dans les futures générations de dispositifs portables contribue au surpeuplement des circuits imprimés. Dans ce contexte, la miniaturisation des composants discrets est impérative pour compenser l'augmentation de leur nombre et pour garder la taille des cartes de circuit imprimé gérable. L'un des composants les plus courants de ce type est le condensateur, qui peut être utilisé pour découpler une partie d'un réseau électrique d'un autre. Cependant, la miniaturisation des condensateurs nécessite une augmentation de leur densité de capacité, impliquant l'intégration de condensateurs haute densité. Le succès d'une telle intégration repose sur l'utilisation à la fois de matériaux à haute constante diélectrique et d'une architecture d'empilement. Dans ce contexte, les couches de titanate-zirconate de plomb (PZT) combinées aux piles multi-MIM sont de bons candidats pour la nouvelle génération de condensateurs. La technologie multi-MIM consiste à empiler deux ou plusieurs structures MIM en parallèle afin d'augmenter la densité de la capacité sans modification effective de la surface. Avec la géométrie multi-MIM, la performance de l'appareil est fortement affectée par la qualité de l'interface Métal/PZT, il est donc important d'élaborer une chimie d'interface qui ne dégrade pas les performances des multi-MIM.Cette thèse soutenue par le projet français «Programme de l'économie numérique des investissements d'Avenir » vise deux axes de développement pour l’améliorer de la qualité des interfaces Pt/Ru/PZT: la première concerne l'optimisation du contenu de Pb en excès dans la couche de PZT, tandis que le second étudie les effets du recuit de post métallisation (PMA).La première partie de la thèse est dédiée aux analyses de densité de capacité réalisées sur les condensateurs Pt/Ru/PZT/Pt en fonction de l'excès de précurseur du Pb dans les couches de PZT déposées par voie sol-gel (10, 15, 20 et 30% de Pb respectivement pour PZT10, PZT15, PZT20 et PZT30).Nous montrons qu'une augmentation de l'excès de Pb de 10 à 20% entraîne une augmentation de la constante diélectrique maximale (environ 8,8%), ainsi qu'une diminution de la tangente de perte (de 4,36 à 3,08%) et du champ de claquage (de 1,68 à 1,26MV/cm). La PMA favorise l'augmentation du maximum de constant diélectrique (jusqu'à 7,5%) et le champ de claquage augmente de 0.5 MV/cm.Ensuite, l'influence de la chimie de surface des PZT est étudiée en fonction de l'excès de précurseur de Pb. Cet excès de Pb permet de compenser l'évaporation du plomb pendant le traitement thermique successif. En utilisant la spectroscopie de photoélectrons par rayons X (XPS), nous montrons la présence d'une phase de surface ZrOx. Les faibles niveaux d'excès de Pb conduisent à la formation de nanostructures ZrOx à la surface de la couche de PZT. Un taux plus élevé en Pb favorise la disparition totale nanostructures ZrOx en surface.Enfin, nous avons sondé l'interface Pt/Ru/PZT en fonction de l'excès de Pb et de la PMA. La microscopie électronique en transmission (TEM) montre que les nanostructures de ZrOx sont présentes à l'interface du Ru/PZT10. Les nanostructures cristallines ZrOx pourraient former une couche non ferroélectrique et ainsi affecter la densité de capacité. L'analyse en mode operando (sous polarisation in situ) par XPS haute-énergie montre une réponse électronique dépendant de la polarisation appliquée, probablement grâce à l’écrantage imparfait du champ dépolarisant à l'interface Pt/Ru/PZT10. En outre, une nouvelle phase (PbOx) est observée au niveau Pt/Ru/PZT30, probablement liée à la quantité de Pb en excès dans le PZT30. Cette phase semble induire la diminution du champ de claquage et la densité de capacité observée au niveau du Pt/Ru/PZT30/Pt. Enfin, PMA sur le Pt/Ru/PZT10 montre la création d'alliage à base de ZrRuOx et PbRuOx qui pourrait être à l'origine de l'amélioration des réponses électriques des condensateurs PZT après PMA. / The growing need for the integration of an increasing number of functions into the new generation of portable devices contributes to overcrowding of printed circuit boards. In this context, the miniaturization of discrete components is imperative to maintain a manageable size of the printed circuit boards. Decoupling capacitors are one of the most important such discrete components. Miniaturization requires an increase of capacitance density, involving the integration of high-density capacitors. The success of such integration relies on the use of both high dielectric permittivity materials and a suitable stacking architecture. Lead zirconate titanate (PZT) in decoupling multiple metal-insulator-metal (multi-MIM) stacks is a good candidate for the new generation of integrated capacitors. The multi-MIM technology consists in stacking two or more PZT film-based MIM structures connected in parallel in order to increase the density of the capacitance without any effective surface area change. Device performance is heavily affected by the quality of the interface with the electrodes, so it is important to engineer interface chemistry which does not degrade the multi-MIM performance.This thesis, supported by the French “Programme de l’économie numérique des investissements d’Avenir” addresses two aspects of development aiming to improve the quality of the Pt/Ru/PZT interfaces: the first one concerns the optimization of Pb excess content in the PZT film, while the second one investigates the Post Metallization Annealing (PMA) done after deposition of electrode/PZT multilayer.The first part of the thesis presents the capacitance density analysis performed on Pt/Ru/PZT/Pt capacitors as a function of Pb excess in the sol-gel precursor solution (10, 15, 20 and 30% of excess Pb for PZT10, PZT15, PZT20 and PZT30, respectively). Pb excess compensates the lead evaporation during calcination.An increase of Pb excess from 10 to 20% leads to an increase of the maximum dielectric constant of 8.8%, a decrease of the loss tangent from 4.36 to 3.08% and breakdown field from 1.68 to 1.26MV/cm. PMA favors the enhancement of the maximum of dielectric constant by 7.5%, and the breakdown field increases to 0.5 MV/cm.The influence of the surface chemistry is studied as a function of Pb precursor excess. X-ray photoelectron spectroscopy (XPS) demonstrates that low level of Pb excess leads to the presence of a ZrOx surface phase in the form of nanostructures. Higher Pb precursor content allows the PZT synthesis to proceed to its end-point, fully consuming the ZrO2 precursor and eliminating the low dielectric constant ZrOx surface phase.We have then studied the Pt/Ru/PZT interface as a function of Pb excess and PMA. Transmission Electron Microscopy (TEM) cross-sectional analysis shows that the crystalline ZrOx nanostructures are still present at the electrode interface, constituting a dielectric layer which contributes to defining capacitor performance. Operando (under bias in situ) hard X-ray photoelectron spectroscopy (HAXPES) analysis using synchrotron radiation highlights an electronic response dependent on the applied polarization, most probably due to imperfect screening of the depolarizing field at the Pt/Ru/PZT10 interface. Furthermore, a new phase (PbOx) is observed at the Pt/Ru/PZT30 due to the high Pb excess. This new phase seems to induce a reduction in breakdown field and capacitance density. Finally, PMA on the Pt/Ru/PZT10 suggests the creation of interface ZrRuOx and PbRuOx which could be at the origin of the improvement of electrical responses of PZT capacitors after PMA.In conclusion, this thesis has provided valuable information and methodology on the correlation between surface and interface physical chemistry of PZT and Pt/Ru/PZT and electric characteristics of PZT based MIM capacitors.

This thesis report presents a new design of a synchronization unit for high power impulse magnetron sputtering (HiPIMS) applications used for depositing thin films. The proposed system is composed of two major hardware parts: a microcontroller unit (MCU) and a field-programmable gate array (FPGA). The control range of the new system is increased by at least ten times compared to existing synchronization unit designed by Ionautics AB.In order to verify the system and benchmark its innovations, several batches of the thin film have been deposited using the new technology. It is shown that HiPIMS with synchronized pulsed substrate bias can effectively improve coating performance. Pulsed substrate bias with user-defined pulse width and delay time is possible to use in the new control mode proposed by this master thesis work; Bias mode. As a result, this master thesis work enables users to flexibly control the HiPIMS processes.

Les copolymères à blocs amphiphiles Polyéthylène-b-Polyéthylène glycol comportent un bloc hydrophile et un bloc hydrophobe, tous deux cristallisables. L’intérêt de cette thèse est de mieux comprendre le comportement de ces copolymères aux interfaces solides et liquides, via l’étude de la structure et de l’organisation des couches adsorbées. Des copolymères PE-b-PEG de différentes compositions ont été étudiés à l’état massique, mettant en évidence que le ratio PEG/PE ainsi que la longueur des blocs jouent un rôle significatif sur le taux de cristallinité, la morphologie et la croissance des structures cristallines. La caractérisation en films minces par spectroscopie PM-IRRAS et AFM a permis de déterminer quantitativement l’orientation des chaînes macromoléculaires de chaque bloc sur des substrats modèles hydrophiles et hydrophobes. L’adsorption des copolymères PE-b-PEG a par ailleurs été étudiée aux interfaces eau/air et eau/hexane par les méthodes de la goutte pendante et de la goutte oscillante. Les résultats, appuyés par des mesures de tailles de particules, ont montré que les copolymères sont capables de former des structures sphériques organisées à l’échelle nanométrique. L’influence de la composition du copolymère et de la nature des interfaces sur l’organisation des copolymères a ainsi permis d’élaborer des modèles d’adsorption des blocs aux interfaces. / Polyethylene-b-Polyethylene amphiphilic diblock copolymers are composed of one hydrophilic and one hydrophobic block, both able to crystallize. The aim of this thesis is to better understand the behaviour of PE-b-PEG copolymers at solid and liquid interfaces, via the study of the structure and the organization of adsorbed layers. The crystallinity of bulk PE-b-PEG copolymers with different composition was characterized, revealing that the ratio PEG/PE and the blocks length impact the crystallinity degree, the morphology and the growth of crystalline structures. Thin films characterization by PM-IRRAS spectrocopy and AFM allowed to determine quantitatively the macromolecular chains orientation on hydrophobic and hydrophilic substrates. PE-b-PEG copolymers adsorption at the water/air and water/hexane interfaces was studied thanks to the pendant drop and the oscillating drop techniques. These results, supported by particle size analysis, revealed that copolymers can organize as nanometric spherical structures. The influence of the copolymer composition and the type of interfaces on the organization then lead to the elaboration of adsorption models of PE and PEG blocks at solid and liquid interfaces.