Neste trabalho é apresentado um estudo sobre a produção e caracterização do nitreto de alumínio (AlN) obtido pela técnica de r.f. Magnetron Sputtering reativo. Aqui reportamos o efeito dos parâmetros de deposição, como densidade de potência de r.f., temperatura e pressão de processo nas propriedades estruturais, morfológicas e elétricas dos filmes de AlN obtidos. Foram realizados estudos sobre os modos vibracionais, pela técnica de espectroscopia de infravermelho por transformada de Fourier (FTIR), das orientações cristalográficas por difração de raios X e da morfologia da superfície pela técnica de microscopia de força atômica (AFM). Estes estudos nos permitiram produzir filmes finos de AlN com uma alta orientação na direção cristalográfica [002] com uma potência de r.f. de 1,23 W/cm2 , uma temperatura de deposição de 200°C e uma pressão de processo de 2 mTorr. Este estudo nos permitiu fabricar filmes de AlN com alta orientação [002] à temperatura ambiente a partir de um alvo de Al. O coeficiente piezoelétrico d33 variou de aproximadamente 4 a 6 pm/V e o d31 2 a 3 pm/V para filmes cristalinos e d33 3 pm/V e d31 1,5 pm/V para filmes amorfos. Os coeficientes piezoelétricos d33 and d31 foram estimados pelo método capacitivo proposto por Mahmoud Al Ahmad and Robert Plana, através da variação das dimensões geométricas induzidas pelo campo elétrico aplicado. / In this work we present a study about the production and characterization of aluminum nitride (AlN) obtained by r.f. Reactive Magnetron Sputtering. Here we report the effect of the deposition parameters, such as r.f. power density, and deposition temperature and pressure, on the morphological, structural and electrical properties of the obtained AlN thin films. In this work we have performed studies concerning the vibrational modes by Fourier Transform Infrared Absorption technique (FTIR), the crystallographic orientations by X-ray diffraction and the surface morphology by Atomic Force Microscopy (AFM). This study allowed us to produce high oriented [002] AlN thin films with a r.f. power density of 1.23 W/cm2, a deposition temperature of 200ºC and a process pressure of 2 mTorr. This study allowed us to produce high oriented [002] AlN thin films at room temperature from a pure Al target. The piezoelectric coefficient d33 was around 4 to 6 pm/V and d31 2 to 3 pm/V to crystalline films and d33 3 pm/V and d31 1.5 pm/V amorphous ones. d33 and d31 piezoelectric coefficients were estimated by the capacitive method proposed by Mahmoud Al Ahmad and Robert Plana, through its geometrical dimensions variation.

O presente trabalho apresenta um estudo do tratamento duplex para o biomaterial Nitinol (NiTi). Este tratamento consiste em nitretação a plasma para a formação do nitreto de titânio (TiN), seguido de deposição de um filme fino de nitreto de zircônio (ZrN) sobre a superfície nitretada. O estudo das fases cristalinas presentes no sistema foi realizado pela técnica de difração de raios X (DRX). A morfologia e espessura da camada nitretada e do filme fino depositado foram avaliadas por microscopia eletrônica de varredura (MEV). As propriedades mecânicas foram estudadas mediante ensaios de nanoindentação. Para avaliar a resistência à corrosão foram realizados testes de polarização potenciodinâmica em solução de saliva artificial. Os resultados mostram que a temperatura de nitretação tem forte influência na formação do TiN na superfície do substrato. O filme de ZrN depositado sobre as amostras nitretadas apresenta propriedades de dureza e resistência à corrosão que dependem da temperatura de nitretação, mesmo tendo sido depositados sem variação de temperatura. Esse comportamento sugere que os filmes são influenciados pela condição inicial da superfície antes da deposição. Os melhores resultados em termos de dureza e resistência à corrosão foram obtidos nas amostras tratadas em temperaturas mais elevadas. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-05T18:07:33Z No. of bitstreams: 1 Dissertacao Juliane Carla Bernardi.pdf: 2940702 bytes, checksum: 376b73745f740260fc19e7a6e8b5d900 (MD5) / Made available in DSpace on 2014-06-05T18:07:33Z (GMT). No. of bitstreams: 1 Dissertacao Juliane Carla Bernardi.pdf: 2940702 bytes, checksum: 376b73745f740260fc19e7a6e8b5d900 (MD5) / The present work aims to study about duplex treatment on the biomaterial Nitinol (NiTi). This treatment consists in titanium nitride (TiN) formed by plasma nitration, followed by zirconium nitride (ZrN) thin film deposition upon the nitrated surface. The study of crystalline phases present in the system was performed by X-ray diffraction technique (XRD). The morphology and thickness of the nitrated layer and thin film were evaluated by scanning electron microscopy (SEM). The mechanical properties were studied by nanoindentation analysis. In order to evaluate corrosive resistance tests of potenciodynamic polarization were performed in solution of saliva artificial. Results demonstrate that nitration temperature has a strong influence in the formation TiN on the substrate surface. The ZrN film depositated upon nitrated samples present hardness and corrosive resistance properties that depend on nitration temperature, even though ZrN films were depositated without temperature variation. This behaviour suggests that films are influenced by the initial surface condition before depositon. The best results in terms of hardness and corrosive resistance were obtained in samples treated at higher temperatures.

Zr-Si-N thin films were deposited by reactive magnetron sputtering to study silicon influence in the structure, morphology and properties such as hardness and oxidation resistance. Six thin films with silicon concentrations from 2.8 to 14.9 at.% were selected. Thin films morphology shows that there are no columnar grains, structure that is commonly observed in films deposited by sputtering. It was identified amorphous and crystalline areas in films microstructure, creating a structure composed by crystalline grains embedded in an amorphous phase, which were characterized by EDS as Zr and Si rich areas, respectively. XRD results indicate ZrN peaks intensity reduction and a broadening increase due silicon nitride segregation to grain boundaries, which is responsible for grain size reduction, that was calculated by Scherrer and reached magnitudes lower than 10 nm. XRD peaks displacement are observed for all samples and it can be explained due formation of a solid solution in which Si replaces Zr atoms in ZrN crystal lattice and due a strong interface between crystalline phase and amorphous one. XPS data reinforce the presence of compounds like ZrN and Si3N4 and it is also possible to infer the formation of a solid solution of Si in ZrN lattice. Oxidation tests were performed at temperatures in the range of 500°C to 1100°C. ZrN film is almost fully oxidized at 500°C, while films with high silicon content maintain ZrN grains stable at 700°C. When oxidized, ZrN films form monoclinic ZrO2 phase, but, in films with silicon addition, the stable phase is the tetragonal one. This happens due ZrN grain size reduction, because tetragonal phase has the lowest surface energy. Oxidation tests results confirm that there is a mechanism acting as diffusion barrier in films, preventing grains coalescence and oxygen diffusion into film structure. This mechanism is a direct consequence of silicon segregation process to grain boundaries, which ensures the formation of a nanostructure composed of ZrN grains embedded by an amorphous Si3N4 layer (nc-ZrN/a-Si3N4), allowing oxidation resistance improvement in at least 200°C. / Filmes finos de Zr-Si-N foram depositados por magnetron sputerring reativo para estudar a influência do teor de silício na estrutura, morfologia e propriedades como dureza e resistência a oxidação. Para tal, foram selecionados seis filmes com teor de Si entre 2,8 e 14,9 at.%. A morfologia demonstra que a estrutura colunar característica dos filmes depositados por sputtering não existe. A estrutura é composta por áreas cristalinas e outras amorfas, na qual os grãos cristalinos estão envolvidos pela fase amorfa, sendo que EDS detectou que estas fases são ricas em Zr e Si, respectivamente. Há redução de intensidade e alargamento dos picos de difração do ZrN, efeito provocado pela segregação do Si3N4 para região dos contornos, fato que propicia a redução do tamanho de grão, o qual foi calculado por Scherrer e atinge magnitude inferior a 10 nm. Os picos do DRX estão deslocados, fato justificado pela formação de uma solução sólida na qual o Si substituiu o Zr no reticulado do ZrN e pela forte interface formada entre as fases cristalina e amorfa. Dados de XPS reforçam a formação de uma estrutura bifásica de ZrN e Si3N4 e mostra indícios de que há uma solução sólida de Si no ZrN. Os ensaios de oxidação foram realizados em temperaturas de 500°C até 1100°C. O filme de ZrN praticamente se oxida a 500°C, enquanto nos filmes com altos teores de silício os grãos de ZrN se mantém estáveis até 700°C. Quando oxidado, os filmes de ZrN formam predominantemente ZrO2 na fase monoclínica, mas, nos filmes com adição de Si há a inversão para a fase tetragonal. Tal fato é fruto da redução do tamanho de grão, pois a fase tetragonal possui menor energia de superfície. Tais resultados ratificam que existe mecanismo atuando como barreira a difusão, o qual impede a coalescência dos grãos e a difusão do oxigênio. Este mecanismo é resultado do processo de segregação do silício para os contornos, o qual assegura a formação da nanoestrutura composta de grãos de ZrN embebidos por camada amorfa de Si3N4 (nc- ZrN/a-Si3N4) e permite aprimorar a resistência a oxidação em pelo menos 200°C.

O presente trabalho apresenta um estudo do tratamento duplex para o biomaterial Nitinol (NiTi). Este tratamento consiste em nitretação a plasma para a formação do nitreto de titânio (TiN), seguido de deposição de um filme fino de nitreto de zircônio (ZrN) sobre a superfície nitretada. O estudo das fases cristalinas presentes no sistema foi realizado pela técnica de difração de raios X (DRX). A morfologia e espessura da camada nitretada e do filme fino depositado foram avaliadas por microscopia eletrônica de varredura (MEV). As propriedades mecânicas foram estudadas mediante ensaios de nanoindentação. Para avaliar a resistência à corrosão foram realizados testes de polarização potenciodinâmica em solução de saliva artificial. Os resultados mostram que a temperatura de nitretação tem forte influência na formação do TiN na superfície do substrato. O filme de ZrN depositado sobre as amostras nitretadas apresenta propriedades de dureza e resistência à corrosão que dependem da temperatura de nitretação, mesmo tendo sido depositados sem variação de temperatura. Esse comportamento sugere que os filmes são influenciados pela condição inicial da superfície antes da deposição. Os melhores resultados em termos de dureza e resistência à corrosão foram obtidos nas amostras tratadas em temperaturas mais elevadas. / The present work aims to study about duplex treatment on the biomaterial Nitinol (NiTi). This treatment consists in titanium nitride (TiN) formed by plasma nitration, followed by zirconium nitride (ZrN) thin film deposition upon the nitrated surface. The study of crystalline phases present in the system was performed by X-ray diffraction technique (XRD). The morphology and thickness of the nitrated layer and thin film were evaluated by scanning electron microscopy (SEM). The mechanical properties were studied by nanoindentation analysis. In order to evaluate corrosive resistance tests of potenciodynamic polarization were performed in solution of saliva artificial. Results demonstrate that nitration temperature has a strong influence in the formation TiN on the substrate surface. The ZrN film depositated upon nitrated samples present hardness and corrosive resistance properties that depend on nitration temperature, even though ZrN films were depositated without temperature variation. This behaviour suggests that films are influenced by the initial surface condition before depositon. The best results in terms of hardness and corrosive resistance were obtained in samples treated at higher temperatures.

In this work, physical phenomena related to the growth and phase formation of alumina, Al2O3, are investigated by experiments and computer calculations. Alumina finds applications in a wide variety of areas, due to many beneficial properties and several existing crystalline phases. For example, the α and κ phases are widely used as wear-resistant coatings due to their hardness and thermal stability, while, e.g., the metastable γ and θ phases find applications as catalysts or catalyst supports, since their surface energies are low and, hence, they have large surface areas available for catalytic reactions. The metastable phases are involved in transition sequences, which all irreversibly end in the transformation to the stable α phase at about 1050 °C. As a consequence, the metastable aluminas, which can be grown at low temperatures, cannot be used in high temperature applications, since they are destroyed by the transformation into α. In contrast, α-alumina, which is the only thermodynamically stable phase, typically require high growth temperatures (~1000 °C), prohibiting the use of temperature sensitive substrates. Thus, there is a need for increasing the thermal stability of metastable alumina and decreasing the growth temperature of the α phase. In the experimental part of this work, hard and single-phased α-alumina thin films were grown by magnetron sputtering at temperatures down to 280 °C. This dramaticdecrease in growth temperature was achieved by two main factors. Firstly, the nucleation stage of growth was controlled by pre-depositing a chromia “template” layer, which is demonstrated to promote nucleation of α-alumina. Secondly, it is shown that energetic bombardment was needed to sustain growth of the α phase. Energy-resolved mass spectrometry measurements demonstrate that the likely source of energetic bombardment, in the present case, was oxygen ions/atoms originating from the target surface. Overall, these results demonstrate that low-temperature α-alumina growth is possible by controlling both the nucleation step of growth as well as the energetic bombardment of the growing film. In addition, the mass spectrometry studies showed that a large fraction of the deposition flux consisted of AlO molecules, which were sputtered from the target. Since the film is formed by chemical bonding between the depositing species, this observation is important for the fundamental understanding of alumina thin film growth. In the computational part of the work, the effect of additives on the phase stability of α- and θ-alumina was investigated by density functional theory calculations. A systematic study was performed of a large number of substitutional dopants in the alumina lattices. Most tested dopants tended to reverse the stability between α- and θ-alumina; so that, e.g., Modoping made the θ phase energetically favored. Thus, it is possible to stabilize the metastable phases by additives. An important reason for this is the physical size of the dopant ions with respect to the space available within the alumina lattices. For example, large ions induced θ stabilization, while ions only slightly larger than Al, e.g., Co and Cu, gave a slight increase in the relative stability of the α phase. We also studied the stability of some of these compounds with respect to pure alumina and other phases, containing the dopants, with the result that phase separations are energetically favored and will most likely occur at elevated temperatures.

La connaissance de l’énergie transférée aux surfaces en contact avec un plasma basse pression est un paramètre clé pour le contrôle des procédés plasmas basse pression. Sa détermination permet une meilleure compréhension des mécanismes mis en jeu lors du dépôt ou la gravure de couches couches minces. Elle dépend des espèces du plasma (les ions, les électrons et les neutres) ainsi que de nombreux mécanismes physiques ou chimiques (réaction, condensation, émission radiative.). Elle peut être déterminée par la simulation du transport des particules dans le plasma, par des estimations de chaque contribution à partir des paramètres plasma ou tout simplement mesurée. Les études dédiées à sa mesure sont principalement basées sur l’utilisation d’une sonde calorimétrique, dont le principe sur l’interpolation du thermogramme mesuré. Ce type de méthode induit un long temps de mesure (2 min) et est source d’incertitudes. Un outil de diagnostic pour la mesure directe de l’énergie transférée a été développé au GREMI. Il est basé sur l’adaptation d’un capteur à thermopile initialement dédié à des mesures à pression atmosphérique. Cette thèse a donc été dédié à son développement et son utilisation pour l’étude de différents procédés plasmas basse pression : un propulseur spatial à effet Hall, un plasma poudreux, mais surtout de décharges magnétron. Des mesures ont été réalisées lors du dépôt de titane, d’aluminium, de TiO2 et de Al2O3. Les influences de la configuration magnétique de la cathode, du type de décharge, de l’échauffement des cibles, sur les conditions énergétiques à la surface du film en croissance ont été étudiées. / The knowledge of the energy flux during plasma/surface interactions is a key parameter for the control of low pressure plasmas, as sputter deposition or etching processes. The energy flux density at a surface depends on plasma species (ions, electrons, neutrals...) elementary processes (condensation, chemical reaction, radiative transfer). It can be obtained by carring out simulation of particule transport through the plasma, by the calculation of each energetic contribution from plasma parameters or by indirect or direct measurement. Most os works focused on the mesurement of the energy flux is based on the using of a calorimetric probe. This method is based on the calculation of the temporal temperature evolution. The main disadvantages are that this methods can cause error of about 10 % and the acquisition time of the thermogram which is about 2 min. A diagnostic tool which provide a direct measurement of the energy flux, with a good sensitivity and a good time resolution was designed in the GREMI.The aim of this PhD thesis was to developped this tool and use for the study of different plasma processes as capacitiv RF discharge, Hall effect plasma thruster and especially magnetron sputter deposition process. In this last process, the influence of the cathode magnetic configuration, the reactive gas, the dicharge type (HiPIMS, DCMS and pDCMS), the heating of the target was studied on the energy flux at the growing thin film duting the sputtering of a titanium and an aluminum target.

Les exigences de plus en plus élevés concernant la qualité et propriétés de couches minces ont soutenu le développement de nouveaux procédés de pulvérisation. Ainsi, la décharge magnétron conventionnelle en courant continu, une des sources d’atomes la plus utilisée pour le dépôt de couches minces, a été améliorée par le couplage avec une décharge additionnelle de radio fréquence pour obtenir le nouveau procédé RF-IPVD (Radio Frequency-Ionized Physical Vapour Deposition). Ce procédé permet de générer un degré d’ionisation supérieur à celui dans la décharge magnétron classique, nécessaire pour contrôler les propriétés des couches minces. Un procédé alternatif pour augmenter d’avantage l’ionisation consiste à appliquer des impulsions haute puissance sur la cathode HPPMS (High Power Pulsed Magnetron Sputtering), pour des durés courtes de l’ordre de ųs ou dizaines de ųs. L’étude menée porte sur les phénomènes de pulvérisation et de transport des espèces du métal dans ces trois versions de la décharge magnétron par les moyens de spectroscopie laser à l’aide des diodes laser accordables. Le développement récent de ces diodes nous a permis de sonder les niveaux fondamentaux du Titane et de l’Aluminium, et de caractériser la dépendance spatiale de la densité et température ainsi que la fonction de distribution en vitesse de ces atomes. L’effet des paramètres clés, comme l’intensité du courant et la pression du gaz, est étudie et décrit pour la décharge magnétron conventionnelle. La distribution spatiale et angulaire de la fonction de distribution en vitesses a été mesurée dans la région devant la cible magnétron, afin de caractériser les flux du métal et leur comportement dans le volume de la décharge. L’étude sur les atomes du métal dans le procédé RF-IPVD est concentrée sur l’effet de la décharge additionnelle sur le dépeuplement du niveau fondamental. Une efficacité plus grande des processus d’ionisation est trouvée à plus haute pression et plus haute puissance RF injecté. On a montré aussi que les atomes affectés par les processus d’ionisation sont ceux thermalisées, tandis que la distribution de atomes rapides n’est quasiment pas affectés par la décharge additionnelle.Le diagnostic de la décharge pulsée a nécessité le développement d’une nouvelle procédure expérimentale, capable de suivre l’évolution de la densité et de la température des espèces neutres avec une résolution de l’ordre de la ųs. Cette procédure nous a servi pour décrire l’évolution spatio-temporel des atomes du métal (Ti et Al) et les atomes métastables d’Ar. Ces études offrent une vue globale sur le transport de atomes pulvérisés pendant la post décharge, ainsi qu’une description du fonctionnement de la décharge pulsé via la création des métastables d’Argon. / The higher requirements on the thin films quality have supported the development of new sputtering techniques. Thus, the conventional DC magnetron discharge, one of the most widely used source of atoms for thin film deposition, has been improved by the addition of an auxiliary radio frequency discharge - new technique called RF-IPVD (Radio Frequency -Ionized Physical Vapor Deposition). This technique highly increases the ionization degree compared to conventional magnetron discharge, which is necessary for a better control of the thin films properties. An alternative method to increase the ionization is based on the use of high power pulses on the cathode, HPPMS (High Power Pulsed Magnetron Sputtering), for short periods of time ranging from ųs to tens of ųs.The present study focuses on the sputtering phenomena and the transport of metal sputtered species in these three versions of the magnetron discharge, by means of laser spectroscopy using tunable laser diodes. The recent developments of these diodes have allowed to probe the fundamental levels of titanium and aluminum, and to characterize the spatial dependency of the density and temperature as well as the velocity distribution functions of these atoms. The effect of key discharge parameters, such as current intensity and gas pressure, is studied and described for the conventional magnetron discharge. The spatial and angular velocity distribution functions were measured in front of the magnetron target, in order to characterize the metal fluxes and their behavior in the discharge volume.The study on the metal atoms in the RF-IPVD process is focused on the effect of the additional discharge on the depopulation of the ground state level. Higher ionization efficiency is found at relatively high pressure and it increases with the injected RF power. It was also showed that the thermalized atoms are the ones involved in the ionization process, while the distribution of fast atoms is almost unaffected by the additional discharge.The diagnostics of the HPPMS discharge required the development of a novel experimental procedure, able to monitor the density and temperature of neutral species with a time resolution of ųs. This procedure was used to describe the spatiotemporal evolution of metal atoms (Ti and Al) and Ar metastable atoms. These studies provide an overview on the transport of sputtered atoms during the afterglow, and a description of the pulsed discharge operation, via the creation of metastable argon atoms.

Revestimentos finos de carboneto de nióbio (NbC) puro e dopados com níquel (Ni) foram obtidos mediante a técnica de deposição reativa por magnetron sputtering, utilizando metano (CH4) como fonte de carbono (C). O filme de NbC usado como referência foi depositado aplicando uma potência de 2500 W ao alvo de Nb e, os revestimentos de NbxNiyCz foram depositados diminuindo a potência aplicada ao alvo de Nb e aumentando a potência aplicada ao alvo de Nb-Ni, dando origem à seis revestimentos com teores de Ni crescentes. As caracterizações microestrutural e estrutural dos revestimentos de NbC e NbxCyNiz foram realizadas por meio das técnicas de difração de raios-X (DRX), Espectroscopia Fotoeletrônica de Raios X (XPS), Espectroscopia Raman, Microscopia Eletrônica de Transmissão (MET) e Microscopia Eletrônica de Varredura (MEV). As propriedades mecânicas dos revestimentos foram estudas mediante a técnica de nanoindentação instrumentada, com o intuito de avaliar a dureza (H) e o módulo de elasticidade (E). A adesão dos revestimentos ao substrato foi avaliada usando ensaios Rockwell C e esclerometria linear instrumentada. A estabilidade térmica dos revestimentos foi realizada em forno com atmosfera controlada em temperaturas de 600 °C e 800 °C por 2h. Finalmente, a resistência à oxidação dos revestimentos foi estudada por meio de ensaios de Termogravimetria (TGA - \"Thermogravimetric Analysis\") de aquecimento contínuo e isotérmicos. Os resultados de adesão obtidos mostraram boa aderência (modo de falha HF1) dos filmes de NbC e NbxNiyCz ao substrato de aço AISI M2, nas condições como recém depositado e revenido a 600 °C, indicando que a deposição do gradiente de intercamadas de Cr, CrC e do gradiente CrC / NbC foi efetiva evitando falhas adesivas. A adição de Ni na estrutura dos revestimentos de NbC promoveu a formação de estruturas nanocompósitas, composta de nanocristalitos de NbC e NiCx. Adicionalmente, a introdução de níquel causou um aumento na dureza nos revestimentos como recém depositados, aumentando de 17 para 25 GPa para teores de Ni de 0 para 13 at. %, respectivamente, e, na resistência à oxidação sobre o revestimento puro de NbC, de 380 °C para 480 °C nos revestimentos com níquel. Finalmente, as análises de estabilidade térmica permitiram observar que os precipitados de NiCx se decompõem durante os tratamentos de recozimento a 600 e 800 °C, o que promoveu um aumento nos valores de dureza e módulo de Young para todos os revestimentos, atribuído ao aumento da cristalinidade dos revestimentos. / Niobium carbide (NbC) coatings doped with Nickel (Ni) were deposited by reactive DC - magnetron sputtering using methane (CH4) as carbon (C) source. Reference NbC coating was deposited with a total power of 2500 W and NbxNiyCz coatings were deposited by decreasing the power applied to the Nb target and increasing the power applied to the Nb-Ni target, giving rise to coatings with increasing Ni content. Structural and microstructural characterizations of NbC and NbxNiyCz coatings were performed using X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Raman Spectroscopy, Transmission Electron Microscopy (MET) and Scanning Electron Microscopy (MEV). Mechanical properties of the coatings were studied using the instrumented nanoindentation technique, in order to evaluate the Hardness (H) and Elastic modulus (E). The adhesion between coatings and substrate was evaluated using Rockwell C test and instrumented linear scratch tests. The tests for studying the thermal stability of the coatings were carried out in a controlled atmosphere chamber furnace at temperatures of 600 °C and 800 °C for 2h. Finally, the oxidation resistance of the coatings was studied by means of Thermogravimetric Analysis (TGA) tests of continuous and isothermal heating. The NbC and NbxNiyCz films in the as-deposited condition and annealed at 600 °C, showed good adhesion (failure mode HF1) to the AISI M2 steel substrate, indicating that the adhesion interlayer of the Cr, CrC and a gradient CrC/NbC layer was effective in avoiding adhesive failures. The increasing of Ni content in the structure of NbC coatings promoted the formation of nanocomposite structures, composed of a mixture of NbC and NiCx nanocrystallites. Additionally, the introduction of nickel allows increasing the hardness for the coatings in the as-deposited condition, from 17 to 25 GPa for Ni contents from 0 to 13 at. %, respectively, and, improving the oxidation resistance over the pure NbC coating, from 380 °C to 480 °C for the Ni-rich coatings. Finally, the thermal stability analyses showed that the NiCx precipitate decompose during the annealing treatments at 600 °C and 800 °C, which promoted an increase in the hardness and Young\'s modulus values for all coatings. These behaviors were attributed to the increase of crystallinity of the coatings.

Avec le développement de nouvelles sources d’énergie, les technologies dédiées à son stockage ont un rôle capital. Le zirconate de Plomb (PZ de structure Pérovskite) présente un grand intérêt pour les futures capacités rapides permettant le stockage de forte densité d’énergie. Cette propriété est associée à la transition de phase ferroélectrique – anti ferroélectrique induite par le champ électrique et qui s’accompagne d’une grande capacité de stockage. Le PZ a été déposé par pulvérisation cathodique RF sur différents types de substrats et notamment le SrTiO3, les cibles sont obtenues par mélange des poudres et pressage à froid. L’étude s’est focalisée sur les effets d’interfaces entre le film et l’électrode inférieure (LaNiO3 dans notre cas), l’orientation préférentielle des films et la réalisation de films épitaxiés de PZ. La structure, la micro structure des films ainsi que leurs épaisseurs ont un impact sur les contraintes existantes dans le film et nous avons évalué ces effets sur la capacité de stockage du PZ dans la phase anti ferroélectrique. L’optimisation des propriétés des interfaces et de l’ingénierie des contraintes permettent d’améliorer la densité d’énergie stockée dans un film anti ferroélectrique. C’est une voie sérieuse pour les supers condensateurs à base de matériaux fonctionnels de type PZ. / With the development of new energy resources, the advanced energy storage technologies are also becoming more and more important. Perovskite lead zirconate PbZrO3 is of great interest for future high-energy and fast-speed storage capacitors, due to the field-forced phase transition into the ferroelectric state accompanied by large charge storage. The material is deposited on SrTiO3 by RF magnetron sputtering from cold pressed target made in laboratory. The study focuses on the effect of interface between films and electrodes, preferred orientations, epitaxial strain and measuring conditions on the energy storage properties of PbZrO3-based antiferroelectric films. The improvement of interface properties and strain engineering enhance the energy storage density of antiferroelectric film, which may open a route to advance studies on PbZrO3-based antiferroelectric functional devices.

Les systèmes électrochromes, dont les propriétés optiques changent sous l’effet d’une excitation électrique, suscitent un intérêt croissant dû au fait qu’ils permettent un contrôle des propriétés optiques dans le domaine du visible et du proche infrarouge. Le but, initié dans des travaux précédents, vise à optimiser la synthèse, par pulvérisation cathodique magnétron, de films minces d’une épaisseur de 300 nm pouvant être intégrés dans un futur dispositif électrochrome « tout céramique » à conduction de sodium. Dans ce travail de thèse, deux matériaux constituant ce dispositif ont été étudiés. Le premier concerné est l’oxyde de tungstène, connu pour servir de couche électrochrome dans les dispositifs. Les couches synthétisées possèdent des propriétés de conduction mixte, une structure amorphe et une morphologie poreuse permettant l’intercalation de cations de sodium Na+ en son sein. Une dégradation du film de WO3 due à une réactivité rédhibitoire vis-à-vis de l’eau a été observée. Pour éliminer cela, deux solutions ont été testées : un cyclage en milieu non aqueux ou le recouvrement du film par un électrolyte solide de type NaSICon. La stoechiométrie en oxygène des films, a permis de régler la conductivité électronique, l’absorption dans le visible et la capacité des films à échanger des ions Na+. Le second matériau étudié est un oxyde de tungstène pré-inséré en sodium NaxWOy. L’influence des conditions de synthèse et celle de la teneur en sodium sur les différentes propriétés des films a été étudiée. Ces propriétés ont ensuite été comparées à celles obtenues pour les films de WO3 et pour des bronzes de tungstène NaxWO3 reportées dans la littérature. / Electrochromic systems, whose optical properties change under the effect of an electrical excitation, see an increasing interest because they allow a control of optical properties in the visible and near infrared. The aim, initiated in previous works, is to optimize the synthesis of 300 nm thin films by magnetron sputtering to be integrated into a future electrochromic "all ceramic" device based on sodium conduction. In this PhD, two materials forming the system have been studied. The first material is the tungsten oxide, known to serve as the electrochromic layer in devices. The synthesized layers possess mixed conducting properties, an amorphous structure and a porous morphology allowing the intercalation of sodium cations. A degradation of the WO3 film due to redhibitory reactivity towards water was observed. To eliminate this reactivity, two solutions were tested: a non-aqueous cycling or covering of the initial film by depositing a solid electrolyte of the type NaSICon. The oxygen stoichiometry of the films, allowed to tune the electronic conductivity, the absorption in the visible and the ability of the film to exchange Na+ cations. The second studied material is a pre-inserted NaxWOy sodium tungsten oxide. The influence of the synthesis conditions and of the sodium content on the various properties of the films was investigated. These properties were then compared with those obtained for the WO3 films and those of NaxWO3 tungsten bronzes reported in the literature.