Ces travaux sont issus d’une thèse CIFRE et de la collaboration entre la société Viessmann Faulquemont et le laboratoire de recherche l’Institut Jean Lamour. Ayant pour objectif de fortement réduire les problèmes liés aux hautes températures de stagnation dans les panneaux solaires thermiques, nous présentons une nouvelle génération d’absorbeur solaire intelligent à base de dioxyde de vanadium. Le dioxyde de vanadium, noté VO2, est un matériau présentant une transition métal-isolant (MIT) à une température critique (Tc) de 68°C. Cette transition s’accompagne d’une modification de la structure cristallographique. Le VO2 se trouve sous une forme monoclinique VO2(M) à basse température, et sous une forme rutile VO2(R) à haute température. Ce changement de structure s’accompagne d’une forte modification des propriétés optiques. La synthèse de ces films est réalisée à partir d’une couche de vanadium métallique déposée par pulvérisation. Un recuit d’oxydation-cristallisation est ensuite effectué pour obtenir une couche d’environ 400 nm de dioxyde de vanadium. Afin d’optimiser et d’augmenter la variation d’émissivité (Δε), la température et la durée du recuit sont étudiées. Dans un second temps, un dopage aluminium est réalisé afin d’augmenter l’effet de la transition thermochrome. Après optimisation, le passage au niveau industriel est un succès et des prototypes de taille 1 sont réalisés à partir de la couche thermochrome et de la couche standard afin d’être comparés dans des conditions normales d’utilisation / This work is a CIFRE thesis between VIESSMANN Faulquemont SAS society and the laboratory Institut Jean Lamour. In order to strongly reduce the problems associated with high stagnation temperature, we present a new generation of solar absorbent layers based on a smart thermochromic vanadium dioxide thin film. Vanadium dioxide (VO2) is a material which exhibit a metal insulator transition (MIT) at a critical temperature of 68°C (Tc). The transition is accompanied by a change in crystallographic structure VO2(M), while a rutile-like structure VO2(R) is obtained at high temperature. This structural change induces a drastic modification of the optical properties. The synthesis of vanadium-based films is performed using magnetron sputtering. We proceed to a subsequent annealing in air to form crystalline films of about 400 nm thickness. In order to increase the thermochromic effect of our thin film (Δε) we study the temperature and duration of the annealing. In a second time we try to increase the emissivity switch between the low and high temperature phase by adding an aluminum doping. After optimization, scale up have been successfully done and the optimized parameters have been used to build a prototype of thermochromic selective layer that has been compared to the standard industrial solar absorber

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In earlier work done at the Laboratory of Magnetism and Magnetic Materials in Santa Maria, spectroscopy measurements of electrical impedance between 100 kHz and 1 GHz were a function of temperature in VO2 thin films along the metal insulator transition undergone by this material. These results suggested [127] that the Impedance Spectroscopy can be a useful tool to separate the contributions from those intrinsic material generated by morphological characteristics. For that such possibility could be actually realized, technological improvements were introduced in the system deposited by Magnetron Sputtering at Laboratory of Magnetism and Magnetic Materials as the addition of a Residual Gas Analyzer and improvements in the heating substrate holder. Spectroscopy measurements were performed in a wider range of frequencies and relaxation times extracted from them were compared with the structural characteristics of the samples obtained by X-ray diffraction and Atomic Force Spectroscopy. / Em trabalhos anteriores realizados no Laboratório de Magnetismo e Materiais Magnéticos em Santa Maria, medidas de espectroscopia de impedância elétrica entre 100 kHz e 1 GHz foram realizadas em função da temperatura em filmes finos de VO2, ao longo da transição metal isolante sofrida por este material. Estes resultados sugeriram [127] que a Espectroscopia de Impedância pode ser uma ferramenta útil para separar as contribuições intrínsecas do material daquelas geradas por características morfológicas. Para que tal possibilidade pudesse ser realmente efetivada, foram introduzidas melhorias técnicas no sistema de deposição por Magnetron Sputtering do Laboratório de Magnetismo e Materiais Magnéticos como a adição de um Analisador de Gás Residual e aperfeiçoamentos no sistema de aquecimento do porta substrato. Foram realizadas medidas de espectroscopia numa faixa mais ampla de freqüências e os tempos de relaxação delas extraídos. Essas medidas foram comparadas com as características estruturais das amostras obtidos por difração de Raios X e Espectroscopia de Força Atômica.

ZrMoN thin films were deposited using reactive magnetron sputtering, with the aim to study the influence of Mo content on structure, mechanical properties and oxidation resistance. Three ZrMoN coatings, having concentrations of 23, 31 and 37 at.% , were selected. Different Ar/N2 ratios were applied on the deposition of pure ZrN, in order to obtain an stoichiometric film and replicate that parameter to the other samples. GIXRD analysis identified an ZrMoN crystalline film with an cfc structure. ZrMoN characteristic peaks followed the pure ZrN pattern, with displacements to larger angles. That fact is attributed to Mo accommodation on ZrN crystalline lattice, forming an substitutional type crystalline solid solution. Nanohardness tests results presented values of 33GPa for the sample with 23 at% of Mo, with posterior reduction after oxidation tests. XPS analysis confirm the formation of a biphasic structure of ZrN and MoN and shows indication of a formed solid solution of Mo inside ZrN, though with no intermetallic bonding between Zr and Mo. Oxidation tests were carried out in 500°C, 600°C and 700°C. Pure ZrN exposed to 500°C maintains the presence of grains related to ZrN phase, though in low intensity. ZrMoN thin films were completely oxidized in 500°C, in any Mo content. / Filmes finos de ZrMoN foram depositados utilizando a técnica de magnetron sputtering reativo com objetivo de estudar a influência do teor de Mo na sua estrutura, propriedades mecânicas e resistência à oxidação. Para tal, foram selecionados três revestimentos de ZrMoN com concentrações de 23, 31 e 37 at.% de Mo. Diferentes razões de Ar/N2 foram utilizadas na deposição da matriz ZrN, a fim de obter um filme estequiométrico, e, assim fazer uso deste parâmetro na deposição dos demais revestimentos. Análises de GIXRD identificaram um filme de ZrMoN cristalino com estrutura cfc. Os picos característicos do ZrMoN seguiram os padrões da matriz ZrN com deslocamentos para ângulos maiores a medida em que mais Mo era adicionado, fato justificado pela acomodação do Mo no reticulado cristalino do ZrN formando uma solução sólida cristalina do tipo substitucional. Resultados de nanodureza demonstraram valores de 33 GPa, para o filme com 23 at.% de Mo com posterior redução após ensaio de oxidação. XPS confirma a formação de uma estrutura bifásica de ZrN e MoN e mostra indícios de que há uma solução sólida de Mo no ZrN, porém sem ligação intermetálica Zr-Mo. Os ensaios de oxidação ocorreram em temperaturas de 500°C, 600°C e 700°C. O ZrN a 500°C ainda mantém com baixa intensidade a presença de grãos relativos a fase do ZrN. O filme de ZrMoN, para qualquer concentração de Mo, oxidou por completo a 500°C.

Pour un bon contrôle du procédé de dépôt par pulvérisation magnétron et donc des propriétés des films déposés, une meilleure connaissance des processus de pulvérisation d’une part, et de croissance du film d’autre part est nécessaire. Une façon de mettre en évidence les différents mécanismes impliqués consiste à étudier les transferts d’énergie plasma/surface en temps réel pendant le procédé. Depuis une dizaine d’année, un outil de diagnostic permettant de mesurer directement l’énergie transférée, appelé ‘fluxmètre’ ou HFM (pour Heat Flux Microsensor), a été développé au GREMI. Il est basé sur l’insertion d’une thermopile dans un système adapté aux enceintes plasma basse pression. Bien que ce capteur de flux constitue un très bon outil de contrôle, son couplage avec d’autres diagnostics de la phase gazeuse (spectromètre de masse, spectroscopie d’émission, analyseur d’énergie etc.) et de caractérisation des films déposés (MEB, DRX, RBS,…) est nécessaire pour avoir une analyse complète du régime étudié. Pendant cette thèse, le fluxmètre a été principalement utilisé pour l’étude de trois régimes particuliers de pulvérisation magnétron en mode DC (Courant Continu); la pulvérisation en condition réactive, la pulvérisation d’une cible magnétique et la pulvérisation d’une cible chaude. Ce travail a permis de mettre en évidence des transitions de régimes dans le cas de la pulvérisation en mode réactif (oxydemétal) et à partir d’une cible magnétique (Ferro-paramagnétique). De plus, lorsqu’une cible monte en température, elle émet un rayonnement IR qui peut être absorbé avec plus ou moins d’efficacité par le film en cours de croissance. Les expériences menées dans le cadre de cette thèse ont contribué à l’étude de l’influence que cette contribution énergétique, différente de celle des processus collisionnels (condensation des atomes pulvérisés, interaction avec les ions, électrons etc.) peut avoir sur les films synthétisés. / For a good control of the magnetron sputtering process and therefore of the properties of the deposited films, a better knowledge of the sputtering processes on the one hand and the growth of the film on the other hand is necessary. One way to demonstrate the different mechanisms involved is to study the plasma / surface energy transfers in real time during the process. For the last ten years, a diagnostic tool has been developed at GREMI to directly measure the transferred energy, called fluxmeter, or HFM (for Heat Flux Microsensor). It is based on the insertion of a thermopile in a system suitable for low pressure plasma reactors. Although this flux sensor is a very good control tool, its coupling with other diagnoses of gas phase (mass spectrometer, emission spectroscopy, energy analyzer etc.) and characterization of deposited films (SEM , DRX, RBS, ...) is necessary to have a complete analysis of the studied regime. During this thesis, the fluxmeter was mainly used for the study of three particular regimes of magnetron sputtering in DC (Continuous Current) mode; the sputtering in a reactive condition, the sputtering of a magnetic target, and the sputtering of a hot target. Transitions of regimes in the case of the reactive sputtering (oxide-metal) and the magnetic target (Ferro-paramagnetic) was studied. In addition, when he target emperature rises, it emits IR radiation that can be absorbed with more or less efficiently by the growing film. The experiments carried out in this thesis contributed to the study of the influence of this energy contribution, different from the collisional processes (condensation of atomized atoms, interaction with ions, electrons etc.) can have on the films Synthesized.

We have deposited bulk, monolayer and few-layers as well as large-scale 2D layered MoS2 thin films by pulsed DC magnetron sputtering from an MoS2 target. MoS2 has gained great attention lately, together with other layered Transition Metal Dichalcogenides (TMDCs), for its unique optical and electrical properties with thickness-dependent bandgap. MoS2 also transitions from an indirect to a direct bandgap when thinned down to monolayer. This is intriguing in the fabrication of novel solar cells and photodetectors. Sputter-deposition has the advantage of producing large-scale, high-quality films, which is paramount for layered MoS2 to be applicable on an industrial level. The quality in terms of crystallinity and c⊥-texture of sputtered bulk MoS2 was evaluated as a function of several deposition process parameters: process pressure, substrate temperature and H2S-to-Ar ratio. X-ray Diffraction (XRD) results revealed that the high substrate temperature of 700 °C together with reactive H2S process gas improved the quality regardless of pressure. However, the quality was slightly improved further with increasing pressure up to 50 mTorr. We also found that the quality improved with increasing temperature up to 700 °C using pure Ar as the process gas. Rutherford Backscattering Spectrometry (RBS) analysis showed that with the addition of H2S the stoichiometry of MoSx improved from MoS1.78 using pure Ar to fully stoichiometric MoS2.01 at 40% H2S in the H2S/Ar mixture. Cross-sectional Transmission Electron Microscopy (TEM) imaging revealed the high-quality 2D layered structure of the MoS2 films and a maximum thickness of 5 nm of c⊥-growth MoS2 before the onset of the undesirable c∥-growth. These results provide a solution with respect to the ongoing challenge of obtaining high quality and good stoichiometry of sputtered TMDC films at elevated temperatures. Formation of monolayer and few-layers MoS2 was confirmed by Raman and Photoluminescence (PL) spectroscopy. The peak separation of the E12g and A1g Raman-active modes for MoS2 monolayer was measured to 19.3 cm-1 on SiO2/Si, increases substantially in the transition to bilayer MoS2 and exhibits bulk values from four layers MoS2 and above. This result serves as a good indicator of monolayer as well as few-layers MoS2 formation. The monolayer film exhibits a strong photoluminescence peak at 1.88 eV owing to its direct optical bandgap, as compared to the indirect one of bilayer and thicker films. X-ray Photoelectron Spectroscopy (XPS) spectra of the monolayer MoSx film indicate successful sulfurization of the molybdenum atoms and absence of residual sulfur. XPS also showed ideal stoichiometric MoS2.03 ± 0.03 of the monolayer film. Furthermore, a uniform MoS2 monolayer was successfully grown on a 4" SiO2/Si wafer, demonstrating the large-scale uniformity that can be achieved by sputter-deposition, making it highly applicable on an industrial level.

This work deals with deposition of yttrium oxide layers on silicon substrate (P – type) by using magnetron and reactive magnetron sputtering. Experiments which were made are further described. After that, work is focused on evaluation of deposited layers by using FTIR measurement technique and spectrophotometry. At the end of the work results of experiments are discussed also with the future progress.

Smooth fluorocarbon plasma polymer films have been for a long time considered for fabrication of hydrophobic and slippery coatings. Interest in fluorocarbon materials was also supported by their excellent self-lubricant, dielectric properties and chemical inertness. This thesis is focused on development of new methods for fabrication of fluorocarbon plasma polymes, which could combine the chemical composition and the physical structure necessary for reaching superhydrophobic character of coatings. Poly(tetrafluoroethylene) was the subject material. RF magnetron sputtering using gas aggregation cluster source was the method adapted to fabricate fluorocarbon nanostructured films with chemical composition close to conventional bulk PTFE, but with high degree of cross- linking and branched structure. A model of growth of such plasma polymer nanostructures was discussed.

This doctoral thesis concerns the preparation of porous cerium oxide/carbon bilayers on silicon substrates. In this regard, carbonaceous films in the form of amorphous carbon (a-C) and nitrogenated amorphous carbon (CNx) are considered. The influence of various process parameters of the cerium oxide deposition on the morphology of the final cerium oxide/carbon bilayer is investigated. A correlation could be found between the morphol- ogy of the bilayer and the stoichiometry of the cerium oxide film determined by means of XPS. Furthermore, a study regarding the chemical composition of the used carbonaceous films by means of various spectroscopic techniques is presented. It was found that the chemical composition of the carbonaceous films strongly depends on the deposition con- ditions of these films and influences the behaviour of these films during oxygen plasma treatment and cerium oxide deposition, respectively. 1

Transparent conductive oxides (TCOs) are key functional materials in existing and future electro-optical devices in the fields of energy efficiency, energy generation and information technology. The main application of TCOs is as thin films transparent electrodes where a combination of maximum electrical conductivity and transmittance in the visible to nearinfrared spectral range is required. However, due to the interdependence of the optical properties and the free electron density and mobility, respectively, these requirements cannot be achieved simultaneously in degenerately doped wide band-gap oxide semiconductors. Therefore, a detailed understanding of the mechanisms governing the generation of free charge carriers by extrinsic doping and the charge transport in these materials is essential for further development of high performance TCOs and corresponding deposition methods. The present work is aimed at a comprehensive investigation of the electrical, optical and structural properties as well as the elemental composition of (Al,Ga) doped ZnO and Nb doped TiO2 thin films prepared by pulsed DC reactive magnetron sputtering. The evolution of the film properties is studied in dependence of various deposition parameters through a combination of characterization techniques including Hall-effect, spectroscopic ellipsometry, spectral photometry, X-ray diffraction, X-ray near edge absorption, Rutherford backscattering spectrometry and particle induced X-ray emission. This approach resulted in the development of an alternative process control method based on the material specific current-voltage pressure characteristics of the reactive magnetron discharge which allows to precisely control the oxygen deficiency of the sputter deposited films. Based on the experimental data, models have been established that describe the room temperature charge transport properties and the dielectric function of the obtained ZnO and TiO2 based transparent conductors. On the one hand, these findings allow the prediction of material specific electron mobility limits by identifying the dominating charge carrier scattering mechanisms. On the other hand, new insight is gained into the origin of the observed transition from highly conductive to electrically insulating ZnO layers upon the incorporation of increasing concentrations of Al at elevated growth temperatures. Moreover, the Al and Ga dopant activation in ZnO have been quantified systematically for a wide range of Al concentrations and deposition conditions. A direct comparison of the Ga and Al doping efficiency demonstrates that Ga is a more efficient electron donor in ZnO. Further, it has been shown that high free electron mobilities in polycrystalline and epitaxial Nb:TiO2 layers can be achieved by reactive magnetron sputtering of TiNb alloy targets. The suppression of rutile phase formation and the control of the Nb dopant activation by fine tuning the oxygen deficiency have been identified as crucial for the growth of high quality TiO2 based TCO layers.

NiTi alloys with nearly equiatomic chemical composition are the most studied and the most practically utilized materials from the group of the shape memory alloys (SMA). The NiTi alloy has a thermoelastic martensitic transfor- mation (MT), which its two most important properties are based on: the shape memory and the superelasticity. Thin films of NiTi alloys with thicknesses from hundreds of nm to units of µm have a wide use mainly in microelectromechanical systems (MEMS). The doctoral thesis deals with a fabrication of thin NiTi films using a deposition on silicon substrates with two techniques - the magnetron sputtering and the pulsed-laser deposition (PLD), an investigation of their mi- crostructure using x-ray diffraction, a heat treatment of amorphous NiTi films and with a verification of MT using resistometry. Furthermore, thermomechan- ical properties of a system NiTi-polyimide (NiTi-PI), namely a dependence of a curvature radius of a NiTi-PI bilayer on temperature, are studied. 1