High power impulse magnetron sputtering (HiPIMS) is a novel pulsed power technique. In HiPIMS, high power pulses are applied to the target for short duration with a low duty factor. It provides a high degree of ionization of the sputtered material (in some cases up to 90%) and a high plasma density (1019 m-3) which results in densification of the grown films. Recently a large side-transport of the sputtered material has been discovered, meaning that the sputtered material is transported radially outwards, parallel to the cathode surface. In this research, we use this effect and study the side-ways deposition of thin films. We designed a new magnetron sputtering system, consisting of two opposing magnetrons with similar polarity. Ti films were grown on Si using the side-ways transport of the sputtered material. Scanning electron microscope was employed to investigate the microstructure of the grown films. Optical emission spectroscopy (OES) measurements were made for investigating the ionized fraction of the sputtered material while Langmuir probe measurements were made for evaluating the plasma parameters such as electron density. The conclusion is that the system works well for side-ways deposition and it can be useful for coating the interior of cylindrically shaped objects. It is a promising technique that should be used in industry.

Vibration problems are still the major constraint in modern machining processes that seek higher material removal rate, shorter process time, longer tool life and better product quality. Depending on the process, the weaker structure element can be the tool/tool holder, workpiece/fixture or both. When the tool/tool holder is the main source of vibration, the stability limit is determined in most cases by the ratio of length-to-diameter. Regenerative chatter is the most significant dynamic phenomenon generated through the interaction between machine tool and machining process. As a rule of thumb, the ratio between the tool’s overhang length and the tool’s diameter shouldn’t exceed 4 to maintain a stable machining process while using a conventional machining tool. While a longer tool overhang is needed for specific machining operations, vibration damping solutions are required to ensure a stable machining process. Vibration damping solutions include both active and passive damping solutions. In the passive damping solutions, damping medium such as viscoelastic material is used to transform the vibration strain energy into heat and thereby reduce vibration amplitude. For a typical cantilever tool, the highest oscillation displacement is near the anti-node regions of a vibration mode and the highest oscillation strain energy is concentrated at the node of a vibration mode. Viscoelastic materials have been successfully applied in these regions to exhibit their damping property. The node region of the 1st bending mode is at the joint interfaces where the cantilever tools are clamped. In this thesis, the general method that can be used to measure and characterize the joint interface stiffness and damping properties is developed and improved, joint interfaces’ importance at optimizing the dynamic stiffness of the joint interface is studied, and a novel advancing material that is designed to possess both high young’s modulus and high damping property is introduced. In the joint interface characterization model, a method that can measure the joint interface’s stiffness and damping over the full frequency range with only the assembled structure is presented. With the influence of a joint interface’s normal pressure on its stiffness and damping, an optimized joint interface normal pressure is selected for delivering a stable machining process against chatter with a boring bar setting at 6.5 times overhang length to diameter ratio in an internal turning process. The novel advancing material utilizes the carbon nano particles mixed in a metal matrix, and it can deliver both high damping property and high elastic stiffness to the mechanical structure. / <p>QC 20130521</p> / PoPJIM, HydroMod, XPRES, NanoComfort

The subject of the master thesis is the extension of the measurement of plasma para- meters by the Langmuir probe in a system with a planar magnetron and a hollow cathode operating in pulse mode. The main tasks are to modify the measuring circuit to increase the maximum probe current and to put the USB oscilloscope into operation for data collection with higher resolution and higher sampling rate. Furthermore, the function of the entire device will be verified using test circuits and also by measuring the probe characteristics in discharges in a system with a magnetron and a hollow cathode in both continuous and pulse mode. 1

High power impulse magnetron sputtering has shown a lot of promise as a way of depositing photocatalytic thin films of titanium dioxide at low temperatures, however, the films deposited are often amorphous and display uncertain photocatalytic abilities. This thesis explores the deposition and characterization of photocatalytic thin films deposited with high power impulse magnetron sputtering.  Multiple films were deposited with reactive sputtering in both the oxide and metal mode of operations at different temperatures, duty cycles and substrate biases. The crystal structure, microstructure and photocatalytic activity of the samples were then characterized in order to correlate to each other as well as the growth conditions. Crystallinities were determined via a combined use of gracing incidence x-ray diffraction and Raman spectroscopy, microstructures were explored in cross-sectional images taken using scanning electron microscopy and the photocatalytic ability was measured by quantifying the rate constant during degradation of stearic acid while under UV-illumination.  It was found that the crystal structure of the sputtered films was influenced by the deposition mode used: oxide mode depositions yielded an anatase structure while metal mode depositions resulted in rutile or mixed structures. The only crystalline films were formed with substrate heating, the application of bias was found to correlate with the formation of more rutile and the most crystalline films were deposited with a higher duty cycle.  Photocatalytic films were successfully deposited at room temperature, even though they were amorphous. Interestingly, the anatase samples were not found to be the most reactive, instead it was found that the crystal structure only displayed a weak correlation to the reactivity of the films. The findings in this work suggest that the reactivity was also heavily influenced by the surface roughness of the samples as well as their microstructures.

The work presented in this thesis involves experimental and theoretical studies related to plasma properties in high power impulse magnetron sputtering (HiPIMS), and more specifically plasma transport. HiPIMS is an ionized PVD method based on conventional direct current magnetron sputtering (dcMS). In dcMS very little of the sputtered material is ionized since the plasma power density is not high enough. This is not the case for HiPIMS, where a substantial part is ionized, and thus presents many new opportunities for thin film growth. Understanding the dynamics of the charged species in the HiPIMS discharge is therefore of essential value when producing high-quality thin film coatings. In the first part of the work a new type of anomalous electron transport was found. Investigations of the transport resulted in the discovery that this phenomenon could quantitatively be described as being related and mediated by highly nonlinear waves, likely due to the modified two-stream instability (MTSI), resulting in electric field oscillations in the MHz-range (the so-called lower hybrid frequency). Measurements in the plasma confirmed these oscillations as well as trends predicted by the theory of these types of waves. The degree of anomalous transport in the plasma could also be determined by measuring the current density ratio between the azimuthal current density (of which the Hall current density is one contribution) and the discharge current density, Jφ / JD. The results provided important insights into understanding the mechanism behind the anomalous transport. It was furthermore found that the current ratio Jφ / JD is inversely proportional to the transverse resistivity, eta_perpendicular , which governs how well momentum is transferred from the electrons to the ions in the plasma. By looking at the forces involved in the charged particle transport it was expected that the azimuthally rotating electrons would exert a volume force on the ions tangentially outwards from the circular race track region. The effect of having an anomalous transport would therefore be a large fraction of highly energetic ions being transported sideways and lost to the walls. In a series of experiments, deposition rates as well as incoming ion energy distributions were measured directly at the side of the magnetron. It was found that a substantial fraction of sputtered material is transported radially away from the cathode and lost to the walls in HiPIMS as well as dcMS, but more so for HiPIMS giving one possible explanation to why the deposition rate for substrates placed in front of the target is lower for HiPIMS compared to dcMS. Furthermore, the recorded, incoming ion energy distributions confirmed theoretical estimations on this type of transport regarding energy and direction.

High entropy alloys (HEAs) are made of at least five principal elements in near-equimolar proportions. The vast number of possible alloys and unconventional combinations of properties are the main benefits of HEAs. Ti, Nb, Cr, Al and N were chosen in order to create a hard, corrosion resistant coating with good thermal stability. TiNbCrAl multicomponent nitride thin films with Ti content between 0 to 14.4 at.% were deposited using multi-magnetron reactive high power impulse magnetron sputtering (R-HiPIMS) to investigate the feasibility of this method and to study how the Ti content affects the properties of the film. The samples deposited using reactive direct current magnetron sputtering (R-DCMS) were used as benchmarks. The settings required for near-equimolar composition were fixed, with Ti magnetron power as the only variable. Substrate was grounded and not intentionally heated. The composition of HiPIMS samples was more stable while the DCMS samples had significant fluctuations in Al and N content when varying the Ti target power, and were understoichiometric in nitrogen, (T iCrN bAl)1N1−δ, due to low degree of ionization of N. All crystalline samples had NaCl-type fcc structure. Crystalline DCMS samples were (111) textured, while the higher ionization characteristic for HiPIMS resulted in samples with competitive growth between two growth directions. The energetic particle bombardment caused the columnar structure of the film to be denser and less jagged, while DCMS samples containing Ti were significantly more porous. Denser, harder and stiffer films with significantly higher compressive stress were produced with HiPIMS. The hardness and stiffness were almost linearly dependent on Ti content, with density slightly decreasing as the Ti content increased. Higher Ti content increased the rate of corrosion of the films.

Grâce à ses excellentes propriétés physiques et chimiques (stable thermiquement, bon conducteur électrique et de chaleur, ductile, très dur mécaniquement, bonne inertie chimique), le matériau tantale et son nitrure TaNx sont utilisés comme revêtement de surface des outils, résistance électrique, barrière de diffusion au cuivre, croissance de nanotubes par un procédé chimique catalytique en phase vapeur. C’est ce matériau et son nitrure que nous avons étudiés lors de cette thèse.Aujourd’hui les exigences des industriels nécessitent que la pulvérisation cathodique magnétron (PCM) puisse être appliquée aux pièces de formes complexes. La principale limitation de cette méthode de dépôt est que la plupart des particules pulvérisées sont neutres. Pour contrôler l’énergie et la trajectoire des particules pulvérisées, des nouveaux procédés IPVD (Ionized Physical Vapor Deposition) ont été développés pour ioniser les atomes pulvérisés. Le procédé RF-IPVD (Radio-Frequency Ionized Physical Vapor Deposition) permet, grâce à une boucle placée entre la cible et le substrat et polarisée en RF, de créer un second plasma permettant d’ioniser la vapeur pulvérisée. Un autre procédé a été développé : nommé HIPIMS (High Power Impulse Magnetron Sputtering), ce procédé utilise une alimentation fournissant des impulsions de courte durée et de forte puissance au lieu d’une alimentation DC. Les particules pulvérisées peuvent être ionisées dans le plasma magnétron qui est très dense lors des impulsions. Nous avons réalisé des couches minces de Ta par PCM, RF-IPVD et HIPIMS, et des couches minces de TaNx par PCM et HIPIMS. Les différentes propriétés des décharges et des couches minces sont étudiées et comparées dans ce mémoire. / Thanks to their excellent physical and chimical characteristics such as good stability with temperature, good conductor of heat and electricity, ductility, hardness, chemical inertness and good corrosion resistance, tantalum and its nitride are used in a wide variety of applications such as wear and corrosion-resistant materials, thin film transistors, diffusion barrier for copper and for carbon nanotube grown by CCVD process (catalytically chemical vapor deposition). For some recent industrial demand, it is necessary to deposit on substrates with complex shape. The main disadvantage of the conventional magnetron sputtering (CMS) is that most of the sputtered particles are neutral. To controle the energy and the path of sputtered particles, new magnetron sputtering techniques have been developed for ionizing a significant fraction of sputtered material. A new sputtering process called RF-IPVD consists in ionizing the sputtered vapor by adding second plasma by a RF coil between the target and the substrate. Another method called HIPIMS (High Power Impulsed Magnetron Sputtering), uses high power impulse instead of DC power. During the impulse, the sputtered Ta atoms are ionized in the dense plasma. We have deposited Ta thin films by CMS, RF-IPVD and HIPIMS and TaNx thin films by CMS and HIPIMS. The objective of this thesis is to compare the properties of discharges and thin films deposited by these different techniques.

La thèse s’inscrit dans la problématique du dépôt de couches minces en procédés de pulvérisation réactive cathodique magnétron continu basse puissance (R-DC) et pulsé haute puissance (R-HiPIMS). Le mode réactif consiste à ajouter, dans l’argon, un gaz réactif tels que l’oxygène ou l’azote. Les oxydes et les nitrures ont de très nombreuses applications industrielles. Néanmoins, les exigences des nouvelles applications nécessitent de mieux comprendre, contrôler et maîtriser les processus fondamentaux gouvernant le transport de la matière pour optimiser ces procédés plasmas. L’objectif principal de cette thèse est d’étudier le transport des atomes pulvérisés de titane (Ti) en mélange Ar/N2 et d’établir des corrélations avec les propriétés des dépôts de type TiN. La fluorescence induite par diode laser (résolue en temps dans le cas du procédé HiPIMS) a été développée pour mesurer les fonctions de distribution en vitesse des atomes neutres Ti à l’état fondamental en fonction de la pression, de la distance par rapport à la cible et du mélange gazeux. Le degré de liberté supplémentaire qu'offre la dimension temporelle du plasma HiPIMS a permis de caractériser leur cinétique de transport en ayant la possibilité de séparer les temps caractéristiques des différents processus, et de mettre en évidence trois populations d’atomes (énergétique, quasi-thermalisée et thermalisée). Les fonctions de distribution en énergie des ions Ti+ ont été mesurées par spectrométrie de masse et des hypothèses sont proposées pour pouvoir expliquer les quatre populations identifiées. Enfin, les couches minces déposées ont été analysées par MEB, DRX et microsonde de Castaing. / The growth of thin layers in reactive-direct current magnetron sputtering (R-DC) and reactive-high power impulse magnetron sputtering (R-HiPIMS) processes is the general framework of this PhD. Reactive processes consist in the addition, in argon gas, of a reactive gas such as oxygen or nitrogen, and allow the deposition of oxides and nitrides which have many industrial applications. Nevertheless, the high level of expectations regarding new applications requires a better understanding, controlling, mastering of basic processes governing atoms transport in the view of process optimization. The main goal of this PhD is to study the transport of sputtered titanium atoms (Ti) in Ar/N2 gas mixture and to establish correlations with TiN film properties. Tunable diode laser induced fluorescence technique (time resolved in the case of HiPIMS process) has been developed in order to measure velocity distribution functions of neutral Ti atoms at the ground state, function of the pressure, the distance from the target and the gas mixture. In HiPIMS, the additional degree of freedom, given by time dimension, allowed to characterize their kinetic of transport while at the same time providing the possibility to separate characteristic time scales of different processes. Three atoms populations have been highlighted (energetic, quasi-thermalized and thermalized ones). Energy distribution functions of Ti+ ions have been measured using mass spectrometry and four populations have been observed and explained. Finally, deposited thin films have been analyzed by means of SEM, XRD and electron microprobe methods.

Émanant d’une collaboration entre le laboratoire CNRS du GREMI et le CEA le Ripault, l’objectif de cette thèse est de réaliser une étude exhaustive sur les conditions d’élaboration des électrodes de pile à combustible PEMFC par procédés plasma, dont l’enjeu est d’améliorer l’activité électro-catalytique du catalyseur employé qu’est le platine (Pt). A même quantité, la répartition du platine sur son support se révèle être un critère déterminant sur les performances délivrées par les PEMFCs. De cette observation, plusieurs axes de recherche ont été proposés et chacun d’entre eux a permis d’obtenir de nouveaux résultats. Le régime de pulvérisation magnétron à haute puissance pulsée (HiPIMS) est étudié dans le cas de dépôt de matériaux nobles pures (Pt, Au, Pd) et alliés (Pt5Pd95 et Pt50Pd50) et a permis de révéler une vapeur métallique ionisée conséquente lors du dépôt (10 % à 90 % selon l’élément). Les résultats obtenus sur le régime HiPIMS ont permis la modification de la distribution d’une faible quantité fixée de Pt (20 μg.cm−2) déposée sur la profondeur des couches de diffusion des gaz (GDL), améliorant incidemment les performances des PEMFCs (+80 % à 0.65 V, la tension à puissance nominale). Ce résultat est complété par ceux obtenus sur l’élaboration de catalyseur alliés, notamment sur la disposition du matériel catalytique au niveau de la structure des agrégats (+93 % à 0.65 V pour Pt5Pd95 en dépôts successifs). Une autre étude a permis d’étudier la modification de répartition du Pt en contact avec la membrane électrolyte. La surface de membrane échangeuses de proton est alors initialement structurée. Ces structurations de surface des membranes montrent une amélioration globale des performances PEMFCs pour les architectures CCB (Catalyst Coated Backing) et CCM (Catalyst Coated Membrane) d’un facteur 1.3 jusqu’à 12, respectivement. / From a collaboration between the CNRS laboratory of the CEA and GREMI Ripault, the objective of this thesis is to conduct a complete study on the conditions for producing electrodes of PEM fuel cell by plasma processes in order to improve the electro-catalytic activity of the catalyst (Pt). The platinum atoms on its support appears to be a one of the most important factor determining the performance delivered by the PEMFCs. From this observation, several lines of research have been proposed and each of them has yielded new results. The High Power Impulse Magnetron Sputtering (HiPIMS) process is studied in case of depositions of noble materials (Pt, Au, Pd) and alloy (Pt5Pd95 and Pt50Pd50) and revealed an ionized metal vapor consequent upon deposition (10 % to 90 % depending of the element). The results obtained on the HIPIMS process have allowed a change in the distribution of a small fixed amount of Pt (20 μg.cm−2) deposited on the depth of the gas diffusion layer (GDL), incidentally improving the performance of PEMFCs (+80% at 0.65 V, the voltage at rated power). This result is complemented by those obtained on the development of allied catalysts, especially with the arrangement of the catalytic material on the aggregates structure (+93 % at 0.65 V for Pt5Pd95 in successive deposits). In order to modify the Pt atoms distribution on the membrane support, another study has been realized. The surface of the proton exchange membrane has been structurated before the Pt deposition. Such structuration have shown an increase of the overall performance of PEMFCs in the case of CCB (Catalyst Coated Backing) and CCM (Catalyst Coated Membrane) architecture with an improvement factor of 1.3 up to 12, respectively.

Les récents besoins de l'industrie, aux exigences de plus en plus sévères, contraint cette dernière à mettre en jeu des matériaux sophistiqués et complexes tels que superalliages, composites ou sandwiches. Ceux-ci nécessitent alors des outils adaptés lorsqu'il s'agit de les mettre en forme. Or actuellement, la solution dite "miracle " reste encore indéterminée. Les outils traditionnels employés s'usent extrêmement vite, et leur coût de revient est exorbitant. Afin de répondre à cette problématique, plusieurs orientations peuvent être envisageables. On note parmi-elles la possibilité de revêtir les outils de films minces afin de figer le plus longtemps possible la géométrie tout lui apportant de nouvelles propriétés. Cependant, afin de garantir une grande efficacité du dépôt malgré le niveau de contraintes élevé exercé pendant les opérations de coupe, il est primordial que le revêtement possède un excellent degré d'adhérence avec le substrat qu'est l'outil coupant. Conditionnée par le décapage ionique, l'adhérence peut être accrue en ayant recours à des procédés favorisant la création des plasmas hautement ionisés et très énergétiques comme l'HIgh Power Impulse Magnetron Sputtering (HIPIMS). Ce procédé permet de contrôler le bombardement ionique par application d'une tension de polarisation négative au niveau des échantillons dans le but d'accroître considérablement l'efficacité du décapage. Les ions, préorientés par les lignes de champs du magnétron, seront donc ainsi attirés vers les substrats et, par effet balistique, vont re-pulvériser les atomes en surface. Les films élaborés sur des échantillons ainsi traités possèdent une excellente accroche avec une bonne homogénéité de l'épaisseur. Le travail de thèse s'est donc orienté sur l'étude de ce nouveau procédé de dépôt afin de comprendre et maîtriser ce type de décharge pour synthétiser des films denses de TiN, AlN et (Al,Ti)N mais aussi et surtout d'améliorer leur adhérence. Dans un premier temps, et à partir des données bibliographiques les plus récentes, les avantages et inconvénients de la décharge HIPIMS qui sont associés à la production d'ions métalliques énergétiques sont renseignés. Dans un second temps, les caractéristiques électriques de la décharge HIPIMS sont mises en avant pour différentes configurations magnétiques, pressions de travail, tensions de décharge et polarisations des substrats afin de mieux comprendre le fonctionnement de cette nouvelle technique, mais également de trouver des conditions permettant un décapage ionique " in situ " efficace. Enfin, pour mener plus loin l'étude, une application aux cas de la synthèse de revêtements (Al,Ti)N est effectuée pour apporter des informations complémentaires sur l'influence d'une décharge HIPIMS sur leurs propriétés chimiques, structurales et mécaniques.