In this study we contribute towards establishing the process-microstructure relationships in thin films grown off-normally by ionized physical vapor deposition. High power impulse magnetron sputtering (HiPIMS) is used at various peak target powers and deposition rates to grow copper (Cu) and chromium (Cr) films from a cathode placed at an angle 90 degrees with respect to the substrate normal. Films are also deposited by direct current magnetron sputtering (DCMS), for reference. Scanning electron microscopy is employed to investigate column tilting and deposition rate while X-ray diffraction techniques are utilized to study crystal structure and grain tilting. It is demonstrated that the columnar structure of Cu tilts less with respect to the substrate normal as the peak target power increases, which has been shown to correspond to a higher ionization degree of the sputtered material [1]. One explanation for this is that the trajectories of the ions are deflected towards the substrate and therefore deposited closer to the normal, as has been suggested in the literature (see e.g. [2]). Energetic bombardment by ions might also increase surface mobility, which further raises the columns. It is also concluded that the change in tilting is not caused by a lower deposition rate obtained when employing HiPIMS. The same is not seen for Cr, where all deposited films exhibit the same tilting angle. When the column tilting of Cu and Cr is compared a large difference is observed, where the columns of Cr are closer to the substrate normal. The reasons for this difference are discussed in light of nucleation and growth characteristics in the two materials. X-ray diffraction analysis reveals that Cu films exhibit an (111) fiber texture. Comparison of films grown by DCMS and HiPIMS shows that in the HiPIMS cases the grains are closer to the surface normal and better oriented with each other. In the case of Cr both DCMS and HiPIMS grown films are (110) biaxially aligned.

In this study, the current densities in three different directions (r, φ and z) have been measured above the target during a HiPIMS discharge by the use of a Rogowski coil. This was done to examine the key transport parameter Jφ/JD┴ = ωge TEFF throughout the whole measured area, which is a key parameter describing how electrons are transported across magnetic field lines. The coil was adapted to the certain plasma environment that is present during a HiPIMS discharge in consideration due to the extreme environment that is present during the experiment. The thin film deposition system, where the measurements were performed, had a background pressure of ~10-6Torr and during the discharges the chamber were filled with an Ar to the partial pressure of 3mTorr. The previously reported anomalous fast transport of charged particles was verified and the faster-than-Bohm cross-B transport was found to be present in the chamber during the whole discharge but occupying a diminishing area closer to pulse turn off.

<p>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.</p><p>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, <em>J</em><em>φ</em><em> / J</em><em>D</em>. The results provided important insights into understanding the mechanism behind the anomalous transport.</p><p>It was furthermore found that the current ratio <em>J</em><em>φ</em><em> / J</em><em>D</em> 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.</p>

The present thesis addresses two research areas related to film growth in a highly ionized magnetron sputtering system: plasma characterization, and thin film growth and analysis. The deposition technique used is called high power pulsed magnetron sputtering (HPPMS). Characteristic for this technique are high energy pulses (a few Joules) of length 50-100 µs that are applied to the target (cathode) with a duty time of less than 1 % of the total pulse time. This results in a high electron density in the discharge (&gt;1x1019 m-3) and leads to an increase of the ionization fraction of the sputtered material reaching up to 70 % for Cu. In this work the spatial and temporal evolution of the plasma parameters, including the electron energy distribution function (EEDF), the electron density and the electron temperature are determined using electrostatic Langmuir probes. Electron temperature measurements reveal a low effective temperature of 2-3 eV. The degree of ionization in the HPPMS discharge is explained in light of the self-sputtering yield of the target material. A simple model is therefore provided in order to compare the sputtering yield in HPPMS and that in dc magnetron sputtering (dcMS) for the same average power. Thin Ta films are grown using HPPMS and dcMS and their properties are studied. It is shown that enhanced microstructure and morphology of the deposited films is achieved by HPPMS. The Ta films are also deposited at a number of substrate inclination angles ranging from 0o (i.e., facing the target surface) up to 180 o (i.e., facing away from the target). Deposition rate measurements performed at all inclination angles for both techniques, reveal that growth made using HPPMS resulted in an improved film thickness at higher inclination. Furthermore, the high ionization of the Ta atoms in HPPMS discharge is found to allow for phase tailoring of the deposited films at all inclination angles by applying a bias voltage to the substrate. Finally, highly ionized magnetron sputtering of a compound MAX-phase material (Ti3SiC2) is performed, demonstrating that the HPPMS discharge could also be used to tailor the composition of the growing Ti-Si-C films. / On the day of the public defence of the doctoral thesis, the status of articles III and IV was Submitted. The titles of papers VI and VII changed between their manuscript forms and when they were published.

<p>A microphone has been used to measure the dynamic pressure inside a vacuum chamber during high power impulse magnetron sputtering with high enough time-resolution (~µs) to track the pressure change during the discharge pulse. An experimental measurement of the dynamic pressure is of interest since it would give information about gas depletion, which is believed to dramatically alter the plasma discharge characteristics. This investigation has shown that the magnitude of the pressure wave, which arises due to the gas depletion, corresponds to a 0.4 - 0.7Pa (3 - 5.5mTorr) pressure difference at a distance of 15cm from the target, with base pressures of 2 - 6mTorr for a peak current of 110A. It has also been shown that another pressure wave, about 250µs later, can be detected. Its explanation is suggested to be that the initial pressure wave is bouncing against the chamber walls and thereby causing another peak.</p>

A microphone has been used to measure the dynamic pressure inside a vacuum chamber during high power impulse magnetron sputtering with high enough time-resolution (~µs) to track the pressure change during the discharge pulse. An experimental measurement of the dynamic pressure is of interest since it would give information about gas depletion, which is believed to dramatically alter the plasma discharge characteristics. This investigation has shown that the magnitude of the pressure wave, which arises due to the gas depletion, corresponds to a 0.4 - 0.7Pa (3 - 5.5mTorr) pressure difference at a distance of 15cm from the target, with base pressures of 2 - 6mTorr for a peak current of 110A. It has also been shown that another pressure wave, about 250µs later, can be detected. Its explanation is suggested to be that the initial pressure wave is bouncing against the chamber walls and thereby causing another peak.

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.

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.

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.