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The onset and development of self-sputtering (SS) in a high power impulse magnetron sputtering (HiPIMS) discharge have been studied using a plasma chemical model and a set of experimental data, taken with an aluminum target and argon gas. The model is tailored to duplicate the discharge in which the data are taken. The pulses are long enough to include both an initial transient and a following steady state. The model is used to unravel how the internal discharge physics evolves with pulse power and time, and how it is related to features in the discharge current-voltage-time characteristics such as current densities, maxima, kinks and slopes. The connection between the self-sputter process and the discharge characteristics is quantified and discussed in terms of three parameters: a critical target current density J(crit) based on the maximum refill rate of process (argon) gas above the target, an SS recycling factor Pi(SS-recycle), and an approximation alpha a of the probabilities of ionization of species that come from the target (both sputtered metal and embedded argon atoms). For low power pulses, discharge voltages UD <= 380V with peak current densities below approximate to 0.2A cm(-2), the discharge is found to be dominated by process gas sputtering. In these pulses there is an initial current peak in time, associated with partial gas rarefaction, which is followed by a steady-state-like plateau in all parameters similar to direct current magnetron sputtering. In contrast, high power pulses, with U-D >= 500V and peak current densities above J(D) approximate to 1.6Acm(-2), make a transition to a discharge mode where SS dominates. The transition is found not to be driven by process gas rarefaction which is only about 10% at this time. Maximum gas rarefaction is found later in time and always after the initial peak in the discharge current. With increasing voltage, and pulse power, the discharge can be described as following a route where the role of SS incr, QC 20140805. Updated from submitted to published.

In most models of sputtering magnetrons, the mechanism for energizing the electrons in the discharge is assumed to be sheath energization. In this process, secondary emitted electrons from the cathode surface are accelerated across the cathode sheath into the plasma, where they either ionize directly or transfer energy to the local lower energy electron population that subsequently ionizes the gas. In this work, we present new modeling results in support of an alternative electron energization mechanism. A model is experimentally constrained, by a fitting procedure, to match a set of experimental data taken over a large range in discharge powers in a high-power impulse magnetron sputtering (HiPIMS) device. When the model is matched to real data in this way, one finding is that the discharge can run with high power and large gas rarefaction without involving the mechanism of secondary electron emission by twice-ionized sputtered metal. The reason for this is that direct Ohmic heating of the plasma electrons is found to dominate over sheath energization by typically an order of magnitude. This holds from low power densities, as typical for dc magnetrons, to so high powers that the discharge is close to self-sputtering, i.e. dominated by the ionized vapor of the sputtered gas. The location of Ohmic heating is identified as an extended presheath with a potential drop of typically 100-150V. Such a feature, here indirectly derived from modeling, is in agreement with probe measurements of the potential profiles in other HiPIMS experiments, as well as in conventional dc magnetrons., QC 20130822

Im Mittelpunkt der vorliegenden Arbeit steht die Herstellung ultradünner epitaktischer Galliumnitrid-Schichten auf einem Siliziumkarbid-Substrat mit dem Verfahren der ionenstrahlgestützten Molekularstrahlepitaxie. Für die Analyse der Oberflächentopographie der Galliumnitrid-Schichten direkt nach der Abscheidung – ohne Unterbrechung der Ultrahochvakuum-Bedingungen – wurde ein Rastersondenmikroskop in die Anlage integriert. Als weitere Hauptanalysenmethode wurde die Reflexionsbeugung hochenergetischer Elektronen zur Bestimmung der Oberflächenstrukturen in situ während der Schichtabscheidung eingesetzt. Weiterhin wurden die Galliumnitrid-Schichten hinsichtlich ihrer strukturellen Eigenschaften mittels Röntgenstrahl-Diffraktometrie, Röntgen-Photoelektronenspektroskopie und Transmissionselektronenmikroskopie ex situ charakterisiert. Wesentliches Ziel dieser Arbeit war die Herausstellung des Einflusses maßgeblicher Abscheidungsparameter (vor allem Substrattemperatur und Gallium-Depositionsrate) auf die Schichteigenschaften sowie die Optimierung dieser Wachstumsparameter. Besonderes Augenmerk lag auf der Untersuchung der Auswirkungen des Stickstoffion-zu-Galliumatom-Verhältnisses und des Einflusses der niederenergetischen Ionenbestrahlung auf das Galliumnitrid-Schichtwachstum im Frühstadium. Dies betrifft hauptsächlich den Wachstumsmodus (zwei- oder dreidimensional) und die Bildung der hexagonalen oder der kubischen Phase.:Kapitel 1 1 Einführung 1 Kapitel 2 5 Grundlagen 5 2.1 Kristallstruktur und Eigenschaften von Galliumnitrid 5 2.2 Wechselwirkung niederenergetischer Ionen mit der Oberfläche 8 2.2.1 Energiefenster für die optimale ionenstrahlgestützte Epitaxie 9 2.3 Einfluss der Teilchenenergie auf die Oberflächenmobilität 11 2.3.1 Strukturzonenmodelle 11 2.3.2 Thermisch induzierte Oberflächenmobilität 13 2.3.3 Ballistisch induzierte Oberflächenmobilität 14 2.4 Herstellungsverfahren 15 2.4.1 Metallorganische Gasphasenepitaxie 15 2.4.2 Molekularstrahlepitaxie 16 2.4.3 Ione

Im Mittelpunkt der vorliegenden Arbeit steht die Herstellung ultradünner epitaktischer Galliumnitrid-Schichten auf einem Siliziumkarbid-Substrat mit dem Verfahren der ionenstrahlgestützten Molekularstrahlepitaxie. Für die Analyse der Oberflächentopographie der Galliumnitrid-Schichten direkt nach der Abscheidung – ohne Unterbrechung der Ultrahochvakuum-Bedingungen – wurde ein Rastersondenmikroskop in die Anlage integriert. Als weitere Hauptanalysenmethode wurde die Reflexionsbeugung hochenergetischer Elektronen zur Bestimmung der Oberflächenstrukturen in situ während der Schichtabscheidung eingesetzt. Weiterhin wurden die Galliumnitrid-Schichten hinsichtlich ihrer strukturellen Eigenschaften mittels Röntgenstrahl-Diffraktometrie, Röntgen-Photoelektronenspektroskopie und Transmissionselektronenmikroskopie ex situ charakterisiert. Wesentliches Ziel dieser Arbeit war die Herausstellung des Einflusses maßgeblicher Abscheidungsparameter (vor allem Substrattemperatur und Gallium-Depositionsrate) auf die Schichteigenschaften sowie die Optimierung dieser Wachstumsparameter. Besonderes Augenmerk lag auf der Untersuchung der Auswirkungen des Stickstoffion-zu-Galliumatom-Verhältnisses und des Einflusses der niederenergetischen Ionenbestrahlung auf das Galliumnitrid-Schichtwachstum im Frühstadium. Dies betrifft hauptsächlich den Wachstumsmodus (zwei- oder dreidimensional) und die Bildung der hexagonalen oder der kubischen Phase.:Kapitel 1 1 Einführung 1 Kapitel 2 5 Grundlagen 5 2.1 Kristallstruktur und Eigenschaften von Galliumnitrid 5 2.2 Wechselwirkung niederenergetischer Ionen mit der Oberfläche 8 2.2.1 Energiefenster für die optimale ionenstrahlgestützte Epitaxie 9 2.3 Einfluss der Teilchenenergie auf die Oberflächenmobilität 11 2.3.1 Strukturzonenmodelle 11 2.3.2 Thermisch induzierte Oberflächenmobilität 13 2.3.3 Ballistisch induzierte Oberflächenmobilität 14 2.4 Herstellungsverfahren 15 2.4.1 Metallorganische Gasphasenepitaxie 15 2.4.2 Molekularstrahlepitaxie 16 2.4.3 Ione

Model studies of 400 mu s long discharge pulses in high-power impulse magnetron sputtering have been made to study the gas dynamics and plasma chemistry in this type of pulsed processing plasma. Data are taken from an experiment using square voltage pulses applied to an Al target in an Ar atmosphere at 1.8 Pa. The study is limited to low power densities, < 0.5 kW cm(-2), in which the discharge is far away from the runaway self-sputtering mode. The model used is the ionization region model, a time-dependent plasma chemistry discharge model developed for the ionization region in magnetron sputtering discharges. It gives a close fit to the discharge current during the whole pulse, both an initial high-current transient and a later plateau value of constant lower current. The discharge current peak is found to precede a maximum in gas rarefaction of the order of Delta n(Ar)/n(Ar),(0) approximate to 50%. The time durations of the high-current transient, and of the rarefaction maximum, are determined by the time it takes to establish a steady-state diffusional refill of process gas from the surrounding volume. The dominating mechanism for gas rarefaction is ionization losses, with only about 30% due to the sputter wind kick-out process. During the high-current transient, the degree of sputtered metal ionization reaches 65-75%, and then drops to 30-35% in the plateau phase. The degree of self-sputtering (defined here as the metal ion fraction of the total ion current to the target) also varies during the pulse. It grows from zero at pulse start to a maximum of 65-70% coinciding in time with the maximum gas rarefaction, and then stabilizes in the range 40-45% during the plateau phase. The loss in deposition rate that can be attributed to the back-attraction of the ionized sputtered species is also estimated from the model. It is low during the initial 10-20 mu s, peaks around 60% during the high-current transient, and finally stabilizes around 30% during the plateau phas, QC 20121010. Updated from submitted to published.

In this study, we have grown silver-containing hydrogenated (a-C:H) and non-hydrogenated (a-C) amorphous carbon coatings by two plasma immersion ion implantation methods: I) chemical vapor deposition of methane combined with pulsed filtered cathodic arc deposition of silver, and II) by alternating arc pulses from graphite and silver in a dual cathodic arc plasma source. This unique “bias selective” feature of the deposition system allowed the deposition of silver with the substrates at ground and avoided the sputtering of the grown a-C film. Chemical composition of the samples was analyzed by acquiring their compositional depth-profiles using radio-frequency Glow Discharge Optical Emission Spectroscopy (rf-GDOES), while the microstructural properties were analyzed by X-ray absorption near edge spectroscopy (XANES) and Raman spectroscopy. In this contribution, we compare mechanical and biomedical properties by means of nanoindentation and cell viability tests, respectively, of a-C(H) films obtained by two different plasma immersion ion implantation techniques.

Hydrogenated diamond-like-carbon (a-C:H) and hydrogen-free amorphous carbon (a-C) coatings are known to be biocompatible and have good chemical inertness. For this reason, both of these materials are strong candidates to be used as a matrix that embeds metallic elements with antimicrobial effect. In this comparative study, we have incorporated silver into standard diamond-like carbon (DLC) coatings by plasma ion implantation and deposition (PIII&D) using methane (CH4) plasma and simultaneously depositing Ag from a pulsed cathodic arc source. In addition, we have grown amorphous carbon – silver composite coatings using a dual-cathode pulsed filtered cathodic-arc (FCA) source. The silver atomic content of the deposited samples was analyzed using glow discharge optical spectroscopy (GDOES). In both cases, the arc pulse frequency of the silver cathode was adjusted in order to obtain samples with approximately 5 at.% of Ag. Surface hardness of the deposited films was analyzed using the nanoindentation technique. Cell viability for both a-C:H/Ag and a-C:/Ag samples deposited on 24-well tissue culture plates has been evaluated.