An Investigation of Target Poisoning during Reactive Magnetron Sputtering

Objective of the present work is a broad investigation of the so called "target poisoning" during magnetron deposition of TiN in an Ar/N2 atmosphere. Investigations include realtime in-situ ion beam analysis of nitrogen incorporation at the Ti sputter target during the deposition process and the analysis of particle uxes towards and from the target by means of energy resolved mass spectrometry. For experiments a planar, circular DC magnetron, equipped with a 2 inch titanium target was installed in an ultrahigh vacuum chamber which was attached to the beam line system of a 5 MV tandem accelerator. A manipulator allows to move the magnetron vertically and thereby the lateral investigation of the target surface. During magnetron operation the inert and reactive gas flow were adjusted using mass flow controllers resulting in an operating pressure of about 0.3 Pa. The argon flow was fixed, whereas the nitrogen flow was varied to realize different states of target poisoning. In a fi?rst step the mass spectrometer was used to verify and measure basic plasma properties e.g. the residual gas composition, the behavior of reactive gas partial pressure, the plasma potential and the dissociation degree of reactive gas molecules. Based on the non-uniform appearance of the magnetron discharge further measurements were performed in order to discuss the role of varying particle fluxes across the target during the poisoning process. Energy and yield of sputtered particles were analyzed laterally resolved, which allows to describe the surface composition of the target. The energy resolving mass spectrometer was placed at substrate position and the target surface was scanned by changing the magnetron position correspondingly. It was found, that the obtained energy distributions (EDF) of sputtered particles are influenced by their origin, showing signi?ficant differences between the center and the erosion zone of the target. These results are interpreted in terms of laterally different states of target poisoning, which results in a variation of the surface binding energy. Consequently the observed energy shift of the EDF indicates the metallic or already poisoned fraction on target surface. Furthermore the EDF's obtained in reactive sputtering mode are broadened. Thus a superposition of two components, which correspond to the metallic and compound fractions of the surface, is assumed. The conclusion of this treatment is an discrete variation of surface binding energy during the transition from metallic to compound target composition. The reactive gas target coverage as derived from the sputtered energy distributions is in reasonable agreement with predictions from model calculations. The target uptake of nitrogen was determined by means of ion beam analysis using the 14N(d, )12C nuclear reaction. Measurements at varying nitrogen gas flow directly demonstrate the poisoning eff?ect. The reactive gas uptake saturates at a maximum nitrogen areal density of about 1.1016 cm-2 which corresponds to the stoichiometric limit of a 3 nm TiN layer. At sufficiently low reactive gas flow a scan across the target surface discloses a pronounced lateral variation of target poisoning, with a lower areal density in the target race track compared to the target center and edge. Again the findings are reproduced by model calculations, which confirm that the balance of reactive gas injection and sputter erosion is shifted towards erosion in the race track. Accomplished computer simulations of the reactive sputtering process are similar to Berg's well known model. Though based on experimental findings the algorithm was extended to an analytical two layer model which includes the adsorption of reactive gas as well as its different kinds of implantation. A distribution of ion current density across the target diameter is introduced, which allows a more detailed characterization of the processes at the surface. Experimental results and computer simulation have shown that at sufficiently low reactive gas flow, metallic and compound fractions may exist together on the target surface, which is in contradiction to previous simulations, where a homogeneous reactive gas coverage is assumed. Based on the results the dominant mechanisms of nitrogen incorporation at different target locations and at varying reactive gas admixture were identified.Gegenstand der Arbeit ist die Untersuchung der Targetvergiftung beim reaktiven Magnetronsputtern von TiN in Argon-Sticksoff Atmosphäre. Die Untersuchungen beinhalten die Echtzeit in-situ Ionenstrahlanalyse des Stickstoffeinbaus in das Titantarget während des Depositionsprozesses sowie die Analyse der Teilchenflüsse vom – und hin zum Sputtertarget mittels energieaufgelöster Massenspektrometrie. Das Magnetron wurde in einer Vakuumkammer installiert, welche an die Beamline des 5 MV Tandembeschleunigers angeschlossen war. Die Position des Magnetrons konnte mittels eines Manipulator verändert werden, was die laterale Untersuchung der Targetoberfläche ermöglichte. Während des Magnetronbetriebes wurde der Argonfluss in die Kammer konstant gehalten, während der Stickstofffluss variiert wurde um verschiedene Ausprägungen der Targetvergiftung zu erreichen. In einem ersten Schritt wurden die Eigenschaften des Plasmas, z.B. die Zusammensetzung des Sputtergases, das Verhalten des Reaktivgaspartialdruckes, das Plasmapotenzial und der Dissoziationsgrad der Reaktivgasmoleküle im Plasma, mit dem Massenspektrometer ermittelt. Aufgrund der ungleichmäßigen Gasentladung vor dem Magnetrontarget, wurden auch lateral variierende Teilchenflüssen und eine ungleichmäßige Targetvergiftung angenommen. Die Energie und die Ausbeute von gesputterten Teilchen wurde deshalb lateral aufgelöst untersucht. Das Massenspektrometer wurde zu diesem Zweck am Ort des Substrates positioniert und die Targetoberfläche konnte gescannt werden indem die Magnetronposition verändert wurde. Die so aufgenommenen Energieverteilungen der gesputterten Teilchen zeigen eine räumliche Abhängigkeit. Teilchen die aus dem Targetzentrum stammen unterscheiden sich hinsichtlich ihrer Energie signifikant von den Teilchen die in der Target-Erosionszone gesputtert werden. Dieses Resultat zeigt die ungleichmäßige Targetvergiftung, wodurch es zu einer Veränderung der Oberflächenbindungsenergie kommt. Über die Verschiebung in der Energieverteilung lässt sich somit der Zustand der Targetoberfläche beschreiben. Diese experimentellen Ergebnisse zeigen Übereinstimmung mit den Ergebnissen der Modellrechnungen. Der Stickstoffgehalt des Targets wurde weiterhin mittels Ionenstrahlanalyse (NRA) bestimmt. Messungen bei verschiedenen Stickstoffflüssen demonstrieren direkt die Vergiftung des Targets. Die maximale Stickstoffkonzentration sättigt bei einem Wert, der dem Stickstoffgehalt in einer ca. 3 nm dicken Titannitridschicht entspricht. Bei ausreichend niedrigem Stickstofffluss zeigt die Messung quer über den Targetdurchmesser eine Variation im Stickstoffgehalt. Die Stickstoffkonzentration in der Erosionszone ist deutlich geringer als im Targetzentrum oder am Targetrand. Die Resultate wurden wiederum durch Modellrechnungen bestätigt. Die durchgeführten Computersimulationen basieren auf Sören Bergs Modell des reaktiven Sputterprozesses. Der Algorithmus wurde jedoch auf der Basis der experimentellen Ergebnisse erweitert. Das Modell beinhaltet nun Mechanismen des Reaktivgaseinbaus in das Target, wie Adsorption, Implantation und Recoilimplantation. Des Weiteren wurde die Ionenstromverteilung als Funktion des Targetdurchmessers in das Modell aufgenommen, was eine detailliertere Beschreibung des Prozesses ermöglicht. Die experimentellen Ergebnisse und die Resultate der Computersimulation zeigen, dass bei niedrigen Reaktivgasflüssen metallische und vergiftete Bereiche auf der Targetoberfläche gemeinsam existieren. Das ist im Widerspruch zu älteren Simulationen, in denen von einer homogenen Targetbedeckung durch das Reaktivgas ausgegangen wird. Basierend auf den Ergebnissen wurden die dominierenden Mechanismen des Reaktivgaseinbaus in das Sputtertarget, in Abhängigkeit von der Position und von der Sputtergaszusammensetzung, identifiziert

An Investigation of Target Poisoning during Reactive Magnetron Sputtering

Objective of the present work is a broad investigation of the so called target poisoning during magnetron deposition of TiN in an Ar/N2 atmosphere. Investigations include realtime in-situ ion beam analysis of nitrogen incorporation at the Ti sputter target during the deposition process and the analysis of particle uxes towards and from the target by means of energy resolved mass spectrometry. For experiments a planar, circular DC magnetron, equipped with a 2 inch titanium target was installed in an ultrahigh vacuum chamber which was attached to the beam line system of a 5 MV tandem accelerator. A manipulator allows to move the magnetron vertically and thereby the lateral investigation of the target surface. During magnetron operation the inert and reactive gas flow were adjusted using mass flow controllers resulting in an operating pressure of about 0.3 Pa. The argon flow was fixed, whereas the nitrogen flow was varied to realize different states of target poisoning. In a fi?rst step the mass spectrometer was used to verify and measure basic plasma properties e.g. the residual gas composition, the behavior of reactive gas partial pressure, the plasma potential and the dissociation degree of reactive gas molecules. Based on the non-uniform appearance of the magnetron discharge further measurements were performed in order to discuss the role of varying particle fluxes across the target during the poisoning process. Energy and yield of sputtered particles were analyzed laterally resolved, which allows to describe the surface composition of the target. The energy resolving mass spectrometer was placed at substrate position and the target surface was scanned by changing the magnetron position correspondingly. It was found, that the obtained energy distributions (EDF) of sputtered particles are influenced by their origin, showing signi?ficant differences between the center and the erosion zone of the target. These results are interpreted in terms of laterally different states of target poisoning, which results in a variation of the surface binding energy. Consequently the observed energy shift of the EDF indicates the metallic or already poisoned fraction on target surface. Furthermore the EDF's obtained in reactive sputtering mode are broadened. Thus a superposition of two components, which correspond to the metallic and compound fractions of the surface, is assumed. The conclusion of this treatment is an discrete variation of surface binding energy during the transition from metallic to compound target composition. The reactive gas target coverage as derived from the sputtered energy distributions is in reasonable agreement with predictions from model calculations. The target uptake of nitrogen was determined by means of ion beam analysis using the 14N(d, )12C nuclear reaction. Measurements at varying nitrogen gas flow directly demonstrate the poisoning eff?ect. The reactive gas uptake saturates at a maximum nitrogen areal density of about 1.1016 cm-2 which corresponds to the stoichiometric limit of a 3 nm TiN layer. At sufficiently low reactive gas flow a scan across the target surface discloses a pronounced lateral variation of target poisoning, with a lower areal density in the target race track compared to the target center and edge. Again the findings are reproduced by model calculations, which confirm that the balance of reactive gas injection and sputter erosion is shifted towards erosion in the race track. Accomplished computer simulations of the reactive sputtering process are similar to Berg's well known model. Though based on experimental findings the algorithm was extended to an analytical two layer model which includes the adsorption of reactive gas as well as its different kinds of implantation. A distribution of ion current density across the target diameter is introduced, which allows a more detailed characterization of the processes at the surface. Experimental results and computer simulation have shown that at sufficiently low reactive gas flow, metallic and compound fractions may exist together on the target surface, which is in contradiction to previous simulations, where a homogeneous reactive gas coverage is assumed. Based on the results the dominant mechanisms of nitrogen incorporation at different target locations and at varying reactive gas admixture were identified

The Physics of Protoplanetesimal Dust Agglomerates. III. Compaction in Multiple Collisions

To study the evolution of protoplanetary dust aggregates, we performed experiments with up to 2600 collisions between single, highly-porous dust aggregates and a solid plate. The dust aggregates consisted of spherical SiO$_2$ grains with 1.5$\mu$m diameter and had an initial volume filling factor (the volume fraction of material) of $\phi_0=0.15$. The aggregates were put onto a vibrating baseplate and, thus, performed multiple collisions with the plate at a mean velocity of 0.2 m s$^{-1}$. The dust aggregates were observed by a high-speed camera to measure their size which apparently decreased over time as a measure for their compaction. After 1000 collisions the volume filling factor was increased by a factor of two, while after $\sim2000$ collisions it converged to an equilibrium of $\phi\approx0.36$. In few experiments the aggregate fragmented, although the collision velocity was well below the canonical fragmentation threshold of $\sim1$ m s$^{-1}$. The compaction of the aggregate has an influence on the surface-to-mass ratio and thereby the dynamic behavior and relative velocities of dust aggregates in the protoplanetary nebula. Moreover, macroscopic material parameters, namely the tensile strength, shear strength, and compressive strength, are altered by the compaction of the aggregates, which has an influence on their further collisional behavior. The occurrence of fragmentation requires a reassessment of the fragmentation threshold velocity.Comment: accepted by the Astrophysical Journa

Dust growth in protoplanetary disks - a comprehensive experimental/theoretical approach

More than a decade of dedicated experimental work on the collisional physics of protoplanetary dust has brought us to a point at which the growth of dust aggregates can - for the first time - be self-consistently and reliably modelled. In this article, the emergent collision model for protoplanetery dust aggregates (G\"uttler et al. 2010) as well as the numerical model for the evolution of dust aggregates in protoplanetary disks (Zsom et al. 2010) are reviewed. It turns out that, after a brief period of rapid collisional growth of fluffy dust aggregates to sizes of a few centimeters, the protoplanetary dust particles are subject to bouncing collisions, in which their porosity is considerably decreased. The model results also show that low-velocity fragmentation can reduce the final mass of the dust aggregates but that it does not trigger a new growth mode as discussed previously. According to the current stage of our model, the direct formation of kilometer-sized planetesimals by collisional sticking seems impossible so that collective effects, such as the streaming instability and the gravitational instability in dust-enhanced regions of the protoplanetary disk, are the best candidates for the processes leading to planetesimals.Comment: to appear in Research in Astronomy and Astrophysics (RAA

Numerical Simulations of Highly Porous Dust Aggregates in the Low-Velocity Collision Regime

A highly favoured mechanism of planetesimal formation is collisional growth. Single dust grains, which follow gas flows in the protoplanetary disc, hit each other, stick due to van der Waals forces and form fluffy aggregates up to centimetre size. The mechanism of further growth is unclear since the outcome of aggregate collisions in the relevant velocity and size regime cannot be investigated in the laboratory under protoplanetary disc conditions. Realistic statistics of the result of dust aggregate collisions beyond decimetre size is missing for a deeper understanding of planetary growth. Joining experimental and numerical efforts we want to calibrate and validate a computer program that is capable of a correct simulation of the macroscopic behaviour of highly porous dust aggregates. After testing its numerical limitations thoroughly we will check the program especially for a realistic reproduction of various benchmark experiments. We adopt the smooth particle hydrodynamics (SPH) numerical scheme with extensions for the simulation of solid bodies and a modified version of the Sirono porosity model. Experimentally measured macroscopic material properties of silica dust are implemented. We calibrate and test for the compressive strength relation and the bulk modulus. SPH has already proven to be a suitable tool to simulate collisions at rather high velocities. In this work we demonstrate that its area of application can not only be extended to low-velocity experiments and collisions. It can also be used to simulate the behaviour of highly porous objects in this velocity regime to a very high accuracy.The result of the calibration process in this work is an SPH code that can be utilised to investigate the collisional outcome of porous dust in the low-velocity regime.Comment: accepted by Astronomy & Astrophysic

Porosities of Protoplanetary Dust Agglomerates from Collision Experiments

Aggregation of dust through sticking collisions is the first step of planet formation. Basic physical properties of the evolving dust aggregates strongly depend on the porosity of the aggregates, e.g. mechanical strength, thermal conductivity, gas-grain coupling time. Also the outcome of further collisions depends on the porosity of the colliding aggregates. In laboratory experiments we study the growth of large aggregates of $\sim$ 3 mm to 3 cm through continuous impacts of small dust agglomerates of 100 $\mu$m size, consisting of $\mu$m grains at different impact velocities. The experiments show that agglomerates grow by direct sticking as well as gravitational reaccretion. The latter can be regarded as suitable analog to reaccretion of fragments by gas drag in protoplanetary disks. Experiments were carried out in the velocity range between 1.5 m/s and 7 m/s. With increasing impact velocities the volume filling factor of the resulting agglomerates increases from $\phi = 0.2$ for 1.5 m/s to $\phi = 0.32$ for 7 m/s. These values are independent of the target size. Extrapolation of the measured velocity dependence of the volume filling factor implies that higher collision velocities will not lead to more compact aggregates. Therefore, $\phi = 0.32$ marks a degree of compaction suitable to describe structures forming at $\rm v > 6\, m/s$. At small collision velocities below 1 m/s highly porous structures with $\phi \approx 0.10$ will form. For intermediate collision velocities porosities vary. Depending on the disk model and resulting relative velocities, objects in protoplanetary disks up to dm-size might evolve from highly porous ($\phi \approx 0.10$) to compact ($\phi = 0.32$) with a more complex intermediate size range of varying porosity.Comment: Accepted by The Astrophysical Journa

The Physics of Protoplanetesimal Dust Agglomerates. IV. Towards a Dynamical Collision Model

Recent years have shown many advances in our knowledge of the collisional evolution of protoplanetary dust. Based on a variety of dust-collision experiments in the laboratory, our view of the growth of dust aggregates in protoplanetary disks is now supported by a deeper understanding of the physics involved in the interaction between dust agglomerates. However, the parameter space, which determines the collisional outcome, is huge and sometimes inaccessible to laboratory experiments. Very large or fluffy dust aggregates and extremely low collision velocities are beyond the boundary of today's laboratories. It is therefore desirable to augment our empirical knowledge of dust-collision physics with a numerical method to treat arbitrary aggregate sizes, porosities and collision velocities. In this article, we implement experimentally-determined material parameters of highly porous dust aggregates into a Smooth Particle Hydrodynamics (SPH) code, in particular an omnidirectional compressive-strength and a tensile-strength relation. We also give a prescription of calibrating the SPH code with compression and low-velocity impact experiments. In the process of calibration, we developed a dynamic compressive-strength relation and estimated a relation for the shear strength. Finally, we defined and performed a series of benchmark tests and found the agreement between experimental results and numerical simulations to be very satisfactory. SPH codes have been used in the past to study collisions at rather high velocities. At the end of this work, we show examples of future applications in the low-velocity regime of collisional evolution.Comment: accepted by The astrophysical Journa

The Christiansen Effect in Saturn's narrow dusty rings and the spectral identification of clumps in the F ring

Stellar occultations by Saturn's rings observed with the Visual and Infrared Mapping Spectrometer (VIMS) onboard the Cassini spacecraft reveal that dusty features such as the F ring and the ringlets in the Encke and the Laplace Gaps have distinctive infrared transmission spectra. These spectra show a narrow optical depth minimum at wavelengths around 2.87 microns. This minimum is likely due to the Christiansen Effect, a reduction in the extinction of small particles when their (complex) refractive index is close to that of the surrounding medium. Simple Mie-scattering models demonstrate that the strength of this opacity dip is sensitive to the size distribution of particles between 1 and 100 microns across. Furthermore, the spatial resolution of the occultation data is sufficient to reveal variations in the transmission spectra within and among these rings. For example, in both the Encke Gap ringlets and F ring, the opacity dip weakens with increasing local optical depth, which is consistent with the larger particles being concentrated near the cores of these rings. The strength of the opacity dip varies most dramatically within the F ring; certain compact regions of enhanced optical depth lack an opacity dip and therefore appear to have a greatly reduced fraction of grains in the few-micron size range.Such spectrally-identifiable structures probably represent a subset of the compact optically-thick clumps observed by other Cassini instruments. These variations in the ring's particle size distribution can provide new insights into the processes of grain aggregation, disruption and transport within dusty rings. For example, the unusual spectral properties of the F-ring clumps could perhaps be ascribed to small grains adhering onto the surface of larger particles in regions of anomalously low velocity dispersion.Comment: 42 pages, 15 figures, accepted for publication in Icarus. A few small typographical errors fixed to match correction in proof