Universität Stuttgart
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Item Open Access Ambient pressure oxidation of Ag(111) surfaces : an in-situ X-ray study(2008) Reicho, Alexander; Dosch, Helmut (Prof. Dr.)The oxidation of metals plays an outstanding role in everyday life. Typical phenomena are the formation of rust on steel or oxide scales on copper, showing up as a green patina. The formation of metal oxides is not always an unwanted process. The functionality of many materials is directly related to their controlled oxidation. The most prominent examples are passivating oxide layers on stainless steel. Relevant for this thesis are industrially applied heterogeneous catalytic reactions for the synthesis of many chemical products, where gaseous reactants are in contact with the solid surface of the catalyst. Oxidation reactions are very important in this context, leading to a big need of understanding of these processes in research and development. Thereby, the active oxygen species on the surface and selectivity and poisoning of the catalyst have to be studied on an atomic scale. The high temperature and high pressure oxidation of the 4d transition metals Ru, Rh, Pd and Ag is a matter of particular interest, because these metals are widely used as oxidation catalysts. On Ruthenium one observes the formation of RuO2(110) bulk oxide islands at elevated temperatures and oxygen pressure. In the case of the Pd(100) and Rh(111) surface oxidation can lead to the formation of so-called surface oxides. These oxides are structurally related to the bulk oxide of the respective element. Furthermore, surface oxides are ultra thin oxides containing one metallic layer surrounded by two oxygen layers, giving rise to an oxygen-metal-oxygen sequence perpendicular to the surface plane. A future vision is to get a direct microscopic control of the emerging surface structures and ultimately of the real-time oxidation/reduction dynamics allowing one to tailor such catalytic reactions to better performance. A necessary prerequisite to the microscopic control is the full atomistic understanding of the surface structures which form at high temperature and at high oxygen pressures. Silver plays a unique role in heterogeneous catalysis. Supported Ag catalysts are used for the selective oxidation ('epoxidation') of ethylene and for the partial oxidation of methanol to formaldehyde. Ethylene oxide and its derivates are basic chemicals for industry, used in a many technologies with a world-wide production of more than 10 million tons as in medicine for disinfection, sterilization, or fumigation, or in transport and energy technologies for engine antifreeze and heat transfer. Because of its ability to kill most bacteria, formaldehyde is extensively used as disinfectant and as preservative in vaccinations. Therefore, the optimisation of these two Ag-supported catalytic reactions is of paramount importance. Current strategies employed in the industrial process to enhance selectivity include the empirical use of inhibitors (Cl) and promoters (Cs), however, on the way to a knowledge-based control of these reactions one has first to understand the surface structure of oxidized silver under relevant conditions in full detail. The formation of extended Ag(111) facets is observed on polycrystalline silver during the above industrial catalytic oxidation reactions, in turn fundamental research (experiment and theory) has been devoted to the detailed understanding of oxidation of this surface. The formation of an oxygen induced p(4x4) reconstruction on the Ag(111) surface is known since the early 70s. A surface oxide trilayer model, based on a three-layer slab of Ag2O(111), was proposed. Accordingly, the Ag(111) surface seemed to show a similar behaviour like Pd and Rh, being neighbours in the periodic table. Further theoretical calculations predicted the stability of this reconstruction under industrially relevant conditions. Nevertheless, several questions remained unsolved: the stability of the p(4x4) reconstruction under industrially relevant conditions was not checked experimentally, the structural model of the p(4x4) structure was not proven by a crystallographic method and previously unknown structures might play an important role for the catalytic activity of Ag(111) facets. Our experimental approach is based on the nowadays routinely available highly brilliant x-ray radiation produced by third generation synchrotron light sources. This radiation is used by us in three surface sensitive x-ray techniques. In-situ surface x-ray diffraction (SXRD) allows the identification and determination of structural models of surface reconstructions under industrially relevant conditions. This technique is combined with high resolution core level spectroscopy (HRCLS) and normal incidence x-ray standing wave absorption (NIXSW), giving insight into the local binding geometry of the oxygen and silver atoms.Item Open Access Towards spin injection into silicon(2007) Dash, Saroj Prasad; Carstanjen, Heinz Dieter (Prof. Dr.)The efficient spin injection into semiconductors could pave the way to a new generation of electronics devices such as spin memories, spin transistors, and spin quantum computers. The most important semiconductor for industrial application, Si has been studied for the purpose of spin injection extensively in this thesis. Three different concepts for spin injection into Si have been addressed: (1) spin injection through a ferromagnet-Si Schottky contact, (2) spin injection using MgO tunnel barriers in between the ferromagnet and Si, and (3) spin injection from Mn-doped Si (DMS) as spin aligner. (1) FM-Si Schottky contact for spin injection: In a heterostructure of a ferromagnetic thin film on a Si substrate, any structural disorder at the interface would drastically reduce the spin polarization at the interface and, hence, the spin injection efficiency. To be able to improve the interface qualities one needs to understand the atomic processes involved in the formation of such silicide phases. In order to obtain more detailed insight into the formation of such silicide phases the initial stages of growth of Co and Fe were studied in situ by HRBS with monolayer depth resolution. As understood, it was important to prohibit the in-diffusion of Co into interstitial sites at the initial stages of growth and the out-diffusion of Si atoms in the latter stages. So in order to control and improve the interface, equilibrium growth conditions were followed (i) by lowering the growth temperature and (ii) by surfactant-mediated growth. Low temperature growth of Co on Si (100): Already at very low coverage Co diffusion into the bulk Si has been observed. The amount of in-diffused Co is, however, less than at room temperature. In contradiction to room temperature growth, Co atoms form layers of pure Co on top of the Si surface already at very low coverage. Every second Si layer, starting with the first Si layer, is Co depleted. This leads to an oscillatory Co distribution in the Si lattice which is preserved up to higher coverages (1.3 ML). Surfactant-mediated growth of Co on Si (100) : The lower surface free energy of Sb in comparison to Co and Si, makes it a potential candidate for surfactant mediated growth. By the use of one monolayer of Sb adsorbed on a Si (100) surface, Co-Si intermixing at the interface is strongly reduced in comparison to the interface without Sb as surfactant. The improved interface quality with Sb-mediated growth is also reflected in magnetic measurements. Co with Sb-mediated growth shows a higher magnetic moment. It was shown that simple solutions can reduce the FM-Si inter diffusion at the interface and improve the interface quality. However these non-equilibrium growth conditions could not stop the silicide formation completely. (2) MgO tunnel barrier for spin injection into Si: On the other hand, using an ultra-thin tunnel barrier between FM and Si will have three advantages: (i) form a chemical barrier between the FM and Si, (ii) circumvent the conductivity mismatch problem, and (iii) in addition act as a spin filter. The fabrication and characterization of ultra-thin crystalline MgO tunnel barriers on Si (100) was presented. Some of the important properties required for tunnel barriers on Si have been addressed. Ultra-thin stoichiometric MgO tunnel barriers with sharp interface with Si (100), very homogeneous, without pin-holes, and crystalline in structure could be fabricated by reactive molecular beam epitaxy. Co and Fe on an ultra thin MgO tunnel barrier were found to have island-like growth with a rough surface. Ultra-thin Co and Fe films are found to be thermally quite stable up to 450 °C. (3) Mn doped Si for spin injection: For spin injection purpose, instead of contacting the Si with a ferromagnetic metal, the contact could be made with another semiconductor, one with ferromagnetic properties. This solves the conductivity mismatch problem by ensuring that the resistivities of the materials on both side of the interface are comparable in magnitude. Si-based diluted magnetic semiconductor samples were prepared by doping Si with Mn by two different methods i) by Mn ion implantation and ii) by in-diffusion of Mn atoms (solid state growth). In the case of implanted samples, Mn atoms do not substitute Si sites. The implanted samples show room temperature ferromagnetism as measured by a SQUID magnetometer. The magnetic moment per Mn atom is found to decrease with increasing implantation dose. It has been observed that the implanted samples show carrier mediated ferromagnetism and, more importantly, mediated by both holes and electrons in contrast to statements in the literature. Solid state growth of Mn doped Si : For evaporation of Mn on Si (100), Mn atoms diffuse deep into the Si bulk already at room temperature, even for very low coverage (0.25 ML) with an oscillatory concentration depth profile as observed by HRBS with monolayer depth resolution. This results in natural MnxSi1-x/Si digital layers on the surface. Surprisingly, the samples prepared by this solid state diffusion process show room-temperature ferromagnetism having a magnetic moment of 1.8 µB per Mn atom, which is much higher than that of the ion-implanted samples. In contrast to ion-implanted samples the ferromagnetism in these samples does not show any carrier mediation.Item Open Access Nanoscale mapping of magnetic auto-oscillations with a single spin sensor(2025) Hache, Toni; Anshu, Anshu; Shalomayeva, Tetyana; Richter, Gunther; Stöhr, Rainer; Kern, Klaus; Wrachtrup, Jörg; Singha, AparajitaSpin Hall nano-oscillators convert DC to magnetic auto-oscillations in the microwave regime. Current research on these devices is dedicated to creating next-generation energy-efficient hardware for communication technologies. Despite intensive research on magnetic auto-oscillations within the past decade, the nanoscale mapping of those dynamics remained a challenge. We image the distribution of free-running magnetic auto-oscillations by driving the electron spin resonance transition of a single spin quantum sensor, enabling fast acquisition (100 ms/pixel). With quantitative magnetometry, we experimentally demonstrate for the first time that the auto-oscillation spots are localized at magnetic field minima acting as local potential wells for confining spin-waves. By comparing the magnitudes of the magnetic stray field at these spots, we decipher the different frequencies of the auto-oscillation modes. The insights gained regarding the interaction between auto-oscillation modes and spin-wave potential wells enable advanced engineering of real devices.Item Open Access The role of dimensionality and geometry in quench-induced nonequilibrium forces(2021) Nejad, Mehrana Raeisian; Khalilian, Hamidreza; Rohwer, Christian M.; Moghaddam, Ali GhorbanzadehWe present an analytical formalism, supported by numerical simulations, for studying forces that act on curved walls following temperature quenches of the surrounding ideal Brownian fluid. We show that, for curved surfaces, the post-quench forces initially evolve rapidly to an extremal value, whereafter they approach their steady state value algebraically in time. In contrast to the previously-studied case of flat boundaries (lines or planes), the algebraic decay for curved geometries depends on the dimension of the system. Specifically, steady-state values of the force are approached in time as t-d/2 in d-dimensional spherical (curved) geometries. For systems consisting of concentric circles or spheres, the exponent does not change for the force on the outer circle or sphere. However, the force exerted on the inner circles or sphere experiences an overshoot and, as a result, does not evolve to the steady state in a simple algebraic manner. The extremal value of the force also depends on the dimension of the system, and originates from curved boundaries and the fact that particles inside a sphere or circle are locally more confined, and diffuse less freely than particles outside the circle or sphere.Item Open Access Fatigue of Al thin films at ultra high frequencies(2005) Eberl, Christoph; Arzt, Eduard (Prof. Dr. phil.)Ultra high-cycle fatigue at frequencies in the GHz regime leads to a characteristic void and extrusion formation in patterned metal thin films. Resulting from the microstructural damage formation a significant degradation in form of a shift of the resonance frequency and failures by short circuits in Surface Acoustic Wave (SAW) test devices take place. To study fatigue at ultra high cycles, SAW test devices were used to test continuous and patterned Al thin films at ultra high frequencies. For stress amplitudes as low as 14 MPa lifetime measurements showed no fatigue limit for 400 nm Al thin films. The resulting damage sites appeared in regions of cyclic stress concentration as identified by Finite Element Analysis. In situ measurements revealed that the characteristic extrusion/void formation mechanism operates on a short time scale. The post-test analysis of microstructural changes reveals extrusion and void formation concentrated at grain boundaries. This finding and the observed grain growth indicates a high material flux at the grain boundaries induced by the cyclic load. Quantitative analysis also shows a correlation between extrusion density and electrical devices performance. This direct correlation shows a functional agreement with a common theory on the influence of crack density on intrinsic stresses in thin metal films. Advanced Finite Element (FEM) calculations simulate very well the sensitivity of the resonance frequency to damage structure in interconnects such as cracks, voids and extrusions. The experimentally observed linear correlation between damage density and frequency shift is reproduced by the FEM model. The estimation of the short circuit probability from the extrusion length distribution revealed an exponential dependency on the electrode distance. The observed damage formation is explained by the combined action of dislocation motion and stress-induced diffusion processes.Item Open Access Shape-dependent guidance of active Janus particles by chemically patterned surfaces(2018) Uspal, William E.; Popescu, Mihail Nicolae; Tasinkevych, Mykola; Dietrich, SiegfriedSelf-phoretic chemically active Janus particles move by inducing-via non-equilibrium chemical reactions occurring on their surfaces-changes in the chemical composition of the solution in which they are immersed. This process leads to gradients in chemical composition along the surface of the particle, as well as along any nearby boundaries, including solid walls. Chemical gradients along a wall can give rise to chemi-osmosis, i.e., the gradients drive surface flows which, in turn, drive flow in the volume of the solution. This bulk flow couples back to the particle, and thus contributes to its self-motility. Since chemi-osmosis strongly depends on the molecular interactions between the diffusing molecular species and the wall, the response flow induced and experienced by a particle encodes information about any chemical patterning of the wall. Here, we extend previous studies on self-phoresis of a sphere near a chemically patterned wall to the case of particles with rod-like, elongated shape. We focus our analysis on the new phenomenology potentially emerging from the coupling-which is inoperative for a spherical shape-of the elongated particle to the strain rate tensor of the chemi-osmotic flow. Via detailed numerical calculations, we show that the dynamics of a rod-like particle exhibits a novel ‘edge-following’ steady state: the particle translates along the edge of a chemical step at a steady distance from the step and with a steady orientation. Moreover, within a certain range of system parameters, the edge-following state co-exists with a ‘docking’ state (the particle stops at the step, oriented perpendicular to the step edge), i.e., a bistable dynamics occurs. These findings are rationalized as a consequence of the competition between the fluid vorticity and the rate of strain by using analytical theory based on the point-particle approximation which captures quasi-quantitatively the dynamics of the system.Item Open Access Investigation of oxide layer development of X6CrNiNb18-10 stainless steel exposed to high-temperature water(2024) Veile, Georg; Hirpara, Radhika; Lackmann, Simon; Weihe, StefanThe oxide layer development of X6CrNiNb18-10 (AISI 347) during exposure to high-temperature water has been investigated. Stainless steels are known to form a dual oxide layer in corrosive environments. The secondary Fe-rich oxide layer has no significant protective effect. In contrast, the primary Cr-rich oxide layer is known to reach a stabilized state, protecting the base metal from further oxidation. This study’s purpose was to determine the development of oxide layer dimensions over exposure time using SEM, TEM and EDX line scans. While a parabolic development of Cr in the protective primary layer and Fe in the secondary layer was observed, the dimensions of the Ni layer remained constant. Ni required the presence of a pronounced Fe-rich secondary layer before being able to reside on the outer secondary layer. With increasing immersion time, the Ni element fraction surpassed the Cr element fraction in the secondary layer. Oxide growth on the secondary layer could be observed. After 480 h, nearly the entire surface was covered by the outer oxide layer. In the metal matrix, no depletion of Cr or Ni could be observed over time; however, an increased presence of Cr and Ni in the primary layer was found at the expense of Fe content. The Nb-stabilized stainless steel was subject to the formation of Niobium pentoxide (Nb2O5), with the quantity and magnitude of element fraction increasing over exposure time.Item Open Access Ab-initio modeling of ultrafast demagnetization after laser irradiation in nickel, iron and cobalt(2013) Illg, Christian Michael; Fähnle, Manfred (Prof. Dr.)This work deals with ultrafast demagnetization within few hundred femtoseconds after laser pulse irradiation in nickel, iron and face-centered cubic (fcc) cobalt. It is examined with ab-initio density-functional theory and physical modeling whether the electron-phonon spin-flip scattering can be considered as underlying mechanism for ultrafast demagnetization.Item Open Access Einfluss der Herstellungsparameter auf die mechanischen Eigenschaften von Si-(B-)C-N-Precursorkeramiken(2002) Bauer, Arndt; Aldinger, Fritz (Prof. Dr.)Ziel dieser Arbeit ist es, den Herstellungsprozess für Precursorkeramiken zu optimieren und den Einfluss einzelner Herstellungsparameter auf die Eigenschaften und insbesondere auf die Hochtemperaturkriechverformung von Si-(B)-C-N-Precursorkeramiken zu charakterisieren. Am Beispiel eines kommerziell erhältlichen Polysilazans Ceraset werden als wichtigste Parameter die Vernetzungstemperatur der Polymere, die Polymerpartikelgröße nach dem Mahlen und Sieben sowie die Press- und Pyrolysebedingungen betrachtet. Dabei zeigt sich, dass die geringste Porosität einer Keramik, die über das Pressen von Polymerpulver erhalten werden kann, bei etwa 11 % liegt. Es stellt sich heraus, dass vor allem die Porosität des gepressten Grünlings für die Enddichte der Keramik ausschlaggebend ist und im optimalen Fall etwa 7 % beträgt. Von spezieller Bedeutung ist dabei die offene Porosität. Die nach außen offene Porenkanäle werden benötigt, um während der Pyrolyse ein Entweichen der Gase aus dem Grünling zu ermöglichen. Die Porosität des Grünlings hängt von der Viskosität des Polymers während des Pressvorgangs ab und kann deshalb über die Parameter Vernetzungsgrad und Warmpresstemperatur gesteuert werden. Zusätzlich zur Dichte und Hochtemperaturstabilität werden weitere Eigenschaften wie die Hochtemperaturverformung, die Bruchzähigkeit, der Elastizitätsmodul und die Biegefestigkeit von Precursorkeramiken in Abhängigkeit von den Herstellungsbedingungen ermittelt. Eine simultane Maximierung aller untersuchten Eigenschaften ist nicht möglich, so dass für bestimmte Anforderungsprofile Kompromisse gesucht werden müssen. Als Parameter mit der größten Wirkung auf die Eigenschaften hat sich die Partikelgröße erwiesen. Große Partikel haben einen positiven Einfluss auf die Bruchzähigkeit und die Hochtemperaturstabilität, wohingegen kleine Partikel sich vorteilhaft auf die Hochtemperaturkriechverformung und die Biegefestigkeit auswirken. Die Hochtemperaturverformung wurde durch Experimente bei konstanten Spannungen und Temperaturen zwischen 1350 und 1500 °C untersucht. Es wurde eine detaillierte Charakterisierung der Zeit-, Spannungs- und Temperaturabhängigkeit sowohl unter Druck- (bis 300 MPa) als auch unter Biegebeanspruchung (bis 50 MPa) durchgeführt. Dabei wird bei beiden Beanspruchungsarten selbst bei einer Versuchsdauer von bis zu zwei Wochen kein stationäres Kriechen beobachtet. Die Dehnraten sinken vielmehr auf Werte unterhalb der Nachweisgrenze ab. Es wird versucht, das Freie-Volumen-Modell, das ursprünglich zur Beschreibung der Relaxation in metallischen Gläsern entwickelt und inzwischen vor kurzem erfolgreich auf Precursorkeramiken übertragen wurde, auch bezüglich der Gültigkeit für die hier untersuchten Materialien zu überprüfen.Item Open Access Precipitation of nitrides in iron-based binary and ternary alloys; influence of defects and transformation-misfit stresses(2015) Akhlaghi, Maryam; Mittemeijer, Eric Jan (Prof. Dr. Ir.)The initial microstructure of the unnitrided specimen has a significant influence on the nitriding response of binary Fe-Me (Me: Mo or Al) alloys specimens. This effect was not investigated until now for the case of nitrided ternary Fe-Me1-Me2 alloys, the role of the initial microstructure was studied upon nitriding Fe-4.1 at.% Cr-7.9 at.% Al specimens. To this end, the recrystallized and cold-rolled specimens were nitrided at low nitriding temperature of 400 °C. Upon precipitation of misfitting coherent nitrides during nitriding of thin-foils of binary Fe-Me (Me: Cr and V) alloys, a hydrostatic tensile lattice-stain component results from the elastic accommodation of volume misfit of nitrides and ferrite matrix. The change of the ferrite-matrix lattice parameter can be traced upon precipitation of the nitrides by X-ray diffraction measurements. The theory originally developed for the case of imperfections (by Eshelby) in solids can be applied for quantitatively describing the lattice-parameter changes of the matrix, the nitrides and the aggregate (matrix+ nitrides) as function of volume fraction and type of nitrides.