Shape Evolution of Nanostructures by Thermal and Ion Beam Processing: Modeling & Atomistic Simulations

Single-crystalline nanostructures often exhibit gradients of surface (and/or interface) curvature that emerge from fabrication and growth processes or from thermal fluctuations. Thus, the system-inherent capillary force can initiate morphological transformations during further processing steps or during operation at elevated temperature. Therefore and because of the ongoing miniaturization of functional structures which causes a general rise in surface-to-volume ratios, solid-state capillary phenomena will become increasingly important: On the one hand diffusion-mediated capillary processes can be of practical use in view of non-conventional nanostructure fabrication methods based on self-organization mechanisms, on the other hand they can destroy the integrity of nanostructures which can go along with the failure of functionality. Additionally, capillarity-induced shape transformations are effected and can thereby be controlled by applied fields and forces (guided or driven evolution). With these prospects and challenges at hand, formation and shape transformation of single-crystalline nanostructures due to the system-inherent capillary force in combination with external fields or forces are investigated in the frame of this dissertation by means of atomistic computer simulations. For the exploration (search, description, and prediction) of reaction pathways of nanostructure shape transformations, kinetic Monte Carlo (KMC) simulations are the method of choice. Since the employed KMC code is founded on a cellular automaton principle, the spatio-temporal development of lattice-based N-particle systems (N up to several million) can be followed for time spans of several orders of magnitude, while considering local phenomena due to atomic-scale effects like diffusion, nucleation, dissociation, or ballistic displacements. In this work, the main emphasis is put on nanostructures which have a cylindrical geometry, for example, nanowires (NWs), nanorods, nanotubes etc

Self-Organization of Nanocluster delta-Layers at Ion-Beam-Mixied Si-SiO2 Interfaces

This diploma thesis presents experimental evidence of a theoretical concept which predicts the self-organization of delta-layers of silicon nanoclusters in the buried oxide of a MOS-like structure. This approach of "bottom-up" structuring might be of eminent importance in view of future semiconductor memory devices. Unconventionally, a 15nm thin SiO2 layer, which is enclosed by a 50nm poly-Si capping layer and the Si substrate, is irradiated with Si+ ions. Ion impact drives the system to a state far from thermodynamic equilibrium, i.e. the local composition of the target is modified to a degree unattainable in common processes. A region of SiOx (x<2) - where x is a function of depth - is formed which is not stable. During annealing, the system relaxes towards equilibrium, i.e. phase separation (via spinodal decomposition and nucleation) sets in. Within a certain time window of annealing, the structure of the system matches with a structure similar to the multidot non-volatile memory device, the principal character of which is a 2D layer of Si nanoclusters of ~3nm in diameter which is embedded in a 3D SiO2 matrix at a distance of ~3nm from the Si substrate. The physical mechanisms of ion mixing of the two Si-SiOx interfaces and subsequent phase separation, which result in the desired sample structure, are elucidated from the viewpoint of computer simulation. In addition, experimental evidence is presented based on various methods, including TEM, RBS, and SIMS. Of particular importance is a novel method of Si nanocluster decoration which applies Ge as contrast enhancing element in TEM studies of tiny Si nanoclusters

Electrolysis in reduced gravitational environments: current research perspectives and future applications

Electrochemical energy conversion technologies play a crucial role in space missions, for example, in the Environmental Control and Life Support System (ECLSS) on the International Space Station (ISS). They are also vitally important for future long-term space travel for oxygen, fuel and chemical production, where a re-supply of resources from Earth is not possible. Here, we provide an overview of currently existing electrolytic energy conversion technologies for space applications such as proton exchange membrane (PEM) and alkaline electrolyzer systems. We discuss the governing interfacial processes in these devices influenced by reduced gravitation and provide an outlook on future applications of electrolysis systems in, e.g., in-situ resource utilization (ISRU) technologies. A perspective of computational modelling to predict the impact of the reduced gravitational environment on governing electrochemical processes is also discussed and experimental suggestions to better understand efficiency-impacting processes such as gas bubble formation and detachment in reduced gravitational environments are outlined

Electrolysis in reduced gravitational environments: current research perspectives and future applications

Electrochemical energy conversion technologies play a crucial role in space missions, for example, in the Environmental Control and Life Support System (ECLSS) on the International Space Station (ISS). They are also vitally important for future long-term space travel for oxygen, fuel and chemical production, where a re-supply of resources from Earth is not possible. Here, we provide an overview of currently existing electrolytic energy conversion technologies for space applications such as proton exchange membrane (PEM) and alkaline electrolyzer systems. We discuss the governing interfacial processes in these devices influenced by reduced gravitation and provide an outlook on future applications of electrolysis systems in, e.g., in-situ resource utilization (ISRU) technologies. A perspective of computational modelling to predict the impact of the reduced gravitational environment on governing electrochemical processes is also discussed and experimental suggestions to better understand efficiency-impacting processes such as gas bubble formation and detachment in reduced gravitational environments are outlined

Bohrtechnische Erschließung submariner Gashydratlagerstätten

Gashydratlagerstätten sind in Permafrostgebieten und unter dem Meeresboden zu finden. Das energetische Potential der weltweiten Gashydratvorkommen, vor allem im submarinen Bereich, ist enorm. Derzeit existiert aber noch keine Technologie mit der sie kommerziell erschlossen werden können. Die größten Herausforderungen bei der bohrtechnischen Erschließung submariner Gashydratlagerstätten werden in der Richtbohrtechnik in geringverfestigten Sedimenten, der Bohrlochstabilität, der Einhaltung eines sehr engen Druckfensters sowie in der Vermeidung ungewollter Dissoziationsvorgänge während des Bohrprozesses gesehen. In der Arbeit werden mögliche Ansätze für die bohrtechnische Erschließung von submarinen Gashydratlagerstätten, speziell für das gerichtete Bohren in unkonsolidierten Formationen, zusammengetragen. Es werden verschiedene Erschließungskonzepte diskutiert und schließlich wird die Machbarkeit von zwei Bohrkonzepten untersucht. Das erste Konzept zielt in erster Linie auf die Herstellung vertikaler Bohrungen zu Produktionstestzwecken in Gashydratlagerstätten ab. Auf Grundlage eines vorhandenen Meeresbodenbohrgerätes wird eine neuartige Technologie entwickelt, mit der eine Tiefsee-Gashydratbohrung abgeteuft, verrohrt und komplettiert werden kann, ohne dass eine Bohrplattform oder ein Bohrschiff eingesetzt werden muss. Das zweite Konzept beinhaltet die Herstellung von horizontalen Produktionsbohrungen für eine kommerzielle Gashydratnutzung. Es wird untersucht, ob und unter welchen Bedingungen solche Bohrungen mit konventionellem Equipment machbar sind. Es wird aufgezeigt, dass die Herausforderungen gemeistert werden können und die bohrtechnische Erschließung submariner Gashydratlagestätten mit beiden Konzepten grundsätzlich machbar erscheint

Shape Evolution of Nanostructures by Thermal and Ion Beam Processing: Modeling &amp;amp; Atomistic Simulations

Single-crystalline nanostructures often exhibit gradients of surface (and/or interface) curvature that emerge from fabrication and growth processes or from thermal fluctuations. Thus, the system-inherent capillary force can initiate morphological transformations during further processing steps or during operation at elevated temperature. Therefore and because of the ongoing miniaturization of functional structures which causes a general rise in surface-to-volume ratios, solid-state capillary phenomena will become increasingly important: On the one hand diffusion-mediated capillary processes can be of practical use in view of non-conventional nanostructure fabrication methods based on self-organization mechanisms, on the other hand they can destroy the integrity of nanostructures which can go along with the failure of functionality. Additionally, capillarity-induced shape transformations are effected and can thereby be controlled by applied fields and forces (guided or driven evolution). With these prospects and challenges at hand, formation and shape transformation of single-crystalline nanostructures due to the system-inherent capillary force in combination with external fields or forces are investigated in the frame of this dissertation by means of atomistic computer simulations. For the exploration (search, description, and prediction) of reaction pathways of nanostructure shape transformations, kinetic Monte Carlo (KMC) simulations are the method of choice. Since the employed KMC code is founded on a cellular automaton principle, the spatio-temporal development of lattice-based N-particle systems (N up to several million) can be followed for time spans of several orders of magnitude, while considering local phenomena due to atomic-scale effects like diffusion, nucleation, dissociation, or ballistic displacements. In this work, the main emphasis is put on nanostructures which have a cylindrical geometry, for example, nanowires (NWs), nanorods, nanotubes etc

Self-Organization of Nanocluster delta-Layers at Ion-Beam-Mixied Si-SiO2 Interfaces

This diploma thesis presents experimental evidence of a theoretical concept which predicts the self-organization of delta-layers of silicon nanoclusters in the buried oxide of a MOS-like structure. This approach of "bottom-up" structuring might be of eminent importance in view of future semiconductor memory devices. Unconventionally, a 15nm thin SiO2 layer, which is enclosed by a 50nm poly-Si capping layer and the Si substrate, is irradiated with Si+ ions. Ion impact drives the system to a state far from thermodynamic equilibrium, i.e. the local composition of the target is modified to a degree unattainable in common processes. A region of SiOx (x<2) - where x is a function of depth - is formed which is not stable. During annealing, the system relaxes towards equilibrium, i.e. phase separation (via spinodal decomposition and nucleation) sets in. Within a certain time window of annealing, the structure of the system matches with a structure similar to the multidot non-volatile memory device, the principal character of which is a 2D layer of Si nanoclusters of ~3nm in diameter which is embedded in a 3D SiO2 matrix at a distance of ~3nm from the Si substrate. The physical mechanisms of ion mixing of the two Si-SiOx interfaces and subsequent phase separation, which result in the desired sample structure, are elucidated from the viewpoint of computer simulation. In addition, experimental evidence is presented based on various methods, including TEM, RBS, and SIMS. Of particular importance is a novel method of Si nanocluster decoration which applies Ge as contrast enhancing element in TEM studies of tiny Si nanoclusters

Shape Evolution of Nanostructures by Thermal and Ion Beam Processing: Modeling &amp;amp; Atomistic Simulations

Single-crystalline nanostructures often exhibit gradients of surface (and/or interface) curvature that emerge from fabrication and growth processes or from thermal fluctuations. Thus, the system-inherent capillary force can initiate morphological transformations during further processing steps or during operation at elevated temperature. Therefore and because of the ongoing miniaturization of functional structures which causes a general rise in surface-to-volume ratios, solid-state capillary phenomena will become increasingly important: On the one hand diffusion-mediated capillary processes can be of practical use in view of non-conventional nanostructure fabrication methods based on self-organization mechanisms, on the other hand they can destroy the integrity of nanostructures which can go along with the failure of functionality. Additionally, capillarity-induced shape transformations are effected and can thereby be controlled by applied fields and forces (guided or driven evolution). With these prospects and challenges at hand, formation and shape transformation of single-crystalline nanostructures due to the system-inherent capillary force in combination with external fields or forces are investigated in the frame of this dissertation by means of atomistic computer simulations. For the exploration (search, description, and prediction) of reaction pathways of nanostructure shape transformations, kinetic Monte Carlo (KMC) simulations are the method of choice. Since the employed KMC code is founded on a cellular automaton principle, the spatio-temporal development of lattice-based N-particle systems (N up to several million) can be followed for time spans of several orders of magnitude, while considering local phenomena due to atomic-scale effects like diffusion, nucleation, dissociation, or ballistic displacements. In this work, the main emphasis is put on nanostructures which have a cylindrical geometry, for example, nanowires (NWs), nanorods, nanotubes etc