No description available.

Stuttgart, Univ., Diss., 2005.

In the last years, there is a rise of interest in investigation and fabrication of nanometer sized magnetic structures due to their various applications (e.g. for data storage or micro sensors). Over the last several decades ion beam implantation became an important tool for the modification of materials and in particular for the manipulation of magnetic properties. Nanopatterning and implantation can be done simultaneously using focused-ion beam (FIB) techniques. FIB implantation and standard ion implantation differ in their beam current densities by 7 orders of magnitude. This difference can strongly influence the structural and magnetic properties, e.g. due to a rise of the local temperature in the sample during ion implantation. In previous investigations both types of implantation techniques were studied separately. The aim of the current research was to compare both implantation techniques in terms of structural changes and changes in magnetic properties using the same material system. Moreover, to separate any possible annealing effects from implantation ones, the influence of temperature on the structural and magnetic properties were additionally investigated. For the current study a model material system which is widely used for industrial applications was chosen: a 50 nm thick non-ordered nano-crystalline permalloy (Ni81Fe19) film grown on a SiO2 buffer layer based onto a (100)-oriented Si substrate. The permalloy films were implanted with a 30 keV Ga+ ion beam; and also a series of as-deposited permalloy films were annealed in an ultra-high vacuum (UHV) chamber. Several investigation techniques were applied to study the film structure and composition, and were mostly based on non-destructive X-ray investigation techniques, which are the primary focus of this work. Besides X-ray diffraction (XRD), providing the long-range order crystal structural information, extended X-ray absorption fine structure (EXAFS) measurements to probe the local structure were performed. Moreover, the film thickness, surface roughness, and interface roughness were obtained from the X-ray reflectivity (XRR) measurements. Additionally cross-sectional transmission electron microscope (XTEM) imaging was used for local structural characterizations. The Ga depth distribution of the samples implanted with a standard ion implanter was measured by the use of Auger electron spectroscopy (AES) and Rutherford backscattering (RBS), and was compared with theoretical TRIDYN calculation. The magnetic properties were characterized via polar magneto-optic Kerr effect (MOKE) measurements at room temperature. It was shown that both implantation techniques lead to a further material crystallization of the partially amorphous permalloy material (i.e. to an increase of the amount of the crystalline material), to a crystallite growth and to a material texturing towards the (111) direction. For low ion fluences a strong increase of the amount of the crystalline material was observed, while for high ion fluences this rise is much weaker. At low ion fluences XTEM images show small isolated crystallites, while for high ones the crystallites start to grow through the entire film. The EXAFS analysis shows that both Ni and Ga atom surroundings have a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter for both implantation techniques increases with increasing ion fluence according to the same linear law. The lattice parameters obtained from the EXAFS measurements for both implantation types are in a good agreement with the results obtained from the XRD measurements. Grazing incidence XRD (GIXRD) measurements of the samples implanted with a standard ion implanter show an increasing value of microstrain with increasing ion fluence (i.e. the lattice parameter variation is increasing with fluence). Both types of implantation result in an increase of the surface and the interface roughness and demonstrate a decrease of the saturation polarization with increasing ion fluence. From the obtained results it follows that FIB and standard ion implantation influence structure and magnetic properties in a similar way: both lead to a material crystallization, crystallite growth, texturing and decrease of the saturation polarization with increasing ion fluence. A further crystallization of the highly defective nano-crystalline material can be simply understood as a result of exchange processes induced by the energy transferred to the system during the ion implantation. The decrease of the saturation polarization of the implanted samples is mainly attributed to the simple presence of the Ga atoms on the lattice sites of the permalloy film itself. For the annealed samples more complex results were found. The corresponding results can be separated into two temperature regimes: into low (≤400°C) and high (>400°C) temperatures. Similar to the implanted samples, annealing results in a material crystallization with large crystallites growing through the entire film and in a material texturing towards the (111) direction. The EXAFS analysis shows a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter of the annealed samples slightly decreases at low annealing temperatures, reaches its minimum at about ~400°C and slightly rises at higher ones. From the GIXRD measurements it can be observed that the permalloy material at temperatures above >400°C reaches its strain-free state. On the other hand, the film roughness increases with increasing annealing temperature and a de-wetting of the film is observed at high annealing temperatures. Regardless of the material crystallization and texturing, the samples annealed at low temperatures demonstrate no change in saturation polarization, while at high temperatures a rise by approximately ~15% at 800°C was observed. The rise of the saturation polarization at high annealing temperatures is attributed to the de-wetting effect.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO^2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and ≈1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960\'s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain \\lq magic\' angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

No description available.

Abstract des Vortrages: Titanium aluminide (TiAl) alloys are attractive lightweight materials for mediumtemperature (500°-750°C) structural applications including components such as jet engine and industrial gas turbine blades, turbocharger rotors and automotive engine valves. However, envisaged service temperatures for future advanced applications will have to be in the range of 750° to 1000°C, over which these alloys suffer from both oxidation and oxygen embrittlement. Therefore, development of surfaceengineering techniques for preventing high-temperature environmental damage is critical in exploiting the advantages of TiAl alloys to their fullest extent. Two efficient approaches to protecting candidate TiAl alloys from high-temperature (>750°C) environmental degradation have been developed at HZDR. The first technique involves a single step, namely treating TiAl alloy components directly by plasma immersion ion implantation (PIII) of fluorine using a mixture of difluoromethane and argon (CH2F2 + 25% Ar) as the precursor gas. The oxidation performance of the fluorine-implanted alloys has been evaluated by thermal gravimetric analysis (TGA) over the temperature range of 750° to 1050°C under conditions of both isothermal and thermal cyclic oxidation in air, and for times as long as 6000 h. This type of surface modification has been shown to produce a stable, adherent and highly protective alumina scale. The second technique involves the fabrication of a durable protective coating in a two-step process, namely formation of a thin aluminum-rich TiAl layer (Ti-60Al) by chemical vapor deposition (CVD) employing a mixture of inorganic precursors, followed by PIII of fluorine. Subsequent long-term oxidation exposures to air at 900°C of a GE 4822 alloy (Ti-48Al-2Cr-2Nb; alloy composition qualified for aerospace applications) have shown that the coating so developed is able to successfully prevent oxidation damage to the base material while maintaining up to 90% of its initial mechanical properties (strength and ductility).

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO^2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and ≈1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960\'s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain \\lq magic\' angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

Abstract des Vortrages: Titanium aluminide (TiAl) alloys are attractive lightweight materials for mediumtemperature (500°-750°C) structural applications including components such as jet engine and industrial gas turbine blades, turbocharger rotors and automotive engine valves. However, envisaged service temperatures for future advanced applications will have to be in the range of 750° to 1000°C, over which these alloys suffer from both oxidation and oxygen embrittlement. Therefore, development of surfaceengineering techniques for preventing high-temperature environmental damage is critical in exploiting the advantages of TiAl alloys to their fullest extent. Two efficient approaches to protecting candidate TiAl alloys from high-temperature (>750°C) environmental degradation have been developed at HZDR. The first technique involves a single step, namely treating TiAl alloy components directly by plasma immersion ion implantation (PIII) of fluorine using a mixture of difluoromethane and argon (CH2F2 + 25% Ar) as the precursor gas. The oxidation performance of the fluorine-implanted alloys has been evaluated by thermal gravimetric analysis (TGA) over the temperature range of 750° to 1050°C under conditions of both isothermal and thermal cyclic oxidation in air, and for times as long as 6000 h. This type of surface modification has been shown to produce a stable, adherent and highly protective alumina scale. The second technique involves the fabrication of a durable protective coating in a two-step process, namely formation of a thin aluminum-rich TiAl layer (Ti-60Al) by chemical vapor deposition (CVD) employing a mixture of inorganic precursors, followed by PIII of fluorine. Subsequent long-term oxidation exposures to air at 900°C of a GE 4822 alloy (Ti-48Al-2Cr-2Nb; alloy composition qualified for aerospace applications) have shown that the coating so developed is able to successfully prevent oxidation damage to the base material while maintaining up to 90% of its initial mechanical properties (strength and ductility).

In the last years, there is a rise of interest in investigation and fabrication of nanometer sized magnetic structures due to their various applications (e.g. for data storage or micro sensors). Over the last several decades ion beam implantation became an important tool for the modification of materials and in particular for the manipulation of magnetic properties. Nanopatterning and implantation can be done simultaneously using focused-ion beam (FIB) techniques. FIB implantation and standard ion implantation differ in their beam current densities by 7 orders of magnitude. This difference can strongly influence the structural and magnetic properties, e.g. due to a rise of the local temperature in the sample during ion implantation. In previous investigations both types of implantation techniques were studied separately. The aim of the current research was to compare both implantation techniques in terms of structural changes and changes in magnetic properties using the same material system. Moreover, to separate any possible annealing effects from implantation ones, the influence of temperature on the structural and magnetic properties were additionally investigated. For the current study a model material system which is widely used for industrial applications was chosen: a 50 nm thick non-ordered nano-crystalline permalloy (Ni81Fe19) film grown on a SiO2 buffer layer based onto a (100)-oriented Si substrate. The permalloy films were implanted with a 30 keV Ga+ ion beam; and also a series of as-deposited permalloy films were annealed in an ultra-high vacuum (UHV) chamber. Several investigation techniques were applied to study the film structure and composition, and were mostly based on non-destructive X-ray investigation techniques, which are the primary focus of this work. Besides X-ray diffraction (XRD), providing the long-range order crystal structural information, extended X-ray absorption fine structure (EXAFS) measurements to probe the local structure were performed. Moreover, the film thickness, surface roughness, and interface roughness were obtained from the X-ray reflectivity (XRR) measurements. Additionally cross-sectional transmission electron microscope (XTEM) imaging was used for local structural characterizations. The Ga depth distribution of the samples implanted with a standard ion implanter was measured by the use of Auger electron spectroscopy (AES) and Rutherford backscattering (RBS), and was compared with theoretical TRIDYN calculation. The magnetic properties were characterized via polar magneto-optic Kerr effect (MOKE) measurements at room temperature. It was shown that both implantation techniques lead to a further material crystallization of the partially amorphous permalloy material (i.e. to an increase of the amount of the crystalline material), to a crystallite growth and to a material texturing towards the (111) direction. For low ion fluences a strong increase of the amount of the crystalline material was observed, while for high ion fluences this rise is much weaker. At low ion fluences XTEM images show small isolated crystallites, while for high ones the crystallites start to grow through the entire film. The EXAFS analysis shows that both Ni and Ga atom surroundings have a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter for both implantation techniques increases with increasing ion fluence according to the same linear law. The lattice parameters obtained from the EXAFS measurements for both implantation types are in a good agreement with the results obtained from the XRD measurements. Grazing incidence XRD (GIXRD) measurements of the samples implanted with a standard ion implanter show an increasing value of microstrain with increasing ion fluence (i.e. the lattice parameter variation is increasing with fluence). Both types of implantation result in an increase of the surface and the interface roughness and demonstrate a decrease of the saturation polarization with increasing ion fluence. From the obtained results it follows that FIB and standard ion implantation influence structure and magnetic properties in a similar way: both lead to a material crystallization, crystallite growth, texturing and decrease of the saturation polarization with increasing ion fluence. A further crystallization of the highly defective nano-crystalline material can be simply understood as a result of exchange processes induced by the energy transferred to the system during the ion implantation. The decrease of the saturation polarization of the implanted samples is mainly attributed to the simple presence of the Ga atoms on the lattice sites of the permalloy film itself. For the annealed samples more complex results were found. The corresponding results can be separated into two temperature regimes: into low (≤400°C) and high (>400°C) temperatures. Similar to the implanted samples, annealing results in a material crystallization with large crystallites growing through the entire film and in a material texturing towards the (111) direction. The EXAFS analysis shows a perfect near-order coordination corresponding to an fcc symmetry. The lattice parameter of the annealed samples slightly decreases at low annealing temperatures, reaches its minimum at about ~400°C and slightly rises at higher ones. From the GIXRD measurements it can be observed that the permalloy material at temperatures above >400°C reaches its strain-free state. On the other hand, the film roughness increases with increasing annealing temperature and a de-wetting of the film is observed at high annealing temperatures. Regardless of the material crystallization and texturing, the samples annealed at low temperatures demonstrate no change in saturation polarization, while at high temperatures a rise by approximately ~15% at 800°C was observed. The rise of the saturation polarization at high annealing temperatures is attributed to the de-wetting effect.

In an electron fluid, both resistive and viscous mechanisms can be present. In systems with perfect translational invariance momentum is a conserved quantity, and as the electrons carry both charge and momentum, the current cannot decay. Predictions from theories at the particle physics-condensed matter physics interface using the `AdS/CFT' correspondence suggest that hydrodynamic charge flow might exist in some exotic metallic states. In the high-Tc cuprates the T-linear resistivity in the strange metal regime is conjectured to be due to hydrodynamic effects. In this dissertation, I start out drawing a theoretical outline of the hydrodynamic theory of electron transport in solids. In the search for a high purity metal that can host such a hydrodynamic electron transport, we looked at the non-magnetic delafossite oxides PdCoO2 and PtCoO2, which have the highest conductivities of any known oxides, and whose key properties I will review. As the signatures of viscosity can only be realised in transport through boundary scattering, the samples had to be taken down to the mesoscopic limit, where the momentum conserving and relaxing scattering mean free paths of the material are comparable to the channel width. I will discuss the focussed ion beam (FIB) micro-structuring technique that I have implemented to fabricate the mesoscopic devices. To interpret the transport in the mesoscopic regime, a comprehensive understanding of the bulk transport is first necessary and I will present my measurements of the magnetoresistance and Hall effect in both materials, which show deviations from the predictions of standard models highlighting some intriguing physics even in the bulk limit. Finally, I will present the data from magnetotransport measurements at the mesoscopic limit. Magnetic field introduces a variable length scale, the cyclotron radius, in the system which can be used to tune through different transport regimes. I will discuss the ballistic and hydrodynamic signatures in the transport that becomes accessible through magnetic field tuning in the mesoscopic samples of the delafossites PdCoO2 and PdCoO2.