Scanning tunneling microscopy (STM) images and scanning tunneling spectroscopy (STS) spectra of galena (PbS) and hematite (a-Fe203) were calculated using ab-initio methods in order to interpret experimental images and spectra that were taken in previous studies. These calculations have helped to understand which states of the mineral surfaces were imaged depending on the bias voltage and tip-sample separation. The computational results also gave insight in electron transfer processes that take place during surface adsorption/oxidation/reduction processes. In this context, different oxidation (using O₂ and ferric iron as oxidants) and gold adsorption/reduction mechanisms on galena were evaluated at an atomic level. On hematite, the main emphasis was determining the differences in the local electronic structure of specific sites above the surface and the electronic structure of the bulk. Hereby, step sites turned out to have an increased local density of states at certain electron binding energies that are absent on flat surfaces. states can explain the highly increased reactivity of step sites as compared to terraces. X-ray photoelectron spectra (XPS) were calculated to compare the photoelectron peaks of the calculated specific surface structures (that do not have a bulk equivalent) with experimentally obtained XPS spectra. Most of the calculated peak chemical shifts coincided with those that were found in experiments and that were previously interpreted in terms of known bulk structures. Therefore, it can be inferred that the conventional way of interpreting XPS spectra might be incomplete if specific surface structures are neglected. In order to understand step velocities on a gypsum (010) surface, step energies of different step directions were calculated using an ab-initio approach. An approximately linear relationship was found between the calculated step energies and the experimentally determined step velocities. / Ph. D.

Among the well-known methods to form or modify the composition and physical properties of thin films, ion implantation has shown to be a very powerful technique. In particular, ion beam syntheses of binary iron silicide have been studied by several groups. Further, the interests in transition metal silicide systems are triggered by their potential use in advanced silicon based opto-electronic devices. In addition, ternary silicides have been by far less studied than their binary counterparts despite the fact that they have interesting magnetic and electronic properties. In this study, we investigate ion beam synthesis of Fe-Si binary structures and Fe-Co-Si ternary structures. This work involves fundamental investigation into development of a scalable synthesis process involving binary and ternary transitional metal silicide thin films and Nano-structures using low energy ion beams. Binary structures were synthesized by implanting Fe- at 50 keV energy. Since ion implantation is a dynamic process, Dynamic simulation techniques were used in these studies to determine saturation fluences for ion implantation. Also, static and dynamic simulation results were compared with experimental results. The outcome of simulations and experimental results indicate, dynamic simulation codes are more suitable than static version of the TRIM to simulate high fluence, low energy and, heavy ion implantation processes. Furthermore, binary Fe-Si phase distribution was determined at different implantation fluences and annealing temperatures. A higher fluence implantation at 2.16×1017 atoms/cm2 and annealing at 500 oC showed three different Fe-Si phase formations (β-FeSi2, FeSi and Fe3Si) in substrate. Further, annealing the samples at 800 oC for 60 minutes converted the Fe3Si phase into FeSi2 and FeSi phases. As an extension, a second set of Fe- ion implantations was carried with the same parameters while the substrate was placed under an external magnetic field. External magnetic fields stimulate the formation of magnetic phase centers in the substrate. X-ray diffraction (XRD) results shows formation of ferromagnetic Fe3Si phase in the Si matrix after annealing at 500 oC for 60 minutes. In addition, X-ray photoelectron spectra (XPS) provide further evidence for ferromagnetic metallic behavior of Fe3Si in the substrate. Ternary Fe-Co-Si structures were synthesized by implanting Fe- & Co- into a Si (100) substrate at an energy of 50 keV at saturation fluences. Both Fe- & Co- co-implantation were performed under external magnetic fields to enhance magnetic phase formation. Fe(1-x)CoxSi B20-type cubic structure can be synthesized on Si(100) substrate with 0.4≤x≤0.55 concentration range using ion implantation under external magnetic field. Moreover, magnetic measurement indicates a possible magnetic phase transformation at ~50 K. Further, XPS results also provide evidence for metallic & ferromagnetic properties in the thin film structure

Diese Arbeit ist eine umfassende und systematische Untersuchung der Adsorption von Wasser auf der Fe2O3(0001)-Oberfläche. Sie deckt eine Vielzahl der Probleme auf, die während des Anfangs der Wasseradsorption auf den Übergangsmetalloxidoberflächen auftreten. Dazu gehören die Stabilität der reinen Oberfläche, die Rolle der Oberflächendefekte, der Einfluss der kristallographischen und elektronischen Strukturen, die elementare Kinetik der adsorbierten Arten von Wasser auf der Oberfläche, die Eigenschaften bei niedrigem und hohem Bedeckungsgrad und die Auswirkungen der Wasserstoffbrückenbindung auf die Adsorption und das XPS-Spektrum. Niedrige und hohe Bedeckungsgrade von 0.25 bis 1 Monolage werden untersucht, um die Grundlage für die folgende Erhöhung der Wasserbedeckung, die normalerweise in Experimenten beobachtet wird, zu ermitteln. Das Einzeladsorptionsregime wurde erweitert, um eine echte Wasserdampfumgebung mittels der Gibbs-Energie zu berücksichtigen. Die Ensemblemethode wurde benutzt, um die durchschnittlichen Werte der energisch entarteten Adsorptionskonfigurationen zu interpretieren. Der Abstandsmatrixansatz wurde entwickelt, um die statistische Analyse zu ermöglichen. Die Methode reduziert mithilfe der Oberflächensymmetrie die Gesamtzahl der Adsorptionskonfigurationen, die zu berücksichtigen sind. Das XPS-Spektrum wird für verschiedene Wasserdampftemperaturen und Drücke simuliert. Es wird eine gute Übereinstimmung zwischen theoretischen und experimentellen Spektren erreicht und die geringen Unterschiede werden erklärt. Die Hauptmerkmale des XPS-Spektrums beim Anstieg von relativer Feuchtigkeit des Wasserdampfs werden beschrieben. Die Ähnlichkeiten und Unterschiede der Wasseradsorption auf Fe2O3 und Al2O3 werden betont und die wichtigsten Tendenzen werden abgeleitet. Auf Grund dieser Arbeit kann der Anfangsprozess der Fe2O3(0001)-Oberflächenbenetzung erklärt werden. / The present study is a comprehensive systematic theoretical investigation of the water adsorption on the Fe2O3(0001) surface. It covers a broad number of problems inherent to the initial stage of the water adsorption on the transition metal oxide surface: clean surface stability, the influence of surface oxygen defects, the role of the crystallographic and electronic structures on the adsorption configuration, elementary kinetics, the particular qualities of the low and high adsorption coverage regimes and the effect of the hydrogen bonding on adsorption and on the XPS spectra simulation. The low and high coverage regimes from 0.25 up to 1 monolayer water coverage were considered to form a basis for the following increase of water loading mainly observed in experiments. A single adsorption energy picture was expanded to take into account the water vapour environment through the Gibbs free energy. The statistical ensemble was employed to classify and interpret the averaged values of the adsorption configurations set rather than the ``invisible'' in experiment quantities intrinsic to the particular single adsorption configuration. In order to make the statistical analysis feasible an effective distance matrix scheme was developed. It helped to reduce the total number of structures to consider without loss of generality by virtue of the surface space symmetry. Based on the statistical contribution of each individual adsorption configuration, the O-1s XPS was simulated for the various water vapour environments. A good agreement between the simulated and experimental spectra was found. Wherever it was important, the similarities and differences between water adsorption on the Fe2O3, Al2O3 and Fe3O4 surfaces were stressed and the main tendencies were deduced. Based on the present study, the whole picture of the initial stage of the Fe2O3(0001) surface wetting process was established.

The subject of this work subscribes to the international preoccupation regarding the elucidation of magnetic properties of solids. The crystallographic, electronic and magnetic structures of Al-Mn-Ni alloys and compounds have been investigated by X-ray diffraction, magnetization and magnetic susceptibility measurements, X-ray photoelectron spectroscopy (XPS), and band structure calculations. The thesis is organized in 6 Chapters, followed by the summary. Chapter 1 contains a brief theoretical introduction into the magnetism of metallic systems, as well the principles of XPS. The sample preparation details and all the techniques employed in the characterization of the systems are described in Chapter 2. The next 4 Chapters contain the experimental results for Mn1-xAlxNi3, Mn1-xAlxNi, Ni1-xMnxAl, Ni0.7-xAlxMn0.3 systems.