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Publication Type: search.filters.UBSTyp.DissertationSubject: search.filters.subject.540Start date: 2017Institute: search.filters.UBSInstitut.Institut für Materialwissenschaft

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    Template controlled mineralization of functional ZnO thin films
    (2017) Blumenstein, Nina; Bill, Joachim (Prof. Dr.)
    In this thesis, the influence of different organic templates on the bioinspired deposition of ZnO thin films is investigated. Depending on the polarity of the templates, the growth and the properties of the films can be influenced. On a non-polar template, film growth is inhibited whereas homogeneous films grow on polar templates. Additionally, it was shown that on a template with high polarity a crystallographic texture is observed. This leads to a macroscopically measurable piezoelectric response of these samples. In the last part of this work, the incorporation of Al, Ga and In into the ZnO films was investigated. Measurements showed a blue shift of the UV photoluminescence emission and an improved electrical conductivity with increasing doping content.
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    Bioinspired structure tailoring of tin oxide based materials for high capacity electrodes
    (2021) Jahnke, Timotheus; Bill, Joachim (Prof. Dr.)
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    Hydrogen transport in thin films : Mg-MgH2 and Ti-TiH2 systems
    (2018) Hadjixenophontos, Efi
    Hydrogen storage has become progressively important due to increasing energy demand. Magne-sium (Mg/MgH2) is one of the most promising elements of hydrogen uptake, however, the slow kinetics and need for high temperatures during dehydrogenation make this material challenging for mobile applications. Meanwhile, Titanium (Ti/TiH2/TiO2) draws attention due to its catalytic effect in hydrogenation of other metals with higher capacities. A comprehensive way to quantitatively char-acterize the kinetics of hydride formation in both systems (Mg and Ti) is shown here. A technique allowing a large range of pressures and temperatures (room temperature to 300 °C and from 0.05 bar up to 100 bar) is developed successfully. Thin films (50-1000 nm), deposited by ion beam sput-tering (PVD), are used because of their smooth surface and defined structure. In order to study hydrogen transport precisely, X-ray diffraction (XRD), electron microscopy (SEM/FIB/TEM) and electric resistance measurements are used. In the case of Mg, while a Pd coating is used as catalyst, the hydride is formed from the surface towards the substrate and transformation in the morpholo-gy is observed. Parabolic law is followed and the diffusion coefficient of hydrogen in MgH2 is ob-tained at room temperature (2.67 · 10-17 cm2/s). Additionally, a model is created to fit the experi-mental change in resistance during hydrogen loading and shows the changes in the behavior of thicker layers. The interface between Pd/Mg is discussed, since Mg5Pd2 and Mg6Pd are formed at high temperatures and are most dominant over dehydrogenation. However, at room temperature, this interface appears to be more stable. The activation energy of hydrogenation is calculated ex-perimentally from an Arrhenius plot to be equal to Ea = 22.6 ± 2.0 kJ/mol and the pre-factor D0 = 3904 cm2/s. Additional attention is given to magnesium hydride as an anode electrode in Li-ion bat-teries. TEM investigations of thin film electrodes demonstrate the complete lithiation of the mate-rial however, with drastic volume changes, leading to bad reversibility. In Ti the thin oxide layer naturally formed on the surface, appears to play a dominant role in the kinetics of hydrogen transport leading to a linear kinetics. A pressure dependency is observed, while an experimental evaluation of the permeation coefficient in the oxide is also discussed. Important information on the hydrogen transport is obtained in both systems, giving an input for further improvements of such hydrides.
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    Growth of oxide materials with Ruddlesden-Popper- and garnet-type structures via the optical float zone method: investigations of scintillation, optical, and magnetic properties, and post-growth modifications of single crystals via topochemical routes
    (2025) Yilmaz, Hasan; Clemens, Oliver (Prof. Dr.)
    With the continuous progress in materials science, the global market demand for high-performance functional materials, especially those with customized optical and magnetic properties, has increased significantly due to their critical role in next-generation technologies such as photonic devices, data storage systems, quantum computing, and biomedical applications. With this motivation, this dissertation is focused on the growth of high-quality oxide single crystals with Ruddlesden-Popper (RP) and garnet-type structures using the optical floating zone (OFZ) method and the detailed investigation of their scintillation, optical and magnetic properties. Furthermore, the use of chemical doping and post-growth topochemical modifications as strategies to modify material properties and stabilise metastable structures is also covered. With these approaches, we can classify this study into two parts: optical and magnetic properties. In the first part of this work, RP-type n = 1 LaSrGaO4 (LSGO) and Garnet-type Gd3In2Ga3O12 (GIGG) single crystals doped with different Rare Earths (RE) including Eu, Sm, Ho, Nd have been grown via OFZ method to investigate their luminescence, decay time kinetics and scintillation properties. To compare the scintillation behaviour, a well-known commercial scintillator, Gd2.98Ce0.02Al2Ga3O12 (0.02Ce:GAGG) single crystal, was synthesised and characterised using the same methods. This limits deviations in scintillation properties caused by different synthesis methods. Powder X-ray diffraction (XRD) and Single Crystal X-ray diffraction (SC-XRD) measurements together with Rietveld analysis confirmed phase purity and crystallinity, while Scanning Electron Microscopy (SEM-EDX) and backscatter electron imaging (BSE) confirmed the homogeneous distribution of the dopants. In addition to these analytical methods, Photoluminescence Spectroscopy (PL) and luminescence decay measurements have demonstrated that these RE-doped single crystals have strong emission, which is related to the low phonon energy of their host lattices. However, scintillation measurements under 137Cs gamma-ray point source excitation resulted in a limited gamma ray response. This response was significantly weaker than observed for the well-known commercial scintillator 0.02Ce:GAGG. Inefficient absorption of high-energy excitation or inadequate energy transfer to the activator ions in these materials are responsible for this relatively low scintillation performance. The second part of the thesis is focused on bilayer Ruddlesden-Popper nickelates. Single crystals of Sr3Ni2-xAlxO7-δ (SNAO) and its Y-substituted modification YᵧSr3-yNi2-xAlxO7-δ (YSNAO) have been grown by using strategically chemical substitutions and high oxygen pressure conditions to stabilize the RP phase. XRD and SC-XRD analysis confirmed the existence of the n = 2 RP-type structure by doping with Al, while thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) indicated successful oxygen incorporation and corresponding changes in the Ni oxidation state. Magnetic susceptibility measurements (SQUID magnetometry) have demonstrated the antiferromagnetic ordering transitions in these doped nickelate single crystals, and transport measurements have shown enhanced electrical conductivity compared to the undoped parent compound. In addition, a topochemical fluorination process has been investigated as a post-growth modification for n = 1 RP-type La2NiO4+δ single crystals. Fluorine has been introduced into the crystal lattice at moderate temperatures using polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and CuF2 as fluorination reagent. PTFE has been found to be the most effective fluorinating agent, resulting in partially fluorinated La2NiO4+δ with a diffusion-limited penetration pattern. EDX and EDX-mapping analyses have demonstrated an inhomogeneous F distribution, indicating that fluorine incorporation is limited by diffusion kinetics. This inhomogeneity should be carefully considered in future structural and functional analyses as it may affect the accurate characterisation of intrinsic properties in fluorinated crystals. In summary, the results of this thesis demonstrate the flexibility of the optical floating zone technique for the growth of high-quality functional oxides and show how structural stability, and functional properties can be modified using specific chemical doping approaches. To optimise scintillation performance in novel garnet-type hosts and to improve the magnetic and electronic behaviour of RP-type nickelates, the combined approach of crystal growth and post-growth modification could provide an additional parameter for material modification.
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    Synthesis and thermoelectric properties of chalcogenide and half-Heusler phases
    (2018) Zou, Tianhua; Weidenkaff, Anke (Prof. Dr.)
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    Atom probe study on CuNi thin films : miscibility gap and grain boundary segregation
    (2023) Duran, Rüya; Schmitz, Guido (Prof. Dr. Dr. h. c.)
    In dieser Arbeit wurde die Lage der Mischungslücke, und die Korngrenzsegregation im Legierungssystem, Kupfer-Nickel, per Atomsondentomographie (APT) analysiert. Zur Untersuchung der Mischungslücke eines binären Systems mit langsamer Diffusion wurde ein neues Verfahren verwendet. Multilagen aus Cu- und Ni- Dünnschichten wurden mittels Ionenstrahlbeschichtung (IBS) auf Wolframpfosten beschichtet und durch fokussierte Ionenstrahlung (FIB) geformt. Bei drei unterschiedlichen Temperaturen, zwischen 573 und 673 K, wurden isotherme Auslagerungssequenzen an einem Ultrahochvakuumofen (UHV) durchgeführt und der Mischungsprozess analysiert. Ein Modell des Diffusionsprozesses wurde mittels mathematischer Überlegungen erstellt. Durch das Fitten der experimentellen Kompositionsprofile mittels dieses Modells konnten die Gleichgewichtskonzentrationen der Schichten auch mit relativ kurzen Auslagerungszeiten ermittelt werden. Darüber hinaus konnten aus den diffusionskontrollierten Zeit- und Temperaturdaten physikalische Eigenschaften wie der effektive Diffusionskoeffizient (Gitterdiffusion einschließlich Defektdiffusion) bestimmt werden. Dieser betrug Deff = 1.86 ∙ 10-10 m2/s ∙ exp(-164 kJ mol-1/RT). Während dem Vermischen wurde die Änderung der multilagigen Mikrostruktur bis zur vollständigen Mischung bei 623 und 673 K beobachtet, wobei Korngrenzen als schneller Diffusionsweg eine wichtige Rolle spielen. Bei 573 K wurde Nichtmischbarkeit experimentell deutlich nachgewiesen, wobei die Phasengrenzen bei cNi=26 at.% und cNi=66 at.% liegen. Mit diesen Phasengrenzen wurde die Mischungslücke über eine Redlich-Kister-Parametrisierung der Gibbs‘schen freien Energie über den gesamten Konzentrationsbereich rekonstruiert. Hierin wurde für die kritische Temperatur, TC, 608 K bei einer Konzentration von 45 at% Ni gefunden. Im zweiten Teil wurde die Korngrenzsegregation durch die FIB/tEBSD- (Transmissions-Elektronen-Rückstreubeugung) Technik, in Korrelation zu APT-Messung charakterisiert. Vier Legierungen mit einem Ni-Anteil zwischen 25 und 85 at.% wurden auf Wolframpfosten per IBS beschichtet, und bei 700 K für 24 h wärmebehandelt. Die Segregation von Cu in die Korngrenzen wurde beobachtet. Durch die Verwendung eines theoretischen Models wurde die Exzess-Kurve über den gesamten Konzentrationsbereich, und die Korngrenz-Formationsenergie auf Basis der experimentellen Daten berechnet. Die tEBSD-Analyse während der FIB-Präparation erlaubt die Identifikation der Körner und deren Orientierung. Ein neues Verfahren wurde entwickelt, um mithilfe der Orientierung benachbarter Körner, Berechnungen zur Ermittlung der Korngrenzorientierung durchzuführen und somit die Orientierung natürlicher Korngrenzen zu bestimmen. Mit diesem Verfahren konnte der zeitliche Aufwand dieser anspruchsvollen Auswertung (verglichen zur herkömmlichen Methode mittels TEM-Untersuchung) stark reduziert werden, so dass eine quantitative Analyse vieler Korngrenzen möglich wurde. Aus den einzelnen Korngrenzorientierungen wurde die Korngrenzrotation, und die jeweiligen Anteile an Kippung und Drehung berechnet. Eine Abhängigkeit der Feststoffsegregation vom Kipp- und Drehanteil der Korngrenze wurde beobachtet, die am kleinsten für die reine Kipp- und Drehrotation war. Die ermittelten Segregationsweiten sind signifikant größer als die strukturellen Korngrenzweiten und bewegen sich zwischen 12 und 85 Å. Dieses Verhalten wurde durch eine künstliche Verbreiterung der Korngrenze erklärt, die durch eine Flugbahnabweichung der Korngrenzatome während der Verdampfung verursacht wurde. Eine Korngrenzweite von w0 = (10.1 ± 1.5) Å wurde für eine unverfälschte Korngrenze gefunden.
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    Atom probe reconstruction with a locally varying tip shape
    (2019) Beinke, Daniel; Schmitz, Guido (Prof. Dr. Dr. h.c.)
    In this thesis, a new approach for the reconstruction of data taken from an atom probe tomography experiment is presented. The goal of the study is to develop an algorithm, which is able to overcome well-known drawbacks of the conventional reconstruction technique, mainly caused by local magnification effects. At the same time, the algorithm should be easy to use and also fast enough, so that it might be routinely used as an improved alternative to the established reconstruction technique. The idea is based on the already existing possibility to simulate an entire atom probe experiment on a realistic length. Since the successive calculation of ion trajectories starting at the emitter surface and hitting the detector after a flight of a few centimeters can be realized, the concept is designed to invert the field evaporation process by making use of this trajectory calculation. To this end, the detected emitter volume needs to be rebuilt from the bottom to the top, which is an important difference compared to the conventional technique. In a first test, this inversion of the simulated experiment is demonstrated for a few prominent example cases. The decisive criterion for the positioning of an atom at a specific lattice site on the current emitter surface is the accordance of the impact position of the corresponding calculated trajectory with the measured coordinates on the detector. For every possible surface position, first an ion trajectory is calculated and its detector impact position is compared to the measured impact position. Finally, the best-matching trajectory defines the reconstruction coordinates. The approach is performed for some prominent example emitter structures with strongly varying evaporation fields of the involved material, which is known for causing tremendous artifacts in the reconstruction derived by the standard technique. In this first attempt, the algorithm is restricted to a rigid lattice, which means that detected atoms can only be positioned at sites belonging to the former lattice of the emitter. In a second step, the restriction to a rigid lattice is dropped. In this way, the reconstruction algorithm describes a more realistic scenario, since the exact lattice structure and its orientation might be unknown in the majority of experiments. The possibilities and limitations of the approach are discussed. It is found that an additional criterion for the determination of the reconstruction coordinates is needed in this case, since the algorithm is very sensitive to the misplacement of atoms. The stability can be significantly improved by the consideration of an inter-atomic potential, which acts as a filter that exclusively allows surface sites with a sufficiently high amount of neighbor atoms. For a perfect detector efficiency the algorithm yields promising results, but a decrease of the efficiency towards realistic values gives rise to artifacts. As a consequence of these numerical experiments, a new concept has been developed, which neglects the consideration of exact ion trajectories in order to make the algorithm more stable and fast. This third approach assumes rotational symmetry for the investigated emitter volume. An absolutely new characteristic of the technique is the capability to extract the shape of a field emitter directly from the observed pattern of ion impacts on the detector. This feature is a very important difference to the conventional technique, which assumes a constant spherical emitter shape. To the best of the authors knowledge, such a technique with this capability did not exist before. The promising features are demonstrated for several simulated but nevertheless realistic emitter structures. The improved quality of the reconstruction that can be achieved by the application of the here developed technique is shown by direct comparison to the result of the established reconstruction approach. The impressive benefits are illustrated for relevant emitter structures containing either precipitates or layers of different materials with strongly varying evaporation fields (44% or 56% relative variation). In addition, a simple modification of the technique is described, which yields homogenized atomic densities in the reconstructed volumes. Without this modification, the emitter surface is treated like a rigid curved plane, which is shifted upwards with every reconstructed atom during reconstruction. Once the surface is no longer considered to be rigid, individual parts can be lifted separately, yielding a significantly homogenized atomic density. Finally, the new concept of shape extraction is extended for the application to arbitrary emitter structures. The main idea of extracting the information about the emitter shape from the local density of measured events on the detector is maintained. In order to extend the approach to the application to structures without rotational symmetry, a relation between the local density of events on the detector and the Gaussian curvature on the emitter surface is derived. With the help of an iterative finite difference method, the Gaussian curvature at several positions on the tip surface is set. Consequently, a reasonable description of the emitter surface can be obtained and the reconstruction of an arbitrary data set can be performed. The concept is tested and discussed for a simulated example emitter structure.
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