Universität Stuttgart
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Item Open Access Spectroscopic investigations of the magnetic anisotropy of lanthanide- and cobalt-based molecular nanomagnets(2016) Rechkemmer, Yvonne; Slageren, Joris van (Prof. Dr.)Single-molecule magnets are metal complexes exhibiting an energy barrier for spin reversal, leading to magnetic bistability and slow relaxation of the magnetization. Their potential for practical applications such as high-density magnetic data storage was recognized early on and with the goal of achieving high energy barriers, different kinds of single-molecule magnets have been synthesized. The quadratic dependence of the barrier height on the spin motivated chemists to synthesize metal complexes with very high total spins; however, with limited success. It was shown that high spins come along with low anisotropies and increased interest thus focused on the synthesis and investigation of (mononuclear) complexes of highly anisotropic metal centers, e.g. lanthanide or cobalt complexes. Although rather high energy barriers can be achieved in such systems, practical application remains problematic and has not been realized yet. Reasons are for example the lack of rational design criteria and the complex interplay of different magnetic relaxation pathways. The aim of this work was therefore the comprehensive magnetic and spectroscopic investigation of selected molecular lanthanide and cobalt compounds in order to obtain a deeper insight into the correlation of molecular and electronic structures as well as the corresponding magnetic properties. The applied spectroscopic methods included electron paramagnetic resonance spectroscopy, far-infrared spectroscopy and optical methods. Special emphasis was placed on magnetic circular dichroism (MCD) spectroscopy, which served as a main tool for electronic structure determination. However, since the MCD-spectrometer was not part of the available experimental equipment at the University of Stuttgart, its design, setup and characterization were the first part of this work. In the further course of this work MCD-spectroscopy was employed for the electronic structure determination of selected lanthanide and cobalt compounds. The studied lanthanide compounds were literature-known molecular tetra-carbonates of erbium (1-Er) and dysprosium (1-Dy). Detailed magnetometric studies showed that both 1-Er and 1-Dy are field-induced single-molecule magnets; however, 1-Er and 1-Dy show significant differences in their magnetic relaxation behavior. The magnetic studies were complemented by detailed spectroscopic investigations.The combination of far-infrared-, luminescence- and MCD-spectroscopy allowed for the experimental determination of 48 energy levels for 1-Er and 55 levels for 1-Dy, which built the foundation for the subsequent crystal field analysis and electronic structure determination. In addition, the results of EPR-spectroscopic studies were used for fine-tuning and verifying the respectively determined crystal field parameters. Calculating the magnetic dipole strengths for transitions between the relevant states led to a quantitative understanding of the magnetic relaxation pathways. Besides the investigation of lanthanide compounds, this thesis deals with two classes of cobalt complexes. The first class comprises mononuclear complexes in which one Co(II) ion is ligated by the nitrogen donors of two doubly deprotonated 1,2-bis(methanesulfonamido)-benzene-ligands. Rather acute N-Co-N bite angles indicate strong deviations from ideal tetrahedral symmetry. The static magnetic properties hint at very high energy barriers for spin reversal and with the help of far-infrared spectroscopy, largely negative axial zero-field splitting parameters were determined. The corresponding energy barriers belong to the highest ever reported for 3d-transition metal complexes and investigating the dynamic magnetic properties confirmed single-molecule magnet behavior. The unique magnetic properties were fully explained by analyzing spectroscopic results. The MCD-spectra showed intense signals that were assigned to spin-allowed d-d-transitions. Subsequent crystal field analysis revealed that the strong axial crystal field generated by the ligands leads to a large splitting of the electronic terms and thus in turn to a relatively small energy gap between the electronic ground state and the first excited state. The resulting increase in second-order spin-orbit coupling explains the high energy barriers observed in the studied complexes. The second class of cobalt compounds studied in this work included dimers of distorted octahedrally coordinated Co(II) ions bridged by symmetrical or asymmetrical quinone based bridging ligands. The main focus of investigation lay on the impact of the bridging ligand on the magnetic coupling between the cobalt centers. Thus, the magnetic properties of the complexes were studied with the help of static susceptibility and magnetization measurements and analyzed by means of different models. Depending on the bridging ligand, different signs for the exchange coupling constants were found. The varying signs can be explained by different relative contributions of possible exchange paths, influenced by the different substituents at the bridging ligands or slight geometry differences. The observations indicate that electron withdrawing substituents favor ferromagnetic couplings, which are preferred in the context of molecular magnetism. All in all, it can be concluded that this work provides a contribution to the deeper understanding of the features relevant for single-molecule magnets. The electronic structure determination for selected lanthanide and cobalt complexes applying advanced magnetometric and spectroscopic techniques not only led to an understanding of the static and dynamic magnetic properties but also allowed for the development of design criteria and new approaches for improved single-molecule magnets in the future.Item Open Access Präzise Fahrzeugpositionierung durch Entzerrung der gepulsten magnetischen Flussdichteverteilung einer Ladespule(2017) Martinovic, Dean; Reuss, Hans-Christian (Prof. Dr.-Ing.)Elektrofahrzeuge werden in Zukunft nicht mehr per Kabel, sondern mittels induktiver Ladesysteme mit Strom versorgt. Um eine hohe Ladeleistung sicher übertragen zu können, müssen die Spulen hinreichend genau übereinander positioniert werden, was für den Fahrer eine kaum lösbare Aufgabe darstellt. Das allgemeine Ziel der vorliegenden Arbeit ist es daher, eine neue Methode zu untersuchen, die ein gepulstes Magnetfeld der Ladespule zu dessen Ortung nutzt. Hierbei wird das magnetische Pulssignal durch den ferromagnetischen Unterboden des Elektrofahrzeugs verzerrt. Dieser verändert die Pulsamplitude entsprechend einer unbekannten Abbildung, ohne deren Kenntnis eine präzise und eindeutige Positionierung nicht möglich ist. Die Herausforderung der vorliegenden Arbeit ist daher die Bestimmung dieser Abbildung samt ihrer Eigenschaften und Abhängigkeiten. Theoretische Untersuchungen zeigen, dass die Abbildung allgemein vom nicht-deterministischen magnetischen Zustand des Unterbodenmaterials abhängt und dessen messtechnische Erfassung kaum möglich ist. Im weiteren Verlauf der Untersuchungen wird jedoch hergeleitet, dass die Ladespule, das Elektrofahrzeug und die umgebende Atmosphäre zusammen einen magnetischen Kreis bilden, der aufgrund der sehr hohen Reluktanz der Atmosphäre linear ist. Änderungen des magnetischen Zustands haben folglich keinen Einfluss auf die Abbildung. Diese ist somit reproduzierbar und kann messtechnisch einfach erfasst werden. Die These wird für unterschiedliche magnetische Zustände experimentell nachgewiesen. Basierend auf den Forschungsergebnissen wird ein vollständiger Prototyp entwickelt und in ein Versuchsfahrzeug integriert. Das Gesamtsystem wird anschließend erfolgreich getestet. Die gefundenen Ergebnisse zeigen, dass mittels gepulster magnetischer Felder eine universelle, kostengünstige, sichere und präzise Positionierung von Elektrofahrzeugen möglich ist. Dies unterstreicht das Potential des neuen, komfortablen Positionierungsverfahrens eine Schlüsseltechnologie für die Elektromobilität zu werden.Item Open Access Chiral metamaterials(2016) Eslami, Sahand; Fischer, Peer (Prof. Dr.)Item Open Access Ion beam lithographic and multilayer fresnel zone plates for soft and hard X-rays: nanofabrication and characterization(2015) Keskinbora, Kahraman; Schütz, Gisela (Prof. Dr.)X-ray microscopy has become an important analytical characterization method for a plethora of applications in materials science, physics, chemistry and biology, thanks to the emergence of modern synchrotron radiation facilities. These facilities enable high brilliance, energy tunable, variable polarization X-rays which gives access to mass density, elemental, chemical, electronic and magnetic properties of materials. In the soft X-ray energies nearly all elements can be probed by spectromicroscopic methods. Another important property of synchrotron radiation is the time structure in the ns to ps range, which can be utilized for sophisticated time resolution studies. These opportunities can be combined with high spatial resolution which is determined by the focusing method and the optic. Focusing of X-rays has historically been a difficult task due to strong absorption and weak phase shift of X-rays within matter. The required phase shift of X-rays, which depends on the real part of the complex refractive index, differs from 1 (the vacuum refractive index) only on the order of 10^-2 to 10^-6 and conventional lenses do not work. One very successful X-ray optic is the Fresnel Zone Plate (FZP), a diffractive optic that act as a lens under certain conditions and can focus X-rays to nanometer sized spots. The resolution of the FZP depends on the width of the outermost zone and is highly correlated with the smallest feature that can be fabricated. Conventionally, the e-beam lithography (EBL) is used for production FZPs which could resolve up to 10 nm structures with serious limitations. One difficulty of EBL is its ever increasing complexity for many-step fabrication of smaller features or intricate geometries. Therefore, EBL is mostly constrained to planar, binary geometries with moderate efficiencies strongly decreasing with energy and not effective for hard X-rays. Special 3D geometries in the form of kinoform lenses can theoretically have 100 % focusing efficiencies. Attempts to approximate these geometries via EBL increased the number of process steps even further. The smallest FZP feature size even for low aspect ratios achievable via EBL is fundamentally limited due to the proximity effect which is the interaction and spread of electrons within the resist material. We addressed these issues by focusing our research on alternative FZP fabrication techniques as high-speed ion beam lithography (IBL), and gray scale ion lithography to realize efficient kinoforms. Another approach towards full-material multilayer FZPs with infinite aspect ratio was based on atomic layer deposition (ALD) with subsequent ion beam slicing. Each of these three methods targets specific challenges faced by the e-beam lithography based FZP fabrication techniques. All the fabricated FZPs were tested for their resolution and efficiency performances at a state of the art scanning transmission X-ray microscope at BESSY for soft X-rays and/or at optical test stations at ESRF and PETRA III for hard X-rays. Using IBL the rapid preparation of a 110 nm thick Au FZP with 50 µm diameter and 50 nm ∆r in less than 13 minutes is demonstrated. Employed for X-ray microscopy, the FZP clearly resolved 28.5 nm features with a cut-off of 24.3 nm at ~1120 eV. Additional process improvements were made towards smaller zones with higher zone quality. They allowed the preparation of a FZP with 30 nm outermost half-period remarkably, in about 8 min. This FZP was shown to clearly resolve 21 nm features on a multilayer test object with large room for improvement. This high through-put FZP production route is of special interest not only concerning the low cost and easy availability. A large array of these optical components is attractive, for experiments such as one-shot ultra-high brilliance FEL investigations due to the radiation damage or for instance for coded-aperture arrays for high-angle resolving X-ray astronomy. Towards fabrication of kinoforms for high efficiency X-ray focusing, we have performed various materials optimization studies in order to achieve a high surface quality optic. After various trials the materials were finally optimized and the fabricated lenses achieved more than 14 % absolute diffraction efficiency that is almost 90 % compared to the theoretical prediction. This confirms how closely we were able to replicate the ideal three dimensional surface relief structure for the first time. It was possible to carry out imaging with these lenses with half-pitch resolutions down to 60 nm. The kinoform lenses were tested at the soft X-ray range where a significant absorption is present in materials. These results also potentially pave the way for very high efficiency hard X-ray focusing which can in principle be utilized in laboratory based X-ray sources, X-ray astronomy and the new rising field of X-ray ptychography. To fabricate high resolution ML-FZPs, Al2O3/Ta2O5multilayers, deposited on a smooth glass optical fiber via atomic layer deposition using non-dedicated instruments were carefully cut-out, sliced and polished to a high quality surface finish using focused ion beams. Following the transfer of the slice to a TEM grid as holder the slices were polished to a high surface finish quality, also via a focused ion beam. Fabricated ML-FZPs were synchrotron tested using an in-house constructed 2-axis tilt stage specially designed for aligning ML-FZP with respect to the X-ray optical axis. The results showed that it was possible to resolve 21 nm features in direct imaging at 1200 eV and sub-30 nm focusing at 8 keV. This is the highest demonstrated resolving power for a multilayer type FZP, to date to the best of our knowledge. Results exhibit the potential for high-resolution hard X-ray focusing where this type of optics are especially efficient. For ultra-high resolution hard and soft X-ray imaging, with potentially achievable ∆r of a few nm is well below what can be achieved through any lithography method available today.Item Open Access Diagnostik und Modellierung eines Mikrowellen-Plasmabrenners bei Atmosphärendruck(2017) Gaiser, Sandra; Hirth, Thomas (Prof. Dr.)Mikrowellen-Plasmaprozesse bei Atmosphärendruck bieten eine Vielzahl von Anwendungsmöglichkeiten. Dazu gehören das Plasmaspritzen zur Beschichtung, die Behandlung von Oberflächen für die Reinigung oder Aktivierung sowie der Abbau schädlicher Abgase. Für die Entwicklung und Optimierung dieser Verfahren sind sowohl experimentelle Untersuchungen als auch eine theoretische Betrachtung von Bedeutung. Diese Arbeit beschäftigt sich deshalb neben der Diagnostik vor allem mit der Modellierung und numerischen Simulation eines bei Atmosphärendruck betriebenen Mikrowellen-Plasmabrenners. Dazu wird die Simulationssoftware Comsol Multiphysics verwendet. Das Ziel ist es, mittels einzelner Modelle die unterschiedlichen physikalischen Vorgänge zu beschreiben und das Brennersystem zu optimieren. Die Simulationen werden schließlich schrittweise miteinander verknüpft, um so ein möglichst selbstkonsistentes Modell der Plasmaquelle zu erhalten. Die Simulationsergebnisse werden zudem mit experimentellen Daten verglichen. Zunächst werden die Verteilung des Mikrowellenfeldes im Plasmabrenner sowie die Resonanzfrequenzen der Resonatoranordnung berechnet, was die Grundlage für eine zuverlässige Zündung und den Betrieb des Plasmas bildet. Anschließend wird ein Modell der kalten Gasströmung erstellt. In dieses wird schließlich eine Wärmequelle implementiert, um den Einfluss des heißen Plasmas auf die Strömung zu untersuchen. Die Gasströmung soll dahingehend optimiert werden, dass sie das Plasma einschließt, um so eine Beschädigung des Gas führenden Quarzrohres zu vermeiden. In einer weiteren Simulation wird das Plasma mit Hilfe des Drude-Modells beschrieben. Hierbei werden dem Plasma eine Permittivität und eine Leitfähigkeit zugewiesen. Eine Erweiterung erfolgt durch das Fluid-Modell, das Bilanzgleichungen für die Elektronendichte sowie Reaktionsmechanismen für ein Argon-Plasma enthält. Die Simulationsergebnisse werden durch den Vergleich mit experimentellen Ergebnissen verifiziert. Dazu wird zum einen die räumliche Lage des Plasmas mit Hilfe von Kameraaufnahmen qualitativ untersucht. Zum anderen stehen Messwerte aus der optischen Emissionsspektroskopie zur Verfügung.Item Open Access Rydberg polaritons and Rydberg superatoms - novel tools for quantum nonlinear optics(2017) Tresp, Christoph; Hofferberth, Sebastian (Dr.)Item Open Access Charakterisierung von Kohlendioxid-Plasmaströmungen zur Simulation von Marseintrittsmanövern(2017) Marynowski, Thomas; Fasoulas, Stefanos (Prof. Dr.-Ing.)Das Thema dieser Arbeit ist die Charakterisierung von CO2-Plasmaströmungen, die die Simulation von Eintrittsmanövern an Planeten ermöglichen. Die Planeten Venus und Mars besitzen eine von CO2 dominierte Atmosphäre und besonders unser direkter Nachbarplanet Mars steht momentan im Fokus aktueller explorativer Missionen. Für eine sicherere und umfangreichere Erkundung der Planeten sind effiziente Technologien erforderlich. Dabei spielen Hitzeschutzmaterialien (engl. Thermal Protection Systems, TPS) eine wichtige Rolle, denn sie ermöglichen erst die Eintrittsmanöver und machen einen erheblichen Masseanteil der Raumfahrzeuge aus. Durch Verbesserung und effizienteren Einsatz der Hitzeschutzmaterialien kann der Nutzlastanteil gesteigert und durch Erhöhung der Sicherheit die Erfolgschancen der Missionen verbessert werden. Das Testen und die Weiterentwicklung solcher Hitzeschutzmaterialien sind mit Hilfe des induktiven Plasmagenerators IPG4 am Plasmawindkanal PWK3 möglich. Die Voraussetzung für solche Tests ist die Kenntnis der wichtigsten Parameter des Freistrahls. Die Messung der Parameter wird mit zwei unterschiedlichen Gruppen von Messmethoden durchgeführt. Als Teil der nicht intrusiven Messmethoden und Schwerpunkt dieser Arbeit wird die laserspektroskopische Methode der Zwei-Photonen laserinduzierten Fluoreszenz (engl. Two-Photon Absorption Laser-Induced Fluorescence, TALIF) eingesetzt. Damit wird zum ersten Mal bei Eintrittsbedingungen in einem induktiv geheizten CO2-Plasma die Grundzustandsdichte von Sauerstoff, als eines der wichtigsten Dissoziationsprodukte einer CO2-Strömung, gemessen. Absolute Aussagen (Grundzustandsdichte, translatorische Temperatur und Geschwindigkeit) über den atomaren Sauerstoff werden durch Messungen an Xenon ermöglicht, das einen passenden Zweiphotonenübergang besitzt und so zur Kalibrierung benutzt werden kann. Zur Erweiterung der Charakterisierung werden auch weitere Messmethoden genutzt. Die optische Emissionsspektroskopie (OES) und ein Hochgeschwindigkeitskamerasystem (HSC) werden als weitere nicht intrusive Diagnostiken eingesetzt. OES ermöglicht die Identifizierung der vorkommenden Spezies sowie die Bestimmung von Vibrations-, Rotations- und elektronischen Anregungstemperaturen. Die Daten der Hochgeschwindigkeitsaufnahmen geben orts- und zeitaufgelöste Informationen über Emissionsverteilungen einzelner identifizierter Spezies in der Strömung, was durch den Einsatz von schmalbandigen Spektralfiltern erreicht wird. Darüber hinaus werden intrusive, also in die Strömung gebrachte, Sonden verwendet, um Totaldruck, Wärmestromdichte und massenspezifische Enthalpie zu messen. Die massenspezifische Enthalpie wird dabei auf zwei unterschiedliche Weisen ermittelt. Dazu wird einerseits eine spezielle Enthalpiesonde und andererseits ein indirekter semiempirischer Ansatz, der sich auf die Messung von Totaldruck und Wärmestromdichte sowie eine benötigte Konstante stützt, verwendet. Durch die Sondenmessung der massenspezifischen Enthalpie ist es möglich, die Konstante aus den Daten dieser Arbeit, durch eine Rückrechnung neu zu ermitteln und mit der Literatur zu vergleichen. Insgesamt geben die Ergebnisse Aufschluss über wichtige Parameter der Strömung wie Geschwindigkeit, Temperaturen, Teilchendichte, Totaldruck, Wärmestromdichte und massenspezifische Enthalpie. Weiter sind über die identifizierten Atome und Moleküle Aussagen über die chemische Zusammensetzung der Strömung möglich, wodurch Betrachtungen des thermo-chemischen Zustandes der Plasmaströmung ermöglicht werden. Für die supersonische Strömung zeichnet sich das Bild eines Nichtgleichgewichtszustandes, das im Einzelnen (chemisch und thermisch) betrachtet wird. Es wird ein Vergleich der vorliegenden Strömungsdaten zu Daten der vergangenen erfolgreichen Marsmissionen sowie weltweit anderer Bodentestanlagen dargestellt. Dabei wird gezeigt, dass der Plasmawindkanal PWK3 mit dem induktiven Plasmagenerator IPG4 in der Lage ist, die Wärmestromdichte und die massenspezifische Enthalpie der bisherigen Eintrittsmissionen im vollen Umfang zu reproduzieren, jedoch der Totaldruck nur auf die frühen Phasen der Eintrittstrajektorien beschränkt simulierbar bleibt. Das Ergebnis dieser Arbeit ist eine sehr gut charakterisierte CO2-Plasmaströmung, die zur Erprobung von Hitzeschutzmaterialien für zukünftige Flüge zum Mars und der Venus verwendet werden kann.Item Open Access 3D printing of sub-micrometer accurate ultra-compact free-form optics(2016) Gissibl, Timo; Giessen, Harald (Prof. Dr.)Additive manufacturing enables novel and unprecedented engineering and production possibilities, which are predicted to have an enormous impact in the 21st century. The technology allows for the straightforward three-dimensional printing of volumetric objects as designed. In this thesis, we present a novel concept in optics, which overcomes many difficulties in the fabrication of micro-optics and opens the new field of 3D printed micro- and nano-optics with complex lens designs. Our work is just at the interface between micro- and nano-optics and represents a paradigm shift for micro-optics. It takes only a few hours from lens design, to production, testing, and the final working optical device. Using dip-in femtosecond two-photon direct laser writing, our method goes far beyond state-of-the art attempts to manufacture simple micro-lenses by lithography. We prove the versatility of this method by writing different optics. Collimation optics, toric lenses, free-form surfaces with polynomials of up to 10th order for intensity beam shaping, as well as chiral photonic crystals for circular polarization filtering, all aligned onto the core of single mode fibers are shown. In addition, we show that three-dimensional direct laser writing is a suitable tool for the fabrication of complex multi-lens optical systems that show high quality optical imaging, beam shaping performance, and tremendous compactness with sizes below 300 µm. We determine the accuracy of our optics by analyzing the imaging and beam shaping quality as well as characterizing the surfaces by atomic force microscope measurements and interferometric measurements. The method yields high fabrication accuracy and allows to manufacture of lenses with a rms (root mean square) surface roughness of less than 15 nm. The surfaces deviate from their designs by less than ±1 µm. Our 3D printed compound lenses feature resolving powers of up to 500 line pairs per millimeter. Our printed micro-optical elements can thus achieve sufficient performance in order to enable compound lenses for high quality imaging. In addition, we show the performance of diffractive optical elements with diameters of just 4.4 µm, which enable beam shaping at the end facet of an optical fiber. The intensity is shaped into a uniform or into a donut-shaped intensity distribution. For this purpose, the diffractive optics are directly fabricated onto the end facet of the optical fiber and show unprecedented performance for optical beam shaping. Our method allows for a plethora of novel applications with tremendous impact on optical trapping of atoms and in-vivo imaging in the human body. In addition, applications for imaging and illumination in endoscopy, multiple sensors, and eyes for micro-robots can be realized.Item Open Access In situ characterization of phase evolution in LiFePO4(2015) Ohmer, Nils; Maier, Joachim (Prof. Dr.)Among the candidates for electrodes in future Li-based batteries, LiFePO4 (LFP) is one of the most important and most frequently studied materials, undergoing a phase transformation upon delithiation to FePO4 (FP). In spite of the great scientific and practical interest in this material, there is still an extensive debate on the mechanism of this phase transformation and the underlying factors of influence. Within the framework of this thesis, first studies are carried out ex situ on multi-particle, full electrode LFP materials, being electrochemically cycled and analyzed at various states of charge by a combination of highly spatially resolved methods (high-resolution transmission electron microscopy and electron energy loss spectroscopy (HRTEM, EELS)) and integral measurement techniques (analyzing the X-ray diffraction and X-ray absorption near edge structure (XRD, XANES)). This combination of characterization techniques allows one to distinguish between the cycling behaviour of differently sized crystallites within the same electrode. It is found that for electrodes with hydrothermally grown LFP as active material, a particle size dependent cycling behaviour exists, with nanosized particles apparently not participating in the charging process at all. A turbostratic stacking of layers in these nanosized particles is found and identified to be responsible for sluggish lithium insertion and extraction. These higher dimensional defects prevent the small particles from participating in the charging process, most likely by disturbing the lithium diffusion along the 1-dimensional channels, as well as impair the transport along the other directions in the LFP host structure and thus blocking the lithium transport, resulting in a comparibly lower practical capacity during electrochemical cycling. To study the lithium exchange mechanism upon charging a LFP thin film cathode, an all-solid-state thin film battery cell with a lateral design concept is developed and realized by pulsed laser deposition (PLD) and thermal evaporation techniques. Using PLD and shadow masks LFP cathode, Li2O-V2O5-SiO2 (LVSO) electrolyte and LiAl anode thin films are deposited sequentially in a way that the Li transport pathway in the resulting battery is along the X-ray transparent commercial Si3N4 membrane substrate. This enables the usability of synchrotron-based energy resolved scanning transmission X-ray microscopy (STXM) with its high chemical and spatial resolution to perform in situ absorption measurements at the Fe L3 edge. Upon delithiation, a shift in the main absorption feature from 708 to 710 eV is used to fingerprint the change in the local state of charge, identifying areas containing Fe2+ (lithiated) and Fe3+ (delithiated), respectively. The initial lithiation process of a LFP thin film cathode material has been followed by in situ STXM, with a lateral resolution of 30 nm, during electrochemical charging of the thin film battery. The observed initial lithiation process does not follow the classical particle by particle mechanism, typical for multi-particle LFP cathodes, but instead a rather simultaneous, although inhomogeneous, lithiation is observed. The reason for this change in mechanism, compared to multi-particle powder electrodes, is found in mechanical interactions within the thin film upon lithiation, i.e. in the corresponding volume expansion and formation of high energy surfaces, changing the shape of the single-particle chemical potential to a monotone form upon lithiation. This has far-reaching consequences: not only the many-particle mechanism is changed to a concurrent lithiation, but also the single-particle mechanism is changed from a two-phase to a single-phase mechanism upon lithiation. Furthermore, a vanishing hysteresis loop and the disappearing of the memory effect is predicted. These findings are rather general and applicable to all kind of thin films of phase separating intercalation materials, undergoing a volume change upon lithium exchange. To fill the gap in literature on in situ observations of the (L)FP phase evolution on a single-particle level with appreciable space and time resolution, a micrometer-sized all-solid-state thin film battery is built with a defect-chemically well characterized LFP single crystal as cathode material with dimensions of 16x1x0.2 micrometer. Using STXM, the phase evolution along the fast (010) orientation is followed during in situ electrochemical (de)lithiation on a micro-meter scale with a lateral resolution of 30 nm and with minutes of time resolution. Furthermore, the STXM measurements performed on this sample are one of the few experiments ever taken on LFP materials with a well defined defect chemistry, even though fundamentally necessary for an overall understanding of the materials behaviour. This combination discloses not only the mechanism of LFP transformation on a single-particle level, but also the significance of elastic effects on the (de)lithiation process. Using a defect chemical analysis, the position of phase formation is found to be determined by the defect chemical situation, while the growth pattern of both LFP and FP is found to be dominated by elastic effects.Item Open Access Linear & nonlinear plasmonic sensing : complex coupled plasmonic structures, functionalization, and nonlinear effects(2016) Mesch, Martin; Giessen, Harald (Prof. Dr.)