@phdthesis{Sapei2007, author = {Sapei, Lanny}, title = {Characterisation of silica in Equisetum hyemale and its transformation into biomorphous ceramics}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-15883}, school = {Universit{\"a}t Potsdam}, year = {2007}, abstract = {Equisetum spp. (horsetail / "Schachtelhalm") is the only surviving genus of the primitive Sphenopsids vascular plants which reached their zenith during the Carboniferous era. It is an herbaceous plant and is distinguished by jointed stems with fused whorl of nodal leaves. The plant has been used for scouring kitchen utensils and polishing wood during the past time due to its high silica encrustations in the epidermis. Equisetum hyemale (scouring rush) can accumulate silica up to 16\% dry weight in its tissue, which makes this plant an interesting candidate as a renewable resource of silica for the synthesis of biomorphous ceramics. The thesis comprises a comprehensive experimental study of silica accumulations in E.hyemale using different characterisation techniques at all hierarchical levels. The obtained results shed light on the local distribution, chemical form, crystallinity, and nanostructure of biogenic silica in E.hyemale which were quite unclear until now. Furthermore, isolation of biogenic silica from E.hyemale to obtain high grade mesoporous silica with high purity is investigated. Finally, syntheses of silicon carbide (b-SiC) by a direct thermoconversion process of E.hyemale is attempted, which is a promising material for high performance ceramics. It is found that silica is deposited continuously on the entire epidermal layer with the highest concentration on the knobs. The highest silicon content is at the knob tips (≈ 33\%), followed by epidermal flank (≈ 17\%), and inner lower knob (≈ 6\%), whereas there is almost no silicon found in the interior parts. Raman spectroscopy reveals the presence of at least two silica modifications in E.hyemale. The first type is pure hydrated amorphous silica restricted to the knob tips. The second type is accumulated on the entire continuous outer layer adjacent to the epidermis cell walls. It is lacking silanol groups and is intimately associated with polysaccharides (cellulose, hemicellulose, pectin) and inorganic compounds. Silica deposited in E.hyemale is found to be mostly amorphous with almost negligible amounts of crystalline silica in the form of a-quartz (< 7\%). The silica primary particles have a plate-like shape with a thickness of about 2 nm. Pure mesoporous amorphous silica with an open surface area up to 400 m2/g can be obtained from E.hyemale after leaching the plant with HCl to remove the inorganic impurities followed by a calcination treatment. The optimum calcination temperature appears to be around 500°C. Calcination of untreated E.hyemale causes a collapse of the biogenic silica structure which is mainly attributed to the detrimental action of alkali ions present in the native plant. Finally, pure b-SiC with a surface area of about 12 m2/g is obtained upon direct pyrolysis of HCl-treated E.hyemale samples in argon atmosphere. The original structure of native E.hyemale is substantially retained in the biomorphous b-SiC. The results of this thesis lead to a better understanding of the silicification process and allow to draw conclusions about the role of silica in E.hyemale. In particular, a templating role of the plant biopolymers for the synthesis of the nanostructured silica within the plant body can be deduced. Moreover, the high grade ultrafine amorphous silica isolated from E.hyemale promises applications as adsorbent and catalyst support and as silica source for the fabrication of silica-based composites. The synthesis of biomorphous b-SiC from sustainable and low-cost E.hyemale is still in its initial stage. The present thesis demonstrates the principal possibility of carbothermal synthesis of SiC from E.hyemale with the prospect of potential applications, for instance as refractory materials, catalyst supports, or high performance advanced ceramics.}, language = {en} } @phdthesis{Widdrat2014, author = {Widdrat, Marc}, title = {Formation and alteration of magnetite nanoparticles}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-72239}, school = {Universit{\"a}t Potsdam}, pages = {113}, year = {2014}, abstract = {Magnetite is an iron oxide, which is ubiquitous in rocks and is usually deposited as small nanoparticulate matter among other rock material. It differs from most other iron oxides because it contains divalent and trivalent iron. Consequently, it has a special crystal structure and unique magnetic properties. These properties are used for paleoclimatic reconstructions where naturally occurring magnetite helps understanding former geological ages. Further on, magnetic properties are used in bio- and nanotechnological applications -synthetic magnetite serves as a contrast agent in MRI, is exploited in biosensing, hyperthermia or is used in storage media. Magnetic properties are strongly size-dependent and achieving size control under preferably mild synthesis conditions is of interest in order to obtain particles with required properties. By using a custom-made setup, it was possible to synthesize stable single domain magnetite nanoparticles with the co-precipitation method. Furthermore, it was shown that magnetite formation is temperature-dependent, resulting in larger particles at higher temperatures. However, mechanistic approaches about the details are incomplete. Formation of magnetite from solution was shown to occur from nanoparticulate matter rather than solvated ions. The theoretical framework of such processes has only started to be described, partly due to the lack of kinetic or thermodynamic data. Synthesis of magnetite nanoparticles at different temperatures was performed and the Arrhenius plot was used determine an activation energy for crystal growth of 28.4 kJ mol-1, which led to the conclusion that nanoparticle diffusion is the rate-determining step. Furthermore, a study of the alteration of magnetite particles of different sizes as a function of their storage conditions is presented. The magnetic properties depend not only on particle size but also depend on the structure of the oxide, because magnetite oxidizes to maghemite under environmental conditions. The dynamics of this process have not been well described. Smaller nanoparticles are shown to oxidize more rapidly than larger ones and the lower the storage temperature, the lower the measured oxidation. In addition, the magnetic properties of the altered particles are not decreased dramatically, thus suggesting that this alteration will not impact the use of such nanoparticles as medical carriers. Finally, the effect of biological additives on magnetite formation was investigated. Magnetotactic bacteria¬¬ are able to synthesize and align magnetite nanoparticles of well-defined size and morphology due to the involvement of special proteins with specific binding properties. Based on this model of morphology control, phage display experiments were performed to determine peptide sequences that preferably bind to (111)-magnetite faces. The aim was to control the shape of magnetite nanoparticles during the formation. Magnetotactic bacteria are also able to control the intracellular redox potential with proteins called magnetochromes. MamP is such a protein and its oxidizing nature was studied in vitro via biomimetic magnetite formation experiments based on ferrous ions. Magnetite and further trivalent oxides were found. This work helps understanding basic mechanisms of magnetite formation and gives insight into non-classical crystal growth. In addition, it is shown that alteration of magnetite nanoparticles is mainly based on oxidation to maghemite and does not significantly influence the magnetic properties. Finally, biomimetic experiments help understanding the role of MamP within the bacteria and furthermore, a first step was performed to achieve morphology control in magnetite formation via co-precipitation.}, language = {en} } @phdthesis{TchoumbaKwamen2018, author = {Tchoumba Kwamen, Christelle Larodia}, title = {Investigating the dynamics of polarization reversal in ferroelectric thin films by time-resolved X-ray diffraction}, doi = {10.25932/publishup-42781}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-427815}, school = {Universit{\"a}t Potsdam}, pages = {xvii, 126, xxiii}, year = {2018}, abstract = {Ferroic materials have attracted a lot of attention over the years due to their wide range of applications in sensors, actuators, and memory devices. Their technological applications originate from their unique properties such as ferroelectricity and piezoelectricity. In order to optimize these materials, it is necessary to understand the coupling between their nanoscale structure and transient response, which are related to the atomic structure of the unit cell. In this thesis, synchrotron X-ray diffraction is used to investigate the structure of ferroelectric thin film capacitors during application of a periodic electric field. Combining electrical measurements with time-resolved X-ray diffraction on a working device allows for visualization of the interplay between charge flow and structural motion. This constitutes the core of this work. The first part of this thesis discusses the electrical and structural dynamics of a ferroelectric Pt/Pb(Zr0.2,Ti0.8)O3/SrRuO3 heterostructure during charging, discharging, and polarization reversal. After polarization reversal a non-linear piezoelectric response develops on a much longer time scale than the RC time constant of the device. The reversal process is inhomogeneous and induces a transient disordered domain state. The structural dynamics under sub-coercive field conditions show that this disordered domain state can be remanent and can be erased with an appropriate voltage pulse sequence. The frequency-dependent dynamic characterization of a Pb(Zr0.52,Ti0.48)O3 layer, at the morphotropic phase boundary, shows that at high frequency, the limited domain wall velocity causes a phase lag between the applied field and both the structural and electrical responses. An external modification of the RC time constant of the measurement delays the switching current and widens the electromechanical hysteresis loop while achieving a higher compressive piezoelectric strain within the crystal. In the second part of this thesis, time-resolved reciprocal space maps of multiferroic BiFeO3 thin films were measured to identify the domain structure and investigate the development of an inhomogeneous piezoelectric response during the polarization reversal. The presence of 109° domains is evidenced by the splitting of the Bragg peak. The last part of this work investigates the effect of an optically excited ultrafast strain or heat pulse propagating through a ferroelectric BaTiO3 layer, where we observed an additional current response due to the laser pulse excitation of the metallic bottom electrode of the heterostructure.}, language = {en} } @phdthesis{vonReppert2021, author = {von Reppert, Alexander}, title = {Magnetic strain contributions in laser-excited metals studied by time-resolved X-ray diffraction}, doi = {10.25932/publishup-53558}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-535582}, school = {Universit{\"a}t Potsdam}, pages = {XV, 311}, year = {2021}, abstract = {In this work I explore the impact of magnetic order on the laser-induced ultrafast strain response of metals. Few experiments with femto- or picosecond time-resolution have so far investigated magnetic stresses. This is contrasted by the industrial usage of magnetic invar materials or magnetostrictive transducers for ultrasound generation, which already utilize magnetostrictive stresses in the low frequency regime. In the reported experiments I investigate how the energy deposition by the absorption of femtosecond laser pulses in thin metal films leads to an ultrafast stress generation. I utilize that this stress drives an expansion that emits nanoscopic strain pulses, so called hypersound, into adjacent layers. Both the expansion and the strain pulses change the average inter-atomic distance in the sample, which can be tracked with sub-picosecond time resolution using an X-ray diffraction setup at a laser-driven Plasma X-ray source. Ultrafast X-ray diffraction can also be applied to buried layers within heterostructures that cannot be accessed by optical methods, which exhibit a limited penetration into metals. The reconstruction of the initial energy transfer processes from the shape of the strain pulse in buried detection layers represents a contribution of this work to the field of picosecond ultrasonics. A central point for the analysis of the experiments is the direct link between the deposited energy density in the nano-structures and the resulting stress on the crystal lattice. The underlying thermodynamical concept of a Gr{\"u}neisen parameter provides the theoretical framework for my work. I demonstrate how the Gr{\"u}neisen principle can be used for the interpretation of the strain response on ultrafast timescales in various materials and that it can be extended to describe magnetic stresses. The class of heavy rare-earth elements exhibits especially large magnetostriction effects, which can even lead to an unconventional contraction of the laser-excited transducer material. Such a dominant contribution of the magnetic stress to the motion of atoms has not been demonstrated previously. The observed rise time of the magnetic stress contribution in Dysprosium is identical to the decrease in the helical spin-order, that has been found previously using time-resolved resonant X-ray diffraction. This indicates that the strength of the magnetic stress can be used as a proxy of the underlying magnetic order. Such magnetostriction measurements are applicable even in case of antiparallel or non-collinear alignment of the magnetic moments and a vanishing magnetization. The strain response of metal films is usually determined by the pressure of electrons and lattice vibrations. I have developed a versatile two-pulse excitation routine that can be used to extract the magnetic contribution to the strain response even if systematic measurements above and below the magnetic ordering temperature are not feasible. A first laser pulse leads to a partial ultrafast demagnetization so that the amplitude and shape of the strain response triggered by the second pulse depends on the remaining magnetic order. With this method I could identify a strongly anisotropic magnetic stress contribution in the magnetic data storage material iron-platinum and identify the recovery of the magnetic order by the variation of the pulse-to-pulse delay. The stark contrast of the expansion of iron-platinum nanograins and thin films shows that the different constraints for the in-plane expansion have a strong influence on the out-of-plane expansion, due to the Poisson effect. I show how such transverse strain contributions need to be accounted for when interpreting the ultrafast out-of-plane strain response using thermal expansion coefficients obtained in near equilibrium conditions. This work contributes an investigation of magnetostriction on ultrafast timescales to the literature of magnetic effects in materials. It develops a method to extract spatial and temporal varying stress contributions based on a model for the amplitude and shape of the emitted strain pulses. Energy transfer processes result in a change of the stress profile with respect to the initial absorption of the laser pulses. One interesting example occurs in nanoscopic gold-nickel heterostructures, where excited electrons rapidly transport energy into a distant nickel layer, that takes up much more energy and expands faster and stronger than the laser-excited gold capping layer. Magnetic excitations in rare earth materials represent a large energy reservoir that delays the energy transfer into adjacent layers. Such magneto-caloric effects are known in thermodynamics but not extensively covered on ultrafast timescales. The combination of ultrafast X-ray diffraction and time-resolved techniques with direct access to the magnetization has a large potential to uncover and quantify such energy transfer processes.}, language = {en} } @phdthesis{Zeuschner2022, author = {Zeuschner, Steffen Peer}, title = {Magnetoacoustics observed with ultrafast x-ray diffraction}, doi = {10.25932/publishup-56109}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-561098}, school = {Universit{\"a}t Potsdam}, pages = {V, 128, IX}, year = {2022}, abstract = {In the present thesis I investigate the lattice dynamics of thin film hetero structures of magnetically ordered materials upon femtosecond laser excitation as a probing and manipulation scheme for the spin system. The quantitative assessment of laser induced thermal dynamics as well as generated picosecond acoustic pulses and their respective impact on the magnetization dynamics of thin films is a challenging endeavor. All the more, the development and implementation of effective experimental tools and comprehensive models are paramount to propel future academic and technological progress. In all experiments in the scope of this cumulative dissertation, I examine the crystal lattice of nanoscale thin films upon the excitation with femtosecond laser pulses. The relative change of the lattice constant due to thermal expansion or picosecond strain pulses is directly monitored by an ultrafast X-ray diffraction (UXRD) setup with a femtosecond laser-driven plasma X-ray source (PXS). Phonons and spins alike exert stress on the lattice, which responds according to the elastic properties of the material, rendering the lattice a versatile sensor for all sorts of ultrafast interactions. On the one hand, I investigate materials with strong magneto-elastic properties; The highly magnetostrictive rare-earth compound TbFe2, elemental Dysprosium or the technological relevant Invar material FePt. On the other hand I conduct a comprehensive study on the lattice dynamics of Bi1Y2Fe5O12 (Bi:YIG), which exhibits high-frequency coherent spin dynamics upon femtosecond laser excitation according to the literature. Higher order standing spinwaves (SSWs) are triggered by coherent and incoherent motion of atoms, in other words phonons, which I quantified with UXRD. We are able to unite the experimental observations of the lattice and magnetization dynamics qualitatively and quantitatively. This is done with a combination of multi-temperature, elastic, magneto-elastic, anisotropy and micro-magnetic modeling. The collective data from UXRD, to probe the lattice, and time-resolved magneto-optical Kerr effect (tr-MOKE) measurements, to monitor the magnetization, were previously collected at different experimental setups. To improve the precision of the quantitative assessment of lattice and magnetization dynamics alike, our group implemented a combination of UXRD and tr-MOKE in a singular experimental setup, which is to my knowledge, the first of its kind. I helped with the conception and commissioning of this novel experimental station, which allows the simultaneous observation of lattice and magnetization dynamics on an ultrafast timescale under identical excitation conditions. Furthermore, I developed a new X-ray diffraction measurement routine which significantly reduces the measurement time of UXRD experiments by up to an order of magnitude. It is called reciprocal space slicing (RSS) and utilizes an area detector to monitor the angular motion of X-ray diffraction peaks, which is associated with lattice constant changes, without a time-consuming scan of the diffraction angles with the goniometer. RSS is particularly useful for ultrafast diffraction experiments, since measurement time at large scale facilities like synchrotrons and free electron lasers is a scarce and expensive resource. However, RSS is not limited to ultrafast experiments and can even be extended to other diffraction techniques with neutrons or electrons.}, language = {en} }