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Giant vesicles may contain several spatial compartments formed by phase separation within their enclosed aqueous solution. This phenomenon might be related to molecular crowding, fractionation and protein sorting in cells. To elucidate this process we used two chemically dissimilar polymers, polyethylene glycol (PEG) and dextran, encapsulated in giant vesicles. The dynamics of the phase separation of this polymer solution enclosed in vesicles is studied by concentration quench, i.e. exposing the vesicles to hypertonic solutions. The excess membrane area, produced by dehydration, can either form tubular structures (also known as tethers) or be utilized to perform morphological changes of the vesicle, depending on the interfacial tension between the coexisting phases and those between the membrane and the two phases. Membrane tube formation is coupled to the phase separation process. Apparently, the energy released from the phase separation is utilized to overcome the energy barrier for tube formation. The tubes may be absorbed at the interface to form a 2-demensional structure. The membrane stored in the form of tubes can be retracted under small tension perturbation. Furthermore, a wetting transition, which has been reported only in a few experimental systems, was discovered in this system. By increasing the polymer concentration, the PEG-rich phase changed from complete wetting to partial wetting of the membrane. If sufficient excess membrane area is available in the vesicle where both phases wet the membrane, one of the phases will bud off from the vesicle body, which leads to the separation of the two phases. This wetting-induced budding is governed by the surface energy and modulated by the membrane tension. This was demonstrated by micropipette aspiration experiments on vesicles encapsulating two phases. The budding of one phase can significantly decrease the surface energy by decreasing the contact area between the coexisting phases. The elasticity of the membrane allows it to adjust its tension automatically to balance the pulling force exerted by the interfacial tension of the two liquid phases at the three-phase contact line. The budding of the phase enriched with one polymer may be relevant to the selective protein transportation among lumens by means of vesicle in cells.
The topic of synchronization forms a link between nonlinear dynamics and neuroscience. On the one hand, neurobiological research has shown that the synchronization of neuronal activity is an essential aspect of the working principle of the brain. On the other hand, recent advances in the physical theory have led to the discovery of the phenomenon of phase synchronization. A method of data analysis that is motivated by this finding - phase synchronization analysis - has already been successfully applied to empirical data. The present doctoral thesis ties up to these converging lines of research. Its subject are methodical contributions to the further development of phase synchronization analysis, as well as its application to event-related potentials, a form of EEG data that is especially important in the cognitive sciences. The methodical contributions of this work consist firstly in a number of specialized statistical tests for a difference in the synchronization strength in two different states of a system of two oscillators. Secondly, in regard of the many-channel character of EEG data an approach to multivariate phase synchronization analysis is presented. For the empirical investigation of neuronal synchronization a classic experiment on language processing was replicated, comparing the effect of a semantic violation in a sentence context with that of the manipulation of physical stimulus properties (font color). Here phase synchronization analysis detects a decrease of global synchronization for the semantic violation as well as an increase for the physical manipulation. In the latter case, by means of the multivariate analysis the global synchronization effect can be traced back to an interaction of symmetrically located brain areas.<BR> The findings presented show that the method of phase synchronization analysis motivated by physics is able to provide a relevant contribution to the investigation of event-related potentials in the cognitive sciences.
In the current paradigm of cosmology, the formation of large-scale structures is mainly driven by non-radiating dark matter, making up the dominant part of the matter budget of the Universe. Cosmological observations however, rely on the detection of luminous galaxies, which are biased tracers of the underlying dark matter. In this thesis I present cosmological reconstructions of both, the dark matter density field that forms the cosmic web, and cosmic velocities, for which both aspects of my work are delved into, the theoretical formalism and the results of its applications to cosmological simulations and also to a galaxy redshift survey.The foundation of our method is relying on a statistical approach, in which a given galaxy catalogue is interpreted as a biased realization of the underlying dark matter density field. The inference is computationally performed on a mesh grid by sampling from a probability density function, which describes the joint posterior distribution of matter density and the three dimensional velocity field. The statistical background of our method is described in Chapter ”Implementation of argo”, where the introduction in sampling methods is given, paying special attention to Markov Chain Monte-Carlo techniques. In Chapter ”Phase-Space Reconstructions with N-body Simulations”, I introduce and implement a novel biasing scheme to relate the galaxy number density to the underlying dark matter, which I decompose into a deterministic part, described by a non-linear and scale-dependent analytic expression, and a stochastic part, by presenting a negative binomial (NB) likelihood function that models deviations from Poissonity. Both bias components had already been studied theoretically, but were so far never tested in a reconstruction algorithm. I test these new contributions againstN-body simulations to quantify improvements and show that, compared to state-of-the-art methods, the stochastic bias is inevitable at wave numbers of k≥0.15h Mpc^−1 in the power spectrum in order to obtain unbiased results from the reconstructions. In the second part of Chapter ”Phase-Space Reconstructions with N-body Simulations” I describe and validate our approach to infer the three dimensional cosmic velocity field jointly with the dark matter density. I use linear perturbation theory for the large-scale bulk flows and a dispersion term to model virialized galaxy motions, showing that our method is accurately recovering the real-space positions of the redshift-space distorted galaxies. I analyze the results with the isotropic and also the two-dimensional power spectrum.Finally, in Chapter ”Phase-space Reconstructions with Galaxy Redshift Surveys”, I show how I combine all findings and results and apply the method to the CMASS (for Constant (stellar) Mass) galaxy catalogue of the Baryon Oscillation Spectroscopic Survey (BOSS). I describe how our method is accounting for the observational selection effects inside our reconstruction algorithm. Also, I demonstrate that the renormalization of the prior distribution function is mandatory to account for higher order contributions in the structure formation model, and finally a redshift-dependent bias factor is theoretically motivated and implemented into our method. The various refinements yield unbiased results of the dark matter until scales of k≤0.2 h Mpc^−1in the power spectrum and isotropize the galaxy catalogue down to distances of r∼20h^−1 Mpc in the correlation function. We further test the results of our cosmic velocity field reconstruction by comparing them to a synthetic mock galaxy catalogue, finding a strong correlation between the mock and the reconstructed velocities. The applications of both, the density field without redshift-space distortions, and the velocity reconstructions, are very broad and can be used for improved analyses of the baryonic acoustic oscillations, environmental studies of the cosmic web, the kinematic Sunyaev-Zel’dovic or integrated Sachs-Wolfe effect.
In the presented thesis, the most advanced photon reconstruction technique of ground-based γ-ray astronomy is adapted to the H.E.S.S. 28 m telescope. The method is based on a semi-analytical model of electromagnetic particle showers in the atmosphere. The properties of cosmic γ-rays are reconstructed by comparing the camera image of the telescope with the Cherenkov emission that is expected from the shower model. To suppress the dominant background from charged cosmic rays, events are selected based on several criteria. The performance of the analysis is evaluated with simulated events. The method is then applied to two sources that are known to emit γ-rays. The first of these is the Crab Nebula, the standard candle of ground-based γ-ray astronomy. The results of this source confirm the expected performance of the reconstruction method, where the much lower energy threshold compared to H.E.S.S. I is of particular importance. A second analysis is performed on the region around the Galactic Centre. The analysis results emphasise the capabilities of the new telescope to measure γ-rays in an energy range that is interesting for both theoretical and experimental astrophysics. The presented analysis features the lowest energy threshold that has ever been reached in ground-based γ-ray astronomy, opening a new window to the precise measurement of the physical properties of time-variable sources at energies of several tens of GeV.
Filaments are omnipresent features in the solar chromosphere, one of the atmospheric layers of the Sun, which is located above the photosphere, the visible surface of the Sun. They are clouds of plasma reaching from the photosphere to the chromosphere, and even to the outer-most atmospheric layer, the corona. They are stabalized by the magnetic field. If the magnetic field is disturbed, filaments can erupt as coronal mass ejections (CME), releasing plasma into space, which can also hit the Earth. A special type of filaments are polar crown filaments, which form at the interface of the unipolar field of the poles and flux of opposite magnetic polarity, which was transported towards the poles. This flux transport is related to the global dynamo of the Sun and can therefore be analyzed indirectly with polar crown filaments. The main objective of this thesis is to better understand the physical properties and environment of high-latitude and polar crown filaments, which can be approached from two perspectives: (1) analyzing the large-scale properties of high-latitude and polar crown filaments with full-disk Hα observations from the Chromospheric Telescope (ChroTel) and (2) determining the relation of polar crown and high-latitude filaments from the chromosphere to the lower-lying photosphere with high-spatial resolution observations of the Vacuum Tower Telescope (VTT), which reveal the smallest details.
The Chromospheric Telescope (ChroTel) is a small 10-cm robotic telescope at Observatorio del Teide on Tenerife (Spain), which observes the entire Sun in Hα, Ca IIK, and He I 10830 Å. We present a new calibration method that includes limb-darkening correction, removal of non-uniform filter transmission, and determination of He I Doppler velocities. Chromospheric full-disk filtergrams are often obtained with Lyot filters, which may display non-uniform transmission causing large-scale intensity variations across the solar disk. Removal of a 2D symmetric limb-darkening function from full-disk images results in a flat background. However, transmission artifacts remain and are even more distinct in these contrast-enhanced images. Zernike polynomials are uniquely appropriate to fit these large-scale intensity variations of the background. The Zernike coefficients show a distinct temporal evolution for ChroTel data, which is likely related to the telescope’s alt-azimuth mount that introduces image rotation. In addition, applying this calibration to sets of seven filtergrams that cover the He I triplet facilitates determining chromospheric Doppler velocities. To validate the method, we use three datasets with varying levels of solar activity. The Doppler velocities are benchmarked with respect to co-temporal high-resolution spectroscopic data of the GREGOR Infrared Spectrograph (GRIS). Furthermore, this technique can be applied to ChroTel Hα and Ca IIK data. The calibration method for ChroTel filtergrams can be easily adapted to other full-disk data exhibiting unwanted large-scale variations. The spectral region of the He I triplet is a primary choice for high-resolution near-infrared spectropolarimetry. Here, the improved calibration of ChroTel data will provide valuable context data.
Polar crown filaments form above the polarity inversion line between the old magnetic flux of the previous cycle and the new magnetic flux of the current cycle. Studying their appearance and their properties can lead to a better understanding of the solar cycle. We use full-disk data of the ChroTel at Observatorio del Teide, Tenerife, Spain, which were taken in three different chromospheric absorption lines (Hα 6563 Å, Ca IIK 3933 Å, and He I 10830 Å), and we create synoptic maps. In addition, the spectroscopic He I data allow us to compute Doppler velocities and to create synoptic Doppler maps. ChroTel data cover the rising and decaying phase of Solar Cycle 24 on about 1000 days between 2012 and 2018. Based on these data, we automatically extract polar crown filaments with image-processing tools and study their properties. We compare contrast maps of polar crown filaments with those of quiet-Sun filaments. Furthermore, we present a super-synoptic map summarizing the entire ChroTel database. In summary, we provide statistical properties, i.e. number and location of filaments, area, and tilt angle for both the maximum and declining phase of Solar Cycle 24. This demonstrates that ChroTel provides a
promising dataset to study the solar cycle.
The cyclic behavior of polar crown filaments can be monitored by regular full-disk Hα observations. ChroTel provides such regular observations of the Sun in three chromospheric wavelengths. To analyze the cyclic behavior and the statistical properties of polar crown filaments, we have to extract the filaments from the images. Manual extraction is tedious, and extraction with morphological image processing tools produces a large number of false positive detections and the manual extraction of these takes too much time. Automatic object detection and extraction in a reliable manner allows us to process more data in a shorter time. We will present an overview of the ChroTel database and a proof of concept of a machine learning application, which allows us a unified extraction of, for example, filaments from ChroTel data.
The chromospheric Hα spectral line dominates the spectrum of the Sun and other stars. In the stellar regime, this spectral line is already used as a powerful tracer of magnetic activity. For the Sun, other tracers are typically used to monitor solar activity. Nonetheless, the Sun is observed constantly in Hα with globally distributed ground-based full-disk imagers. The aim of this study is to introduce Hα as a tracer of solar activity and compare it to other established indicators. We discuss the newly created imaging Hα excess in the perspective of possible application for modelling of stellar atmospheres. In particular, we try to determine how constant is the mean intensity of the Hα excess and number density of low-activity regions between solar maximum and minimum. Furthermore, we investigate whether the active region coverage fraction or the changing emission strength in the active regions dominates time variability in solar Hα observations. We use ChroTel observations of full-disk Hα filtergrams and morphological image processing techniques to extract the positive and negative imaging Hα excess, for bright features (plage regions) and dark absorption features (filaments and sunspots), respectively. We describe the evolution of the Hα excess during Solar Cycle 24 and compare it to other well established tracers: the relative sunspot number, the F10.7 cm radio flux, and the Mg II index. Moreover, we discuss possible applications of the Hα excess for stellar activity diagnostics and the contamination of exoplanet transmission spectra. The positive and negative Hα excess follow the behavior of the solar activity over the course of the cycle. Thereby, positive Hα excess is closely correlated to the chromospheric Mg II index. On the other hand, the negative Hα excess, created from dark features like filaments and sunspots, is introduced as a tracer of solar activity for the first time. We investigated the mean intensity distribution for active regions for solar minimum and maximum and found that the shape of both distributions is very similar but with different amplitudes. This might be related with the relatively stable coronal temperature component during the solar cycle. Furthermore, we found that the coverage fraction of Hα excess and the Hα excess of bright features are strongly correlated, which will influence modelling of stellar and exoplanet atmospheres.
High-resolution observations of polar crown and high-latitude filaments are scarce. We present a unique sample of such filaments observed in high-resolution Hα narrow-band filtergrams and broad-band images, which were obtained with a new fast camera system at the VTT. ChroTel provided full-disk context observations in Hα, Ca IIK, and He I 10830 Å. The Helioseismic and Magnetic Imager (HMI) and the Atmospheric Imaging Assembly (AIA) on board the Solar Dynamics Observatory (SDO) provided line-of-sight magnetograms and ultraviolet (UV) 1700 Å filtergrams, respectively. We study filigree in the vicinity of polar crown and high-latitude filaments and relate their locations to magnetic concentrations at the filaments’ footpoints. Bright points are a well studied phenomenon in the photosphere at low latitudes, but they were not yet studied in the quiet network close to the poles. We examine size, area, and eccentricity of bright points and find that their morphology is very similar to their counterparts at lower latitudes, but their sizes and areas are larger. Bright points at the footpoints of polar crown filaments are preferentially located at stronger magnetic flux concentrations, which are related to bright regions at the border of supergranules as observed in UV filtergrams. Examining the evolution of bright points on three consecutive days reveals that their amount increases while the filament decays, which indicates they impact the equilibrium of the cool plasma contained in filaments.
This thesis investigates the application of polyelectrolyte multilayers in plasmonics and picosecond acoustics. The observed samples were fabricated by the spin-assisted layer-by-layer deposition technique that allowed a precise tuning of layer thickness in the range of few nanometers.
The first field of interest deals with the interaction of light-induced localized surface plasmons (LSP) of rod-shaped gold nanoparticles with the particles' environment. The environment consists of an air phase and a phase of polyelectrolytes, whose ratio affects the spectral position of the LSP resonance.
Measured UV-VIS spectra showed the shift of the LSP absorption peak as a function of the cover layer thickness of the particles. The data are modeled using an average dielectric function instead of the dielectric functions of air and polyelectrolytes. In addition using a measured dielectric function of the gold nanoparticles, the position of the LSP absorption peak could be simulated with good agreement to the data.
The analytic model helps to understand the optical properties of metal nanoparticles in an inhomogeneous environment.
The second part of this work discusses the applicability of PAzo/PAH and dye-doped PSS/PAH polyelectrolyte multilayers as transducers to generate hypersound pulses. The generated strain pulses were detected by time-domain Brillouin scattering (TDBS) using a pump-probe laser setup. Transducer layers made of polyelectrolytes were compared qualitatively to common aluminum transducers in terms of measured TDBS signal amplitude, degradation due to laser excitation, and sample preparation.
The measurements proved that fast and easy prepared polyelectrolyte transducers provided stronger TDBS signals than the aluminum transducer. AFM topography measurements showed a degradation of the polyelectrolyte structures, especially for the PAzo/PAH sample.
To quantify the induced strain, optical barriers were introduced to separate the transducer material from the medium of the hypersound propagation. Difficulties in the sample preparation prohibited a reliable quantification. But the experiments showed that a coating with transparent polyelectrolytes increases the efficiency of aluminum transducers and modifies the excited phonon distribution.
The adoption of polyelectrolytes to the scientific field of picosecond acoustics enables a cheap and fast fabrication of transducer layers on most surfaces. In contrast to aluminum layers the polyelectrolytes are transparent over a wide spectral range. Thus, the strain modulation can be probed from surface and back.
Polymers at membranes
(2000)
The surface of biological cells consists of a lipid membrane and a large amount of various proteins and polymers, which are embedded in the membrane or attached to it. We investigate how membranes are influenced by polymers, which are anchored to the membrane by one end. The entropic pressure exerted by the polymer induces a curvature, which bends the membrane away from the polymer. The resulting membrane shape profile is a cone in the vicinity of the anchor segment and a catenoid far away from it. The perturbative calculations are confirmed by Monte-Carlo simulations. An additional attractive interaction between polymer and membrane reduces the entropically induced curvature. In the limit of strong adsorption, the polymer is localized directly on the membrane surface and does not induce any pressure, i.e. the membrane curvature vanishes. If the polymer is not anchored directly on the membrane surface, but in a non-vanishing anchoring distance, the membrane bends towards the polymer for strong adsorption. In the last part of the thesis, we study membranes under the influence of non-anchored polymers in solution. In the limit of pure steric interactions between the membrane and free polymers, the membrane curves towards the polymers (in contrast to the case of anchored polymers). In the limit of strong adsorption the membrane bends away from the polymers.
The life of microorganisms is characterized by two main tasks, rapid growth under conditions permitting growth and survival under stressful conditions. The environments, in which microorganisms dwell, vary in space and time. The microorganisms innovate diverse strategies to readily adapt to the regularly fluctuating environments. Phenotypic heterogeneity is one such strategy, where an isogenic population splits into subpopulations that respond differently under identical environments. Bacterial persistence is a prime example of such phenotypic heterogeneity, whereby a population survives under an antibiotic attack, by keeping a fraction of population in a drug tolerant state, the persister state. Specifically, persister cells grow more slowly than normal cells under growth conditions, but survive longer under stress conditions such as the antibiotic administrations. Bacterial persistence is identified experimentally by examining the population survival upon an antibiotic treatment and the population resuscitation in a growth medium. The underlying population dynamics is explained with a two state model for reversible phenotype switching in a cell within the population. We study this existing model with a new theoretical approach and present analytical expressions for the time scale observed in population growth and resuscitation, that can be easily used to extract underlying model parameters of bacterial persistence. In addition, we recapitulate previously known results on the evolution of such structured population under periodically fluctuating environment using our simple approximation method. Using our analysis, we determine model parameters for Staphylococcus aureus population under several antibiotics and interpret the outcome of cross-drug treatment. Next, we consider the expansion of a population exhibiting phenotype switching in a spatially structured environment consisting of two growth permitting patches separated by an antibiotic patch. The dynamic interplay of growth, death and migration of cells in different patches leads to distinct regimes in population propagation speed as a function of migration rate. We map out the region in parameter space of phenotype switching and migration rate to observe the condition under which persistence is beneficial. Furthermore, we present an extended model that allows mutation from the two phenotypic states to a resistant state. We find that the presence of persister cells may enhance the probability of resistant mutation in a population. Using this model, we explain the experimental results showing the emergence of antibiotic resistance in a Staphylococcus aureus population upon tobramycin treatment. In summary, we identify several roles of bacterial persistence, such as help in spatial expansion, development of multidrug tolerance and emergence of antibiotic resistance. Our study provides a theoretical perspective on the dynamics of bacterial persistence in different environmental conditions. These results can be utilized to design further experiments, and to develop novel strategies to eradicate persistent infections.
The correlations between the chemical structures of the 2,5-diphenyl-1,3,4-oxadiazole compounds and their corresponding vapour deposited film structures on Si/SiO2 were systematically investigated with AFM, XSR and IR for the first time. The result shows that the film structure depends strongly on the substrate temperature (Ts). For the compounds with ether bridge group, the film periodicity depends linearly on the length of the aliphatic chain. The films based on those oxadiazols have ordered structure in the investigated substrate temperature region, while die amide bridged compounds form ordered film only at high Ts due to the formation of intermolecular H-bond. The tilt angle of most molecules is determined by the pi-pi complexes between the molecules. The intermolecular interaction between head groups leads to the structural transformation during the thermal treatment after deposition. All the ether bridged oxadiazoles form films with bilayer structure, while amide bridged oxadiazole form film bilayer structure only when the molecule has a head group.
Preparation and investigation of polymer-foam films and polymer-layer systems for ferroelectrets
(2010)
Piezoelectric materials are very useful for applications in sensors and actuators. In addition to traditional ferroelectric ceramics and ferroelectric polymers, ferroelectrets have recently become a new group of piezoelectrics. Ferroelectrets are functional polymer systems for electromechanical transduction, with elastically heterogeneous cellular structures and internal quasi-permanent dipole moments. The piezoelectricity of ferroelectrets stems from linear changes of the dipole moments in response to external mechanical or electrical stress. Over the past two decades, polypropylene (PP) foams have been investigated with the aim of ferroelectret applications, and some products are already on the market. PP-foam ferroelectrets may exhibit piezoelectric d33 coefficients of 600 pC/N and more. Their operating temperature can, however, not be much higher than 60 °C. Recently developed polyethylene-terephthalate (PET) and cyclo-olefin copolymer (COC) foam ferroelectrets show slightly better d33 thermal stabilities, but usually at the price of smaller d33 values. Therefore, the main aim of this work is the development of new thermally stable ferroelectrets with appreciable piezoelectricity. Physical foaming is a promising technique for generating polymer foams from solid films without any pollution or impurity. Supercritical carbon dioxide (CO2) or nitrogen (N2) are usually employed as foaming agents due to their good solubility in several polymers. Polyethylene propylene (PEN) is a polyester with slightly better properties than PET. A “voiding + inflation + stretching” process has been specifically developed to prepare PEN foams. Solid PEN films are saturated with supercritical CO2 at high pressure and then thermally voided at high temperatures. Controlled inflation (Gas-Diffusion Expansion or GDE) is applied in order to adjust the void dimensions. Additional biaxial stretching decreases the void heights, since it is known lens-shaped voids lead to lower elastic moduli and therefore also to stronger piezoelectricity. Both, contact and corona charging are suitable for the electric charging of PEN foams. The light emission from the dielectric-barrier discharges (DBDs) can be clearly observed. Corona charging in a gas of high dielectric strength such as sulfur hexafluoride (SF6) results in higher gas-breakdown strength in the voids and therefore increases the piezoelectricity. PEN foams can exhibit piezoelectric d33 coefficients as high as 500 pC/N. Dielectric-resonance spectra show elastic moduli c33 of 1 − 12 MPa, anti-resonance frequencies of 0.2 − 0.8 MHz, and electromechanical coupling factors of 0.016 − 0.069. As expected, it is found that PEN foams show better thermal stability than PP and PET. Samples charged at room temperature can be utilized up to 80 − 100 °C. Annealing after charging or charging at elevated temperatures may improve thermal stabilities. Samples charged at suitable elevated temperatures show working temperatures as high as 110 − 120 °C. Acoustic measurements at frequencies of 2 Hz − 20 kHz show that PEN foams can be well applied in this frequency range. Fluorinated ethylene-propylene (FEP) copolymers are fluoropolymers with very good physical, chemical and electrical properties. The charge-storage ability of solid FEP films can be significantly improved by adding boron nitride (BN) filler particles. FEP foams are prepared by means of a one-step procedure consisting of CO2 saturation and subsequent in-situ high-temperature voiding. Piezoelectric d33 coefficients up to 40 pC/N are measured on such FEP foams. Mechanical fatigue tests show that the as-prepared PEN and FEP foams are mechanically stable for long periods of time. Although polymer-foam ferroelectrets have a high application potential, their piezoelectric properties strongly depend on the cellular morphology, i.e. on size, shape, and distribution of the voids. On the other hand, controlled preparation of optimized cellular structures is still a technical challenge. Consequently, new ferroelectrets based on polymer-layer system (sandwiches) have been prepared from FEP. By sandwiching an FEP mesh between two solid FEP films and fusing the polymer system with a laser beam, a well-designed uniform macroscopic cellular structure can be formed. Dielectric resonance spectroscopy reveals piezoelectric d33 coefficients as high as 350 pC/N, elastic moduli of about 0.3 MPa, anti-resonance frequencies of about 30 kHz, and electromechanical coupling factors of about 0.05. Samples charged at elevated temperatures show better thermal stabilities than those charged at room temperature, and the higher the charging temperature, the better is the stability. After proper charging at 140 °C, the working temperatures can be as high as 110 − 120 °C. Acoustic measurements at frequencies of 200 Hz − 20 kHz indicate that the FEP layer systems are suitable for applications at least in this range.
We investigate the rotational and thermal properties of star-forming molecular clouds using hydrodynamic simulations. Stars form from molecular cloud cores by gravoturbulent fragmentation. Understanding the angular momentum and the thermal evolution of cloud cores thus plays a fundamental role in completing the theoretical picture of star formation. This is true not only for current star formation as observed in regions like the Orion nebula or the ρ-Ophiuchi molecular cloud but also for the formation of stars of the first or second generation in the universe. In this thesis we show how the angular momentum of prestellar and protostellar cores evolves and compare our results with observed quantities. The specific angular momentum of prestellar cores in our models agree remarkably well with observations of cloud cores. Some prestellar cores go into collapse to build up stars and stellar systems. The resulting protostellar objects have specific angular momenta that fall into the range of observed binaries. We find that collapse induced by gravoturbulent fragmentation is accompanied by a substantial loss of specific angular momentum. This eases the "angular momentum problem" in star formation even in the absence of magnetic fields. The distribution of stellar masses at birth (the initial mass function, IMF) is another aspect that any theory of star formation must explain. We focus on the influence of the thermodynamic properties of star-forming gas and address this issue by studying the effects of a piecewise polytropic equation of state on the formation of stellar clusters. We increase the polytropic exponent γ from a value below unity to a value above unity at a certain critical density. The change of the thermodynamic state at the critical density selects a characteristic mass scale for fragmentation, which we relate to the peak of the IMF observed in the solar neighborhood. Our investigation generally supports the idea that the distribution of stellar masses depends mainly on the thermodynamic state of the gas. A common assumption is that the chemical evolution of the star-forming gas can be decoupled from its dynamical evolution, with the former never affecting the latter. Although justified in some circumstances, this assumption is not true in every case. In particular, in low-metallicity gas the timescales for reaching the chemical equilibrium are comparable or larger than the dynamical timescales. In this thesis we take a first approach to combine a chemical network with a hydrodynamical code in order to study the influence of low levels of metal enrichment on the cooling and collapse of ionized gas in small protogalactic halos. Our initial conditions represent protogalaxies forming within a fossil HII region -- a previously ionized HII region which has not yet had time to cool and recombine. We show that in these regions, H2 is the dominant and most effective coolant, and that it is the amount of H2 formed that controls whether or not the gas can collapse and form stars. For metallicities Z <= 10<sup>-3 Zsun, metal line cooling alters the density and temperature evolution of the gas by less than 1% compared to the metal-free case at densities below 1 cm<sup>-3 and temperatures above 2000 K. We also find that an external ultraviolet background delays or suppresses the cooling and collapse of the gas regardless of whether it is metal-enriched or not. Finally, we study the dependence of this process on redshift and mass of the dark matter halo.
The electronic charge distributions of transition metal complexes fundamentally determine their chemical reactivity. Experimental access to the local valence electronic structure is therefore crucial in order to determine how frontier orbitals are delocalized between different atomic sites and electronic charge is spread throughout the transition metal complex. To that end, X-ray spectroscopies are employed in this thesis to study a series of solution-phase iron complexes with respect to the response of their local electronic charge distributions to different external influences. Using resonant inelastic X-ray scattering (RIXS) and X-ray absorption spectroscopy (XAS) at the iron L-edge, changes in local charge densities are investigated at the iron center depending on different ligand cages as well as solvent environments. A varying degree of charge delocalization from the metal center onto the ligands is observed, which is governed by the capabilities of the ligands to accept charge density into their unoccupied orbitals. Specific solvents are furthermore shown to amplify this process. Solvent molecules of strong Lewis-acids withdraw charge from the ligand allowing in turn for more metal charge to be delocalized onto the ligand. The resulting local charge deficiencies at the metal center are, however, counteracted by competing electron-donation channels from the ligand towards the iron, which are additionally revealed. This is interpreted as a compensating effect which strives to maintain local charge densities at the iron center. This mechanism of charge density preservation is found to be of general nature. Using time-resolved RIXS and XAS at the iron L-edge, an analogous interplay of electron donation and back-donation channels is also revealed for the case of charge-transfer excited states. In such transient configurations, the electronic occupation of iron-centered frontier orbitals has been altered by an optical excitation. Changes in local charge densities that are expected to follow an increased or decreased population of iron-centered orbitals are, however, again counteracted. By scaling the degree of electron donation from the ligand onto the metal, local charge densities at the iron center can be efficiently maintained. Since charge-transfer excitations, however, often constitute the initial step in many electron transfer processes, these findings challenge common notions of charge-separation in transition metal dyes.
Organic semiconductors are a promising class of materials. Their special properties are the particularly good absorption, low weight and easy processing into thin films. Therefore, intense research has been devoted to the realization of thin film organic solar cells (OPVs). Because of the low dielectric constant of organic semiconductors, primary excitations (excitons) are strongly bound and a type II heterojunction needs to be introduced to split these excitations into free charges. Therefore, most organic solar cells consist of at least an electron donor and electron acceptor material. For such donor acceptor systems mainly three states are relevant; the photoexcited exciton on the donor or acceptor material, the charge transfer state at the donor-acceptor interface and the charge separated state of a free electron and hole. The interplay between these states significantly determines the efficiency of organic solar cells. Due to the high absorption and the low charge carrier mobilities, the active layers are usually thin but also, exciton dissociation and free charge formation proceeds rapidely, which makes the study of carrier dynamics highly challenging.
Therefore, the focus of this work was first to install new experimental setups for the investigation of the charge carrier dynamics in complete devices with superior sensitivity and time resolution and, second, to apply these methods to prototypical photovoltaic materials to address specific questions in the field of organic and hybrid photovoltaics.
Regarding the first goal, a new setup combining transient absorption spectroscopy (TAS) and time delayed collection field (TDCF) was designed and installed in Potsdam. An important part of this work concerned the improvement of the electronic components with respect to time resolution and sensitivity. To this end, a highly sensitive amplifier for driving and detecting the device response in TDCF was developed. This system was then applied to selected organic and hybrid model systems with a particular focus on the understanding of the loss mechanisms that limit the fill factor and short circuit current of organic solar cells.
The first model system was a hybrid photovoltaic material comprising inorganic quantum dots decorated with organic ligands. Measurements with TDCF revealed fast free carrier recombination, in part assisted by traps, while bias-assisted charge extraction measurements showed high mobility. The measured parameters then served as input for a successful description of the device performance with an analytical model.
With a further improvement of the instrumentation, a second topic was the detailed analysis of non-geminate recombination in a disordered polymer:fullerene blend where an important question was the effect of disorder on the carrier dynamics. The measurements revealed that early time highly mobile charges undergo fast non-geminate recombination at the contacts, causing an apparent field dependence of free charge generation in TDCF experiments if not conducted properly. On the other hand, recombination the later time scale was determined by dispersive recombination in the bulk of the active layer, showing the characteristics of carrier dynamics in an exponential density of state distribution. Importantly, the comparison with steady state recombination data suggested a very weak impact of non-thermalized carriers on the recombination properties of the solar cells under application relevant illumination conditions.
Finally, temperature and field dependent studies of free charge generation were performed on three donor-acceptor combinations, with two donor polymers of the same material family blended with two different fullerene acceptor molecules. These particular material combinations were chosen to analyze the influence of the energetic and morphology of the blend on the efficiency of charge generation. To this end, activation energies for photocurrent generation were accurately determined for a wide range of excitation energies. The results prove that the formation of free charge is via thermalized charge transfer states and does not involve hot exciton splitting. Surprisingly, activation energies were of the order of thermal energy at room temperature. This led to the important conclusion that organic solar cells perform well not because of predominate high energy pathways but because the thermalized CT states are weakly bound. In addition, a model is introduced to interconnect the dissociation efficiency of the charge transfer state with its recombination observable with photoluminescence, which rules out a previously proposed two-pool model for free charge formation and recombination. Finally, based on the results, proposals for the further development of organic solar cells are formulated.
Understanding the changes that follow UV-excitation in thionucleobases is of great importance for the study of light-induced DNA lesions and, in a broader context, for their applications in medicine and biochemistry. Their ultrafast photophysical reactions can alter the chemical structure of DNA - leading to damages to the genetic code - as proven by the increased skin cancer risk observed for patients treated with thiouracil for its immunosuppressant properties.
In this thesis, I present four research papers that result from an investigation of the ultrafast dynamics of 2-thiouracil by means of ultrafast x-ray probing combined with electron spectroscopy. A molecular jet in the gas phase is excited with a uv pulse and then ionized with x-ray radiation from a Free Electron Laser. The kinetic energy of the emitted electrons is measured in a magnetic bottle spectrometer. The spectra of the measured photo and Auger electrons are used to derive a picture of the changes in the geometrical and electronic configurations. The results allow us to look at the dynamical processes from a new perspective, thanks to the element- and site- sensitivity of x-rays. The custom-built URSA-PQ apparatus used in the experiment is described. It has been commissioned and used at the FL24 beamline of the FLASH2 FEL, showing an electron kinetic energy resolution of ∆E/E ~ 40 and a pump-probe timing resolution of 190 f s. X-ray only photoelectron and Auger spectra of 2-thiouracil are extracted from the data and used as reference. Photoelectrons following the formation a 2p core hole are identified, as well as resonant and non-resonant Auger electrons. At the L 1 edge, Coster-Kronig decay is observed from the 2s core hole.
The UV-induced changes in the 2p photoline allow the study the electronic-state dynamics. With the use of an Excited-State Chemical Shift (ESCS) model, we observe a ultrafast ground-state relaxation within 250 f s. Furthermore, an oscillation with a 250 f s period is observed in the 2p binding energy, showing a coherent population exchange between electronic states. Auger electrons from the 2p core hole are analyzed and used to deduce a ultrafast C −S bond expansion on a sub 100 f s scale. A simple Coulomb-model, coupled to quantum chemical calculations, can be used to infer the geometrical changes in the molecular structure.
The Lyman-𝛼 (Ly𝛼) line commonly assists in the detection of high-redshift galaxies, the so-called Lyman-alpha emitters (LAEs). LAEs are useful tools to study the baryonic matter distribution of the high-redshift universe. Exploring their spatial distribution not only reveals the large-scale structure of the universe at early epochs, but it also provides an insight into the early formation and evolution of the galaxies we observe today. Because dark matter halos (DMHs) serve as sites of galaxy formation, the LAE distribution also traces that of the underlying dark matter. However, the details of this relation and their co-evolution over time remain unclear. Moreover, theoretical studies predict that the spatial distribution of LAEs also impacts their own circumgalactic medium (CGM) by influencing their extended Ly𝛼 gaseous halos (LAHs), whose origin is still under investigation. In this thesis, I make several contributions to improve the knowledge on these fields using samples of LAEs observed with the Multi Unit Spectroscopic Explorer (MUSE) at redshifts of 3 < 𝑧 < 6.
Stars are born in turbulent molecular clouds that fragment and collapse under the influence of their own gravity, forming a cluster of hundred or more stars. The star formation process is controlled by the interplay between supersonic turbulence and gravity. In this work, the properties of stellar clusters created by numerical simulations of gravoturbulent fragmentation are compared to those from observations. This includes the analysis of properties of individual protostars as well as statistical properties of the entire cluster. It is demonstrated that protostellar mass accretion is a highly dynamical and time-variant process. The peak accretion rate is reached shortly after the formation of the protostellar core. It is about one order of magnitude higher than the constant accretion rate predicted by the collapse of a classical singular isothermal sphere, in agreement with the observations. For a more reasonable comparison, the model accretion rates are converted to the observables bolometric temperature, bolometric luminosity, and envelope mass. The accretion rates from the simulations are used as input for an evolutionary scheme. The resulting distribution in the Tbol-Lbol-Menv parameter space is then compared to observational data by means of a 3D Kolmogorov-Smirnov test. The highest probability found that the distributions of model tracks and observational data points are drawn from the same population is 70%. The ratios of objects belonging to different evolutionary classes in observed star-forming clusters are compared to the temporal evolution of the gravoturbulent models in order to estimate the evolutionary stage of a cluster. While it is difficult to estimate absolute ages, the realtive numbers of young stars reveal the evolutionary status of a cluster with respect to other clusters. The sequence shows Serpens as the youngest and IC 348 as the most evolved of the investigated clusters. Finally the structures of young star clusters are investigated by applying different statistical methods like the normalised mean correlation length and the minimum spanning tree technique and by a newly defined measure for the cluster elongation. The clustering parameters of the model clusters correspond in many cases well to those from observed ones. The temporal evolution of the clustering parameters shows that the star cluster builds up from several subclusters and evolves to a more centrally concentrated cluster, while the cluster expands slower than new stars are formed.
The non-linear behaviour of the atmospheric dynamics is not well understood and makes the evaluation and usage of regional climate models (RCMs) difficult. Due to these non-linearities, chaos and internal variability (IV) within the RCMs are induced, leading to a sensitivity of RCMs to their initial conditions (IC). The IV is the ability of RCMs to realise different solutions of simulations that differ in their IC, but have the same lower and lateral boundary conditions (LBC), hence can be defined as the across-member spread between the ensemble members.
For the investigation of the IV and the dynamical and diabatic contributions generating the IV four ensembles of RCM simulations are performed with the atmospheric regional model HIRHAM5. The integration area is the Arctic and each ensemble consists of 20 members. The ensembles cover the time period from July to September for the years 2006, 2007, 2009 and 2012. The ensemble members have the same LBC and differ in their IC only. The different IC are arranged by an initialisation time that shifts successively by six hours. Within each ensemble the first simulation starts on 1st July at 00 UTC and the last simulation starts on 5th July at 18 UTC and each simulation runs until 30th September. The analysed time period ranges from 6th July to 30th September, the time period that is covered by all ensemble members. The model runs without any nudging to allow a free development of each simulation to get the full internal variability within the HIRHAM5.
As a measure of the model generated IV, the across-member standard deviation and the across-member variance is used and the dynamical and diabatic processes influencing the IV are estimated by applying a diagnostic budget study for the IV tendency of the potential temperature developed by Nikiema and Laprise [2010] and Nikiema and Laprise [2011]. The diagnostic budget study is based on the first law of thermodynamics for potential temperature and the mass-continuity equation. The resulting budget equation reveals seven contributions to the potential temperature IV tendency.
As a first study, this work analyses the IV within the HIRHAM5. Therefore, atmospheric circulation parameters and the potential temperature for all four ensemble years are investigated. Similar to previous studies, the IV fluctuates strongly in time. Further, due to the fact that all ensemble members are forced with the same LBC, the IV depends on the vertical level within the troposphere, with high values in the lower troposphere and at 500 hPa and low values in the upper troposphere and at the surface. By the same reason, the spatial distribution shows low values of IV at the boundaries of the model domain.
The diagnostic budget study for the IV tendency of potential temperature reveals that the seven contributions fluctuate in time like the IV. However, the individual terms reach different absolute magnitudes. The budget study identifies the horizontal and vertical ‘baroclinic’ terms as the main contributors to the IV tendency, with the horizontal ‘baroclinic’ term producing and the vertical ‘baroclinic’ term reducing the IV. The other terms fluctuate around zero, because they are small in general or are balanced due to the domain average.
The comparison of the results obtained for the four different ensembles (summers 2006, 2007, 2009 and 2012) reveals that on average the findings for each ensemble are quite similar concerning the magnitude and the general pattern of IV and its contributions. However, near the surface a weaker IV is produced with decreasing sea ice extent. This is caused by a smaller impact of the horizontal 'baroclinic' term over some regions and by the changing diabatic processes, particularly a more intense reducing tendency of the IV due to condensative heating. However, it has to be emphasised that the behaviour of the IV and its dynamical and diabatic contributions are influenced mainly by complex atmospheric feedbacks and large-scale processes and not by the sea ice distribution.
Additionally, a comparison with a second RCM covering the Arctic and using the same LBCs and IC is performed. For both models very similar results concerning the IV and its dynamical and diabatic contributions are found. Hence, this investigation leads to the conclusion that the IV is a natural phenomenon and is independent from the applied RCM.
The purpose of Probabilistic Seismic Hazard Assessment (PSHA) at a construction site is to provide the engineers with a probabilistic estimate of ground-motion level that could be equaled or exceeded at least once in the structure’s design lifetime. A certainty on the predicted ground-motion allows the engineers to confidently optimize structural design and mitigate the risk of extensive damage, or in worst case, a collapse. It is therefore in interest of engineering, insurance, disaster mitigation, and security of society at large, to reduce uncertainties in prediction of design ground-motion levels.
In this study, I am concerned with quantifying and reducing the prediction uncertainty of regression-based Ground-Motion Prediction Equations (GMPEs). Essentially, GMPEs are regressed best-fit formulae relating event, path, and site parameters (predictor variables) to observed ground-motion values at the site (prediction variable). GMPEs are characterized by a parametric median (μ) and a non-parametric variance (σ) of prediction. μ captures the known ground-motion physics i.e., scaling with earthquake rupture properties (event), attenuation with distance from source (region/path), and amplification due to local soil conditions (site); while σ quantifies the natural variability of data that eludes μ. In a broad sense, the GMPE prediction uncertainty is cumulative of 1) uncertainty on estimated regression coefficients (uncertainty on μ,σ_μ), and 2) the inherent natural randomness of data (σ). The extent of μ parametrization, the quantity, and quality of ground-motion data used in a regression, govern the size of its prediction uncertainty: σ_μ and σ.
In the first step, I present the impact of μ parametrization on the size of σ_μ and σ. Over-parametrization appears to increase the σ_μ, because of the large number of regression coefficients (in μ) to be estimated with insufficient data. Under-parametrization mitigates σ_μ, but the reduced explanatory strength of μ is reflected in inflated σ. For an optimally parametrized GMPE, a ~10% reduction in σ is attained by discarding the low-quality data from pan-European events with incorrect parametric values (of predictor variables).
In case of regions with scarce ground-motion recordings, without under-parametrization, the only way to mitigate σ_μ is to substitute long-term earthquake data at a location with short-term samples of data across several locations – the Ergodic Assumption. However, the price of ergodic assumption is an increased σ, due to the region-to-region and site-to-site differences in ground-motion physics. σ of an ergodic GMPE developed from generic ergodic dataset is much larger than that of non-ergodic GMPEs developed from region- and site-specific non-ergodic subsets - which were too sparse to produce their specific GMPEs. Fortunately, with the dramatic increase in recorded ground-motion data at several sites across Europe and Middle-East, I could quantify the region- and site-specific differences in ground-motion scaling and upgrade the GMPEs with 1) substantially more accurate region- and site-specific μ for sites in Italy and Turkey, and 2) significantly smaller prediction variance σ. The benefit of such enhancements to GMPEs is quite evident in my comparison of PSHA estimates from ergodic versus region- and site-specific GMPEs; where the differences in predicted design ground-motion levels, at several sites in Europe and Middle-Eastern regions, are as large as ~50%.
Resolving the ergodic assumption with mixed-effects regressions is feasible when the quantified region- and site-specific effects are physically meaningful, and the non-ergodic subsets (regions and sites) are defined a priori through expert knowledge. In absence of expert definitions, I demonstrate the potential of machine learning techniques in identifying efficient clusters of site-specific non-ergodic subsets, based on latent similarities in their ground-motion data. Clustered site-specific GMPEs bridge the gap between site-specific and fully ergodic GMPEs, with their partially non-ergodic μ and, σ ~15% smaller than the ergodic variance.
The methodological refinements to GMPE development produced in this study are applicable to new ground-motion datasets, to further enhance certainty of ground-motion prediction and thereby, seismic hazard assessment. Advanced statistical tools show great potential in improving the predictive capabilities of GMPEs, but the fundamental requirement remains: large quantity of high-quality ground-motion data from several sites for an extended time-period.
The Thesis is focused on the properties of self-organized nanostructures. Atomic and electronic properties of different systems have been investigated using methods of electron diffraction, scanning tunneling microscopy and photoelectron spectroscopy. Implementation of the STM technique (including design, construction, and tuning of the UHV experimental set-up) has been done in the framework of present work. This time-consuming work is reported to greater detail in the experimental part of this Thesis. The scientific part starts from the study of quantum-size effects in the electronic structure of a two-dimensional Ag film on the supporting substrate Ni(111). Distinct quantum well states in the sp-band of Ag were observed in photoelectron spectra. Analysis of thickness- and angle-dependent photoemission supplies novel information on the properties of the interface. For the first time the Ni(111) relative band gap was indirectly probed in the ground-state through the electronic structure of quantum well states in the adlayer. This is particularly important for Ni where valence electrons are strongly correlated. Comparison of the experiment with calculations performed in the formalism of the extended phase accumulation model gives the substrate gap which is fully consistent with the one obtained by ab-initio LDA calculations. It is, however, in controversy to the band structure of Ni measured directly by photoemission. These results lend credit to the simplest view of photoemission from Ni, assigning early observed contradictions between theory and experiments to electron correlation effects in the final state of photoemission. Further, nanosystems of lower dimensionality have been studied. Stepped surfaces W(331) and W(551) were used as one-dimensional model systems and as templates for self-organization of Au nanoclusters. Photon energy dependent photoemission revealed a surface resonance which was never observed before on W(110) which is the base plane of the terrace microsurfaces. The dispersion E(k) of this state measured on stepped W(331) and W(551) with angle-resolved photoelectron spectroscopy is modified by a strong umklapp effect. It appears as two parabolas shifted symmetrically relative to the microsurface normal by half of the Brillouin zone of the step superlattice. The reported results are very important for understanding of the electronic properties of low-dimensional nanostructures. It was also established that W(331) and W(551) can serve as templates for self-organization of metallic nanostructures. A combined study of electronic and atomic properties of sub-monolayer amounts of gold deposited on these templates have shown that if the substrate is slightly pre-oxidized and the temperature is elevated, then Au can alloy with the first monolayer of W. As a result, a nanostructure of uniform clusters of a surface alloy is produced all over the steps. Such clusters feature a novel sp-band in the vicinity of the Fermi level, which appears split into constant energy levels due to effects of lateral quantization. The last and main part of this work is devoted to large-scale reconstructions on surfaces and nanostructures self-assembled on top. The two-dimensional surface carbide W(110)/C-R(15x3) has been extensively investigated. Photoemission studies of quantum size effects in the electronic structure of this reconstruction, combined with an investigation of its surface geometry, lead to an advanced structural model of the carbide overlayer. It was discovered that W(110)/C-R(15x3) can control self-organization of adlayers into nanostructures with extremely different electronic and structural properties. Thus, it was established that at elevated temperature the R(15x3) superstructure controls the self-assembly of sub-monolayer amounts of Au into nm-wide nanostripes. Based on the results of core level photoemission, the R(15x3)-induced surface alloying which takes place between Au and W can be claimed as driving force of self-organization. The observed stripes exhibit a characteristic one-dimensional electronic structure with laterally quantized d-bands. Obviously, these are very important for applications, since dimensions of electronic devices have already stepped into the nm-range, where quantum-size phenomena must undoubtedly be considered. Moreover, formation of perfectly uniform molecular clusters of C60 was demonstrated and described in terms of the van der Waals formalism. It is the first experimental observation of two-dimensional fullerene nanoclusters with "magic numbers". Calculations of the cluster potentials using the static approach have revealed characteristic minima in the interaction energy. They are achieved for 4 and 7 molecules per cluster. The obtained "magic numbers" and the corresponding cluster structures are fully consistent with the results of the STM measurements.
Percolation process, which is intrinsically a phase transition process near the critical point, is ubiquitous in nature. Many of its applications embrace a wide spectrum of natural phenomena ranging from the forest fires, spread of contagious diseases, social behaviour dynamics to mathematical finance, formation of bedrocks and biological systems. The topology generated by the percolation process near the critical point is a random (stochastic) fractal. It is fundamental to the percolation theory that near the critical point, a unique infinite fractal structure, namely the infinite cluster, would emerge. As de Gennes suggested, the properties of the infinite cluster could be deduced by studying the dynamical behaviour of the random walk process taking place on it. He coined the term the ant in the labyrinth. The random walk process on such an infinite fractal cluster exhibits a subdiffusive dynamics in the sense that the mean squared displacement grows as ~t2/dw, where dw, called the fractal dimension of the random walk path, is greater than 2. Thus, the random walk process on the infinite cluster is classified as a process exhibiting the properties of anomalous diffusions. Yet near the critical point, the infinite cluster is not the sole emergent topology, but it coexists with other clusters whose size is finite. Though finite, on specific length scales these finite clusters exhibit fractal properties as well. In this work, it is assumed that the random walk process could take place on these finite size objects as well. Bearing this assumption in mind requires one address the non-equilibrium initial condition. Due to the lack of knowledge on the propagator of the random walk process in stochastic random environments, a phenomenological correspondence between the renowned Ornstein-Uhlenbeck process and the random walk process on finite size clusters is established. It is elucidated that when an ensemble of these finite size clusters and the infinite cluster is considered, the anisotropy and size of these finite clusters effects the mean squared displacement and its time averaged counterpart to grow in time as ~t(d+df (t-2))/dw, where d is the embedding Euclidean dimension, df is the fractal dimension of the infinite cluster, and , called the Fisher exponent, is a critical exponent governing the power-law distribution of the finite size clusters. Moreover, it is demonstrated that, even though the random walk process on a specific finite size cluster is ergodic, it exhibits a persistent non-ergodic behaviour when an ensemble of finite size and the infinite clusters is considered.
Over the last decades, the Arctic regions of the earth have warmed at a rate 2–3 times faster than the global average– a phenomenon called Arctic Amplification. A complex, non-linear interplay of physical processes and unique pecularities in the Arctic climate system is responsible for this, but the relative role of individual processes remains to be debated. This thesis focuses on the climate change and related processes on Svalbard, an archipelago in the North Atlantic sector of the Arctic, which is shown to be a "hotspot" for the amplified recent warming during winter. In this highly dynamical region, both oceanic and atmospheric large-scale transports of heat and moisture interfere with spatially inhomogenous surface conditions, and the corresponding energy exchange strongly shapes the atmospheric boundary layer. In the first part, Pan-Svalbard gradients in the surface air temperature (SAT) and sea ice extent (SIE) in the fjords are quantified and characterized. This analysis is based on observational data from meteorological stations, operational sea ice charts, and hydrographic observations from the adjacent ocean, which cover the 1980–2016 period. It is revealed that typical estimates of SIE during late winter range from 40–50% (80–90%) in the western (eastern) parts of Svalbard. However, strong SAT warming during winter of the order of 2–3K per decade dictates excessive ice loss, leaving fjords in the western parts essentially ice-free in recent winters. It is further demostrated that warm water currents on the west coast of Svalbard, as well as meridional winds contribute to regional differences in the SIE evolution. In particular, the proximity to warm water masses of the West Spitsbergen Current can explain 20–37% of SIE variability in fjords on west Svalbard, while meridional winds and associated ice drift may regionally explain 20–50% of SIE variability in the north and northeast. Strong SAT warming has overruled these impacts in recent years, though.
In the next part of the analysis, the contribution of large-scale atmospheric circulation changes to the Svalbard temperature development over the last 20 years is investigated. A study employing kinematic air-back trajectories for Ny-Ålesund reveals a shift in the source regions of lower-troposheric air over time for both the winter and the summer season. In winter, air in the recent decade is more often of lower-latitude Atlantic origin, and less frequent of Arctic origin. This affects heat- and moisture advection towards Svalbard, potentially manipulating clouds and longwave downward radiation in that region. A closer investigation indicates that this shift during winter is associated with a strengthened Ural blocking high and Icelandic low, and contributes about 25% to the observed winter warming on Svalbard over the last 20 years. Conversely, circulation changes during summer include a strengthened Greenland blocking high which leads to more frequent cold air advection from the central Arctic towards Svalbard, and less frequent air mass origins in the lower latitudes of the North Atlantic. Hence, circulation changes during winter are shown to have an amplifying effect on the recent warming on Svalbard, while summer circulation changes tend to mask warming.
An observational case study using upper air soundings from the AWIPEV research station in Ny-Ålesund during May–June 2017 underlines that such circulation changes during summer are associated with tropospheric anomalies in temperature, humidity and boundary layer height.
In the last part of the analysis, the regional representativeness of the above described changes around Svalbard for the broader Arctic is investigated. Therefore, the terms in the diagnostic temperature equation in the Arctic-wide lower troposphere are examined for the Era-Interim atmospheric reanalysis product. Significant positive trends in diabatic heating rates, consistent with latent heat transfer to the atmosphere over regions of increasing ice melt, are found for all seasons over the Barents/Kara Seas, and in individual months in the vicinity of Svalbard. The above introduced warm (cold) advection trends during winter (summer) on Svalbard are successfully reproduced. Regarding winter, they are regionally confined to the Barents Sea and Fram Strait, between 70°–80°N, resembling a unique feature in the whole Arctic. Summer cold advection trends are confined to the area between eastern Greenland and Franz Josef Land, enclosing Svalbard.
Transport processes in and of cells are of major importance for the survival of the organism. Muscles have to be able to contract, chromosomes have to be moved to opposing ends of the cell during mitosis, and organelles, which are compartments enclosed by membranes, have to be transported along molecular tracks. Molecular motors are proteins whose main task is moving other molecules.For that purpose they transform the chemical energy released in the hydrolysis of ATP into mechanical work. The motors of the cytoskeleton belong to the three super families myosin, kinesin and dynein. Their tracks are filaments of the cytoskeleton, namely actin and the microtubuli. Here, we examine stochastic models which are used for describing the movements of these linear molecular motors. The scale of the movements comprises the regime of single steps of a motor protein up to the directed walk along a filament. A single step bridges around 10 nm, depending on the protein, and takes about 10 ms, if there is enough ATP available. Our models comprise M states or conformations the motor can attain during its movement along a one-dimensional track. At K locations along the track transitions between the states are possible. The velocity of the protein depending on the transition rates between the single states can be determined analytically. We calculate this velocity for systems of up to four states and locations and are able to derive a number of rules which are helpful in estimating the behaviour of an arbitrary given system. Beyond that we have a look at decoupled subsystems, i.e., one or a couple of states which have no connection to the remaining system. With a certain probability a motor undergoes a cycle of conformational changes, with another probability an independent other cycle. Active elements in real transport processes by molecular motors will not be limited to the transitions between the states. In distorted networks or starting from the discrete Master equation of the system, it is possible to specify horizontal rates, too, which furthermore no longer have to fulfill the conditions of detailed balance. Doing so, we obtain unique, complete paths through the respective network and rules for the dependence of the total current on all the rates of the system. Besides, we view the time evolutions for given initial distributions. In enzymatic reactions there is the idea of a main pathway these reactions follow preferably. We determine optimal paths and the maximal flow for given networks. In order to specify the dependence of the motor's velocity on its fuel ATP, we have a look at possible reaction kinetics determining the connection between unbalanced transitions rates and ATP-concentration. Depending on the type of reaction kinetics and the number of unbalanced rates, we obtain qualitatively different curves connecting the velocity to the ATP-concentration. The molecular interaction potentials the motor experiences on its way along its track are unknown. We compare different simple potentials and the effects the localization of the vertical rates in the network model has on the transport coefficients in comparison to other models.
Recurrence plots, a rather promising tool of data analysis, have been introduced by Eckman et al. in 1987. They visualise recurrences in phase space and give an overview about the system's dynamics. Two features have made the method rather popular. Firstly they are rather simple to compute and secondly they are putatively easy to interpret. However, the straightforward interpretation of recurrence plots for some systems yields rather surprising results. For example indications of low dimensional chaos have been reported for stock marked data, based on recurrence plots. In this work we exploit recurrences or ``naturally occurring analogues'' as they were termed by E. Lorenz, to obtain three key results. One of which is that the most striking structures which are found in recurrence plots are hinged to the correlation entropy and the correlation dimension of the underlying system. Even though an eventual embedding changes the structures in recurrence plots considerably these dynamical invariants can be estimated independently of the special parameters used for the computation. The second key result is that the attractor can be reconstructed from the recurrence plot. This means that it contains all topological information of the system under question in the limit of long time series. The graphical representation of the recurrences can also help to develop new algorithms and exploit specific structures. This feature has helped to obtain the third key result of this study. Based on recurrences to points which have the same ``recurrence structure'', it is possible to generate surrogates of the system which capture all relevant dynamical characteristics, such as entropies, dimensions and characteristic frequencies of the system. These so generated surrogates are shadowed by a trajectory of the system which starts at different initial conditions than the time series in question. They can be used then to test for complex synchronisation.
Recurrences in past climates
(2023)
Our ability to predict the state of a system relies on its tendency to recur to states it has visited before. Recurrence also pervades common intuitions about the systems we are most familiar with: daily routines, social rituals and the return of the seasons are just a few relatable examples. To this end, recurrence plots (RP) provide a systematic framework to quantify the recurrence of states. Despite their conceptual simplicity, they are a versatile tool in the study of observational data. The global climate is a complex system for which an understanding based on observational data is not only of academical relevance, but vital for the predurance of human societies within the planetary boundaries. Contextualizing current global climate change, however, requires observational data far beyond the instrumental period. The palaeoclimate record offers a valuable archive of proxy data but demands methodological approaches that adequately address its complexities. In this regard, the following dissertation aims at devising novel and further developing existing methods in the framework of recurrence analysis (RA). The proposed research questions focus on using RA to capture scale-dependent properties in nonlinear time series and tailoring recurrence quantification analysis (RQA) to characterize seasonal variability in palaeoclimate records (‘Palaeoseasonality’).
In the first part of this thesis, we focus on the methodological development of novel approaches in RA. The predictability of nonlinear (palaeo)climate time series is limited by abrupt transitions between regimes that exhibit entirely different dynamical complexity (e.g. crossing of ‘tipping points’). These possibly depend on characteristic time scales. RPs are well-established for detecting transitions and capture scale-dependencies, yet few approaches have combined both aspects. We apply existing concepts from the study of self-similar textures to RPs to detect abrupt transitions, considering the most relevant time scales. This combination of methods further results in the definition of a novel recurrence based nonlinear dependence measure. Quantifying lagged interactions between multiple variables is a common problem, especially in the characterization of high-dimensional complex systems. The proposed ‘recurrence flow’ measure of nonlinear dependence offers an elegant way to characterize such couplings. For spatially extended complex systems, the coupled dynamics of local variables result in the emergence of spatial patterns. These patterns tend to recur in time. Based on this observation, we propose a novel method that entails dynamically distinct regimes of atmospheric circulation based on their recurrent spatial patterns. Bridging the two parts of this dissertation, we next turn to methodological advances of RA for the study of Palaeoseasonality. Observational series of palaeoclimate ‘proxy’ records involve inherent limitations, such as irregular temporal sampling. We reveal biases in the RQA of time series with a non-stationary sampling rate and propose a correction scheme.
In the second part of this thesis, we proceed with applications in Palaeoseasonality. A review of common and promising time series analysis methods shows that numerous valuable tools exist, but their sound application requires adaptions to archive-specific limitations and consolidating transdisciplinary knowledge. Next, we study stalagmite proxy records from the Central Pacific as sensitive recorders of mid-Holocene El Niño-Southern Oscillation (ENSO) dynamics. The records’ remarkably high temporal resolution allows to draw links between ENSO and seasonal dynamics, quantified by RA. The final study presented here examines how seasonal predictability could play a role for the stability of agricultural societies. The Classic Maya underwent a period of sociopolitical disintegration that has been linked to drought events. Based on seasonally resolved stable isotope records from Yok Balum cave in Belize, we propose a measure of seasonal predictability. It unveils the potential role declining seasonal predictability could have played in destabilizing agricultural and sociopolitical systems of Classic Maya populations.
The methodological approaches and applications presented in this work reveal multiple exciting future research avenues, both for RA and the study of Palaeoseasonality.
One of the most striking features of ecological systems is their ability to undergo sudden outbreaks in the population numbers of one or a small number of species. The similarity of outbreak characteristics, which is exhibited in totally different and unrelated (ecological) systems naturally leads to the question whether there are universal mechanisms underlying outbreak dynamics in Ecology. It will be shown into two case studies (dynamics of phytoplankton blooms under variable nutrients supply and spread of epidemics in networks of cities) that one explanation for the regular recurrence of outbreaks stems from the interaction of the natural systems with periodical variations of their environment. Natural aquatic systems like lakes offer very good examples for the annual recurrence of outbreaks in Ecology. The idea whether chaos is responsible for the irregular heights of outbreaks is central in the domain of ecological modeling. This question is investigated in the context of phytoplankton blooms. The dynamics of epidemics in networks of cities is a problem which offers many ecological and theoretical aspects. The coupling between the cities is introduced through their sizes and gives rise to a weighted network which topology is generated from the distribution of the city sizes. We examine the dynamics in this network and classified the different possible regimes. It could be shown that a single epidemiological model can be reduced to a one-dimensional map. We analyze in this context the dynamics in networks of weighted maps. The coupling is a saturation function which possess a parameter which can be interpreted as an effective temperature for the network. This parameter allows to vary continously the network topology from global coupling to hierarchical network. We perform bifurcation analysis of the global dynamics and succeed to construct an effective theory explaining very well the behavior of the system.
In this thesis the magnetohydrodynamic jet formation and the effects of magnetic diffusion on the formation of axisymmetric protostellar jets have been investigated in three different simulation sets. The time-dependent numerical simulations have been performed, using the magnetohydrodynamic ZEUS-3D code.
The problem under consideration in the thesis is a two level atom in a photonic crystal and a pumping laser. The photonic crystal provides an environment for the atom, that modifies the decay of the exited state, especially if the atom frequency is close to the band gap. The population inversion is investigated als well as the emission spectrum. The dynamics is analysed in the context of open quantum systems. Due to the multiple reflections in the photonic crystal, the system has a finite memory that inhibits the Markovian approximation. In the Heisenberg picture the equations of motion for the system variables form a infinite hierarchy of integro-differential equations. To get a closed system, approximations like a weak coupling approximation are needed. The thesis starts with a simple photonic crystal that is amenable to analytic calculations: a one-dimensional photonic crystal, that consists of alternating layers. The Bloch modes inside and the vacuum modes outside a finite crystal are linked with a transformation matrix that is interpreted as a transfer matrix. Formulas for the band structure, the reflection from a semi-infinite crystal, and the local density of states in absorbing crystals are found; defect modes and negative refraction are discussed. The quantum optics section of the work starts with the discussion of three problems, that are related to the full resonance fluorescence problem: a pure dephasing model, the driven atom and resonance fluorescence in free space. In the lowest order of the system-environment coupling, the one-time expectation values for the full problem are calculated analytically and the stationary states are discussed for certain cases. For the calculation of the two time correlation functions and spectra, the additional problem of correlations between the two times appears. In the Markovian case, the quantum regression theorem is valid. In the general case, the fluctuation dissipation theorem can be used instead. The two-time correlation functions are calculated by the two different methods. Within the chosen approximations, both methods deliver the same result. Several plots show the dependence of the spectrum on the parameters. Some examples for squeezing spectra are shown with different approximations. A projection operator method is used to establish two kinds of Markovian expansion with and without time convolution. The lowest order is identical with the lowest order of system environment coupling, but higher orders give different results.
LCST-type synthetic thermoresponsive polymers can reversibly respond to certain stimuli in aqueous media with a massive change of their physical state. When fluorophores, that are sensitive to such changes, are incorporated into the polymeric structure, the response can be translated into a fluorescence signal. Based on this idea, this thesis presents sensing schemes which transduce the stimuli-induced variations in the solubility of polymer chains with covalently-bound fluorophores into a well-detectable fluorescence output. Benefiting from the principles of different photophysical phenomena, i.e. of fluorescence resonance energy transfer and solvatochromism, such fluorescent copolymers enabled monitoring of stimuli such as the solution temperature and ionic strength, but also of association/disassociation mechanisms with other macromolecules or of biochemical binding events through remarkable changes in their fluorescence properties. For instance, an aqueous ratiometric dual sensor for temperature and salts was developed, relying on the delicate supramolecular assembly of a thermoresponsive copolymer with a thiophene-based conjugated polyelectrolyte. Alternatively, by taking advantage of the sensitivity of solvatochromic fluorophores, an increase in solution temperature or the presence of analytes was signaled as an enhancement of the fluorescence intensity. A simultaneous use of the sensitivity of chains towards the temperature and a specific antibody allowed monitoring of more complex phenomena such as competitive binding of analytes. The use of different thermoresponsive polymers, namely poly(N-isopropylacrylamide) and poly(meth)acrylates bearing oligo(ethylene glycol) side chains, revealed that the responsive polymers differed widely in their ability to perform a particular sensing function. In order to address questions regarding the impact of the chemical structure of the host polymer on the sensing performance, the macromolecular assembly behavior below and above the phase transition temperature was evaluated by a combination of fluorescence and light scattering methods. It was found that although the temperature-triggered changes in the macroscopic absorption characteristics were similar for these polymers, properties such as the degree of hydration or the extent of interchain aggregations differed substantially. Therefore, in addition to the demonstration of strategies for fluorescence-based sensing with thermoresponsive polymers, this work highlights the role of the chemical structure of the two popular thermoresponsive polymers on the fluorescence response. The results are fundamentally important for the rational choice of polymeric materials for a specific sensing strategy.
Robotic telescopes & Doppler imaging : measuring differential rotation on long-period active stars
(2004)
The sun shows a wide variety of magnetic-activity related phenomena. The magnetic field responsible for this is generated by a dynamo process which is believed to operate in the tachocline, which is located at the bottom of the convection zone. This dynamo is driven in part by differential rotation and in part by magnetic turbulences in the convection zone. The surface differential rotation, one key ingredient of dynamo theory, can be measured by tracing sunspot positions.To extend the parameter space for dynamo theories, one can extend these measurements to other stars than the sun. The primary obstacle in this endeavor is the lack of resolved surface images on other stars. This can be overcome by the Doppler imaging technique, which uses the rotation-induced Doppler-broadening of spectral lines to compute the surface distribution of a physical parameter like temperature. To obtain the surface image of a star, high-resolution spectroscopic observations, evenly distributed over one stellar rotation period are needed. This turns out to be quite complicated for long period stars. The upcoming robotic observatory STELLA addresses this problem with a dedicated scheduling routine, which is tailored for Doppler imaging targets. This will make observations for Doppler imaging not only easier, but also more efficient.As a preview of what can be done with STELLA, we present results of a Doppler imaging study of seven stars, all of which show evidence for differential rotation, but unfortunately the errors are of the same order of magnitude as the measurements due to unsatisfactory data quality, something that will not happen on STELLA. Both, cross-correlation analysis and the sheared image technique where used to double check the results if possible. For four of these stars, weak anti-solar differential rotation was found in a sense that the pole rotates faster than the equator, for the other three stars weak differential rotation in the same direction as on the sun was found.Finally, these new measurements along with other published measurements of differential rotation using Doppler imaging, were analyzed for correlations with stellar evolution, binarity, and rotation period. The total sample of stars show a significant correlation with rotation period, but if separated into antisolar and solar type behavior, only the subsample showing anti-solar differential rotation shows this correlation. Additionally, there is evidence for binary stars showing less differential rotation as single stars, as is suggested by theory. All other parameter combinations fail to deliver any results due to the still small sample of stars available.
Extreme weather events like heatwaves and floods severely affect societies with impacts ranging from economic damages to losses in human lifes. Global warming caused by anthropogenic greenhouse gas emissions is expected to increase their frequency and intensity, particularly in the warm season. Next to these thermodynamic changes, climate change might also impact the large scale atmospheric circulation.Such dynamic changes might additionally act on the occurence of extreme weather events, but involved mechanisms are often highly non-linear. Therefore, large uncertainty exists on the exact nature of these changes and the related risks to society. Particularly in the densely populated mid-latitudes weather patterns are governed by the large scale circulation like the jet-streams and storm tracks. Extreme weather in this region is often related to persistent weather systems associated with a strongly meandering jet-stream. Such meanders are called Rossby waves. Under specific conditions they can become slow moving, stretched around the entire hemisphere and generate simultaneaous heat- and rainfall extremes in far-away regions.
This thesis aims at enhancing the understanding of synoptic-scale, circumglobal Rossby waves and the associated risks of dynamical changes to society. More specific, the analyses investigate their relation to extreme weather, regions at risk, under which conditions they are generated, and the influence of anthropogenic climate change on those conditions now, in the past and in the future.
I find that circumglobal Rossby waves promoted simultaneous occuring weather extremes across the northern hemisphere in several recent summers. Further, I present evidence that they are often linked to quasiresonant-amplification of planetary waves. These events include the 2003 European heatwave and the Moscow heatwave of 2010. This non-linear mechanism acts on the upper level flow through trapping and amplification of stationary synoptic scale waves. I show that this resonance mechanism acts in both hemispheres and is related to extreme weather. A main finding is that circumglobal Rossby waves primarily occur as two specific teleconnection patterns associated with a wave 5 and wave 7 pattern in the northern hemisphere, likely due to the favourable longitudinal distance of prominent mountain ridges here. Furthermore, I identify those regions which are particularly at risk: The central United States, western Europe and the Ukraine/Russian region. Moreover, I present evidence that the wave 7 pattern has and extreme weather in these regions. My results suggest that the increase in frequency can be linked to favourable changes in large scale temperature gradients, which I show to be largely underestimated by model simulations. Using surface temperature fingerprint as proxy for investigating historic and future model ensembles, evidence is presented that anthropogenic warming has likely increased the probability for the occurence of circumglobal Rossby waves. Further it is shown that this might lead to a doubling of such events until the end of the century under a high-emission scenario.
Overall, this thesis establishes several atmosphere-dynamical pathways by which changes in large scale temperature gradients might link to persistent boreal summer weather. It highlights the societal risks associated with the increasing occurence of a newly discovered Rossby wave teleconnection pattern, which has the potential to cause simultaneaous heat-extremes in the mid-latitudinal bread-basket regions. In addition, it provides further evidence that the traditional picture by which quasi-stationary Rossby waves occur only in the low wavenumber regime, should be reconsidered.
Samarium hexaboride
(2018)
Subject of this work is the investigation of universal scaling laws which are observed in coupled chaotic systems. Progress is made by replacing the chaotic fluctuations in the perturbation dynamics by stochastic processes. First, a continuous-time stochastic model for weakly coupled chaotic systems is introduced to study the scaling of the Lyapunov exponents with the coupling strength (coupling sensitivity of chaos). By means of the the Fokker-Planck equation scaling relations are derived, which are confirmed by results of numerical simulations. Next, the new effect of avoided crossing of Lyapunov exponents of weakly coupled disordered chaotic systems is described, which is qualitatively similar to the energy level repulsion in quantum systems. Using the scaling relations obtained for the coupling sensitivity of chaos, an asymptotic expression for the distribution function of small spacings between Lyapunov exponents is derived and compared with results of numerical simulations. Finally, the synchronization transition in strongly coupled spatially extended chaotic systems is shown to resemble a continuous phase transition, with the coupling strength and the synchronization error as control and order parameter, respectively. Using results of numerical simulations and theoretical considerations in terms of a multiplicative noise partial differential equation, the universality classes of the observed two types of transition are determined (Kardar-Parisi-Zhang equation with saturating term, directed percolation).
In the western hemisphere, the piano is one of the most important instruments. While its evolution lasted for more than three centuries, and the most important physical aspects have already been investigated, some parts in the characterization of the piano remain not well understood. Considering the pivotal piano soundboard, the effect of ribs mounted on the board exerted on the sound radiation and propagation in particular, is mostly neglected in the literature. The present investigation deals exactly with the sound wave propagation effects that emerge in the presence of an array of equally-distant mounted ribs at a soundboard. Solid-state theory proposes particular eigenmodes and -frequencies for such arrangements, which are comparable to single units in a crystal. Following this 'linear chain model' (LCM), differences in the frequency spectrum are observable as a distinct band structure. Also, the amplitudes of the modes are changed, due to differences of the damping factor. These scattering effects were not only investigated for a well-understood conceptional rectangular soundboard (multichord), but also for a genuine piano resonance board manufactured by the piano maker company 'C. Bechstein Pianofortefabrik'. To obtain the possibility to distinguish between the characterizing spectra both with and without mounted ribs, the typical assembly plan for the Bechstein instrument was specially customized. Spectral similarities and differences between both boards are found in terms of damping and tone. Furthermore, specially prepared minimal-invasive piezoelectric polymer sensors made from polyvinylidene fluoride (PVDF) were used to record solid-state vibrations of the investigated system. The essential calibration and characterization of these polymer sensors was performed by determining the electromechanical conversion, which is represented by the piezoelectric coefficient. Therefore, the robust 'sinusoidally varying external force' method was applied, where a dynamic force perpendicular to the sensor's surface, generates movable charge carriers. Crucial parameters were monitored, with the frequency response function as the most important one for acousticians. Along with conventional condenser microphones, the sound was measured as solid-state vibration as well as airborne wave. On this basis, statements can be made about emergence, propagation, and also the overall radiation of the generated modes of the vibrating system. Ultimately, these results acoustically characterize the entire system.
Search for light primordial black holes with VERITAS using gamma γ-ray and optical observations
(2023)
The Very Energetic Radiation Imaging Telescope Array System (VERITAS) is an array of four imaging atmospheric Cherenkov telescopes (IACTs). VERITAS is sensitive to very-high-energy gamma-rays in the range of 100 GeV to >30 TeV. Hypothesized primordial black holes (PBHs) are attractive targets for IACTs. If they exist, their potential cosmological impact reaches beyond the candidacy for constituents of dark matter. The sublunar mass window is the largest unconstrained range of PBH masses. This thesis aims to develop novel concepts searching for light PBHs with VERITAS. PBHs below the sublunar window lose mass due to Hawking radiation. They would evaporate at the end of their lifetime, leading to a short burst of gamma-rays. If PBHs formed at about 10^15 g, the evaporation would occur nowadays. Detecting these signals might not only confirm the existence of PBHs but also prove the theory of Hawking radiation. This thesis probes archival VERITAS data recorded between 2012 and 2021 for possible PBH signals. This work presents a new automatic approach to assess the quality of the VERITAS data. The array-trigger rate and far infrared temperature are well suited to identify periods with poor data quality. These are masked by time cuts to obtain a consistent and clean dataset which contains about 4222 hours. The PBH evaporations could occur at any location in the field of view or time within this data. Only a blind search can be performed to identify these short signals. This thesis implements a data-driven deep learning based method to search for short transient signals with VERITAS. It does not depend on the modelling of the effective area and radial acceptance. This work presents the first application of this method to actual observational IACT data. This thesis develops new concepts dealing with the specifics of the data and the transient detection method. These are reflected in the developed data preparation pipeline and search strategies. After correction for trial factors, no candidate PBH evaporation is found in the data. Thus, new constraints of the local rate of PBH evaporations are derived. At the 99% confidence limit it is below <1.07 * 10^5 pc^-3 yr^-1. This constraint with the new, independent analysis approach is in the range of existing limits for the evaporation rate.
This thesis also investigates an alternative novel approach to searching for PBHs with IACTs. Above the sublunar window, the PBH abundance is constrained by optical microlensing studies. The sampling speed, which is of order of minutes to hours for traditional optical telescopes, is a limiting factor in expanding the limits to lower masses. IACTs are also powerful instruments for fast transient optical astronomy with up to O(ns) sampling. This thesis investigates whether IACTs might constrain the sublunar window with optical microlensing observations. This study confirms that, in principle, the fast sampling speed might allow extending microlensing searches into the sublunar mass window. However, the limiting factor for IACTs is the modest sensitivity to detect changes in optical fluxes. This thesis presents the expected rate of detectable events for VERITAS as well as prospects of possible future next-generation IACTs. For VERITAS, the rate of detectable microlensing events in the sublunar range is ~10^-6 per year of observation time. The future prospects for a 100 times more sensitive instrument are at ~0.05 events per year.
The presented work describes new concepts of fast switching elements based on principles of photonics. The waveguides working in visible and infra-red ranges are put in a basis of these elements. And as materials for manufacturing of waveguides the transparent polymers, dopped by molecules of the dyes possessing second order nonlinear-optical properties are proposed. The work shows how nonlinear-optical processes in such structures can be implemented by electro-optical and opto-optical control circuit signals. In this paper we consider the complete cycle of fabrication of several types of integral photonic elements. The theoretical analysis of high-intensity beam propagation in media with second-order optical nonlinearity is performed. Quantitative estimations of necessary conditions of occurrence of the nonlinear-optical phenomena of the second order taking into account properties of used materials are made. The paper describes the various stages of manufacture of the basic structure of the integrated photonics: a planar waveguide. Using the finite element method the structure of the electromagnetic field inside the waveguide in different modes was analysed. A separate part of the work deals with the creation of composite organic materials with high optical nonlinearity. Using the methods of quantum chemistry, the dependence of nonlinear properties of dye molecules from its structure were investigated in details. In addition, the paper discusses various methods of inducing of an optical nonlinearity in dye-doping of polymer films. In the work, for the first time is proposed the use of spatial modulation of nonlinear properties of waveguide according Fibonacci law. This allows involving several different nonlinear optical processes simultaneously. The final part of the work describes various designs of integrated optical modulators and switches constructed of organic nonlinear optical waveguides. A practical design of the optical modulator based on Mach-Zehnder interferometer made by a photolithography on polymer film is presented.
Semi-empirical sea-level models (SEMs) exploit physically motivated empirical relationships between global sea level and certain drivers, in the following global mean temperature. This model class evolved as a supplement to process-based models (Rahmstorf (2007)) which were unable to fully represent all relevant processes. They thus failed to capture past sea-level change (Rahmstorf et al. (2012)) and were thought likely to underestimate future sea-level rise. Semi-empirical models were found to be a fast and useful tool for exploring the uncertainties in future sea-level rise, consistently giving significantly higher projections than process-based models.
In the following different aspects of semi-empirical sea-level modelling have been studied. Models were first validated using various data sets of global sea level and temperature. SEMs were then used on the glacier contribution to sea level, and to infer past global temperature from sea-level data via inverse modelling. Periods studied encompass the instrumental period, covered by tide gauges (starting 1700 CE (Common Era) in Amsterdam) and satellites (first launched in 1992 CE), the era from 1000 BCE (before CE) to present, and the full length of the Holocene (using proxy data). Accordingly different data, model formulations and implementations have been used. It could be shown in Bittermann et al. (2013) that SEMs correctly predict 20th century sea-level when calibrated with data until 1900 CE. SEMs also turned out to give better predictions than the Intergovernmental Panel on Climate Change (IPCC) 4th assessment report (AR4, IPCC (2007)) models, for the period from 1961–2003 CE.
With the first multi-proxy reconstruction of global sea-level as input, estimate of the human-induced component of modern sea-level change and projections of future sea-level rise were calculated (Kopp et al. (2016)). It turned out with 90% confidence that more than 40 % of the observed 20th century sea-level rise is indeed anthropogenic. With the new semi-empirical and IPCC (2013) 5th assessment report (AR5) projections the gap between SEM and process-based model projections closes, giving higher credibility to both. Combining all scenarios, from strong mitigation to business as usual, a global sea-level rise of 28–131 cm relative to 2000 CE, is projected with 90% confidence. The decision for a low carbon pathway could halve the expected global sea-level rise by 2100 CE.
Present day temperature and thus sea level are driven by the globally acting greenhouse-gas forcing. Unlike that, the Milankovich forcing, acting on Holocene timescales, results mainly in a northern-hemisphere temperature change. Therefore a semi-empirical model can be driven with northernhemisphere temperatures, which makes it possible to model the main subcomponent of sea-level change over this period. It showed that an additional positive constant rate of the order of the estimated Antarctic sea-level contribution is then required to explain the sea-level evolution over the Holocene. Thus the global sea level, following the climatic optimum, can be interpreted as the sum of a temperature induced sea-level drop and a positive long-term contribution, likely an ongoing response to deglaciation coming from Antarctica.
This thesis contains several theoretical studies on optomechanical systems, i.e. physical devices where mechanical degrees of freedom are coupled with optical cavity modes. This optomechanical interaction, mediated by radiation pressure, can be exploited for cooling and controlling mechanical resonators in a quantum regime. The goal of this thesis is to propose several new ideas for preparing meso- scopic mechanical systems (of the order of 10^15 atoms) into highly non-classical states. In particular we have shown new methods for preparing optomechani-cal pure states, squeezed states and entangled states. At the same time, proce-dures for experimentally detecting these quantum effects have been proposed. In particular, a quantitative measure of non classicality has been defined in terms of the negativity of phase space quasi-distributions. An operational al- gorithm for experimentally estimating the non-classicality of quantum states has been proposed and successfully applied in a quantum optics experiment. The research has been performed with relatively advanced mathematical tools related to differential equations with periodic coefficients, classical and quantum Bochner’s theorems and semidefinite programming. Nevertheless the physics of the problems and the experimental feasibility of the results have been the main priorities.
A polymer is a large molecule made up of many elementary chemical units, joined together by covalent bonds (for example, polyethylene). Polyelectrolytes (PELs) are polymer chains containing a certain amount of ionizable monomers. With their specific properties PELs acquire big importance in molecular and cell biology as well as in technology. Compared to neutral polymers the theory of PELs is less understood. In particular, this is valid for PELs in poor solvents. A poor solvent environment causes an effective attraction between monomers. Hence, for PELs in a poor solvent, there occurs a competition between attraction and repulsion. Strong or quenched PELs are completely dissociated at any accessible pH. The position of charges along the chain is fixed by chemical synthesis. On the other hand, in weak or annealed PELs dissociation of charges depends on solution pH. For the first time the simulation results have given direct evidence that at rather poor solvents an annealed PEL indeed undergoes a first-order phase transition when the chemical potential (solution pH) reaches at a certain value. The discontinuous transition occurs between a weakly charged compact globular structure and a strongly charged stretched configuration. At not too poor solvents theory predicts that globule would become unstable with respect to the formation of pearl-necklaces. The results show that pearl-necklaces exist in annealed PELs indeed. Furthermore, as predicted by theory, the simulation results have shown that annealed PELs display a sharp transition from a highly charged stretched state to a weakly charged globule at a critical salt concentration.
Soft nanocomposites with enhanced electromechanical response for dielectric elastomer actuators
(2011)
Electromechanical transducers based on elastomer capacitors are presently considered for many soft actuation applications, due to their large reversible deformation in response to electric field induced electrostatic pressure. The high operating voltage of such devices is currently a large drawback, hindering their use in applications such as biomedical devices and biomimetic robots, however, they could be improved with a careful design of their material properties. The main targets for improving their properties are increasing the relative permittivity of the active material, while maintaining high electric breakdown strength and low stiffness, which would lead to enhanced electrostatic storage ability and hence, reduced operating voltage. Improvement of the functional properties is possible through the use of nanocomposites. These exploit the high surface-to-volume ratio of the nanoscale filler, resulting in large effects on macroscale properties. This thesis explores several strategies for nanomaterials design. The resulting nanocomposites are fully characterized with respect to their electrical and mechanical properties, by use of dielectric spectroscopy, tensile mechanical analysis, and electric breakdown tests. First, nanocomposites consisting of high permittivity rutile TiO2 nanoparticles dispersed in thermoplastic block copolymer SEBS (poly-styrene-coethylene-co-butylene-co-styrene) are shown to exhibit permittivity increases of up to 3.7 times, leading to 5.6 times improvement in electrostatic energy density, but with a trade-off in mechanical properties (an 8-fold increase in stiffness). The variation in both electrical and mechanical properties still allows for electromechanical improvement, such that a 27 % reduction of the electric field is found compared to the pure elastomer. Second, it is shown that the use of nanofiller conductive particles (carbon black (CB)) can lead to a strong increase of relative permittivity through percolation, however, with detrimental side effects. These are due to localized enhancement of the electric field within the composite, which leads to sharp reductions in electric field strength. Hence, the increase in permittivity does not make up for the reduction in breakdown strength in relation to stored electrical energy, which may prohibit their practical use. Third, a completely new approach for increasing the relative permittivity and electrostatic energy density of a polymer based on 'molecular composites' is presented, relying on chemically grafting soft π-conjugated macromolecules to a flexible elastomer backbone. Polarization caused by charge displacement along the conjugated backbone is found to induce a large and controlled permittivity enhancement (470 % over the elastomer matrix), while chemical bonding, encapsulates the PANI chains manifesting in hardly any reduction in electric breakdown strength, and hence resulting in a large increase in stored electrostatic energy. This is shown to lead to an improvement in the sensitivity of the measured electromechanical response (83 % reduction of the driving electric field) as well as in the maximum actuation strain (250 %). These results represent a large step forward in the understanding of the strategies which can be employed to obtain high permittivity polymer materials with practical use for electro-elastomer actuation.
In this thesis, I study ultrafast dynamics in perovskite oxides using time resolved broadband spectroscopy. I focus on the observation of coherent phonon propagation by time resolved Brillouin scattering: following the excition of metal transducer films with a femtosecond infrared pump pulse, coherent phonon dynamics in the GHz frequency range are triggered. Their propagation is monitored using a delayed white light probe pulse. The technique is illustrated on various thin films and multilayered samples. I apply the technique to investigate the linear and nonlinear acoustic response in bulk SrTiO_3, which displays a ferroelastic phase transition from a cubic to a tetragonal structural phase at T_a=105 K. In the linear regime, I observe a coupling of the observed acoustic phonon mode to the softening optic modes describing the phase transition. In the nonlinear regime, I find a giant slowing down of the sound velocity in the low temperature phase that is only observable for a strain amplitude exceeding the tetragonality of the material. It is attributed to a coupling of the high frequency phonons to ferroelastic domain walls in the material. I propose a new mechanism for the coupling of strain waves to the domain walls that is only effective for high amplitude strain. A detailed study of the phonon attenuation across a wide temperature range shows that the phonon attenuation at low temperatures is influenced by the domain configuration, which is determined by interface strain. Preliminary measurements on magnetic-ferroelectric multilayers reveal that the excitation fluence needs to be carefully controlled when dynamics at phase transitions are studied.
This thesis is focussed on the electronic properties of the new material class named topological insulators. Spin and angle resolved photoelectron spectroscopy have been applied to reveal several unique properties of the surface state of these materials. The first part of this thesis introduces the methodical background of these quite established experimental techniques.
In the following chapter, the theoretical concept of topological insulators is introduced. Starting from the prominent example of the quantum Hall effect, the application of topological invariants to classify material systems is illuminated. It is explained how, in presence of time reversal symmetry, which is broken in the quantum Hall phase, strong spin orbit coupling can drive a system into a topologically non trivial phase. The prediction of the spin quantum Hall effect in two dimensional insulators an the generalization to the three dimensional case of topological insulators is reviewed together with the first experimental realization of a three dimensional topological insulator in the Bi1-xSbx alloys given in the literature.
The experimental part starts with the introduction of the Bi2X3 (X=Se, Te) family of materials. Recent theoretical predictions and experimental findings on the bulk and surface electronic structure of these materials are introduced in close discussion to our own experimental results. Furthermore, it is revealed, that the topological surface state of Bi2Te3 shares its orbital symmetry with the bulk valence band and the observation of a temperature induced shift of the chemical potential is to a high probability unmasked as a doping effect due to residual gas adsorption.
The surface state of Bi2Te3 is found to be highly spin polarized with a polarization value of about 70% in a macroscopic area, while in Bi2Se3 the polarization appears reduced, not exceeding 50%. We, however, argue that the polarization is most likely only extrinsically limited in terms of the finite angular resolution and the lacking detectability of the out of plane component of the electron spin. A further argument is based on the reduced surface quality of the single crystals after cleavage and, for Bi2Se3 a sensitivity of the electronic structure to photon exposure.
We probe the robustness of the topological surface state in Bi2X3 against surface impurities in Chapter 5. This robustness is provided through the protection by the time reversal symmetry. Silver, deposited on the (111) surface of Bi2Se3 leads to a strong electron doping but the surface state is observed up to a deposited Ag mass equivalent to one atomic monolayer. The opposite sign of doping, i.e., hole-like, is observed by exposing oxygen to Bi2Te3. But while the n-type shift of Ag on Bi2Se3 appears to be more or less rigid, O2 is lifting the Dirac point of the topological surface state in Bi2Te3 out of the valence band minimum at $\Gamma$. After increasing the oxygen dose further, it is possible to shift the Dirac point to the Fermi level, while the valence band stays well beyond. The effect is found reversible, by warming up the samples which is interpreted in terms of physisorption of O2.
For magnetic impurities, i.e., Fe, we find a similar behavior as for the case of Ag in both Bi2Se3 and Bi2Te3. However, in that case the robustness is unexpected, since magnetic impurities are capable to break time reversal symmetry which should introduce a gap in the surface state at the Dirac point which in turn removes the protection. We argue, that the fact that the surface state shows no gap must be attributed to a missing magnetization of the Fe overlayer. In Bi2Te3 we are able to observe the surface state for deposited iron mass equivalents in the monolayer regime. Furthermore, we gain control over the sign of doping through the sample temperature during deposition.
Chapter6 is devoted to the lifetime broadening of the photoemission signal from the topological surface states of Bi2Se3 and Bi2Te3. It is revealed that the hexagonal warping of the surface state in Bi2Te3 introduces an anisotropy for electrons traveling along the two distinct high symmetry directions of the surface Brillouin zone, i.e., $\Gamma$K and $\Gamma$M. We show that the phonon coupling strength to the surface electrons in Bi2Te3 is in nice agreement with the theoretical prediction but, nevertheless, higher than one may expect. We argue that the electron-phonon coupling is one of the main contributions to the decay of photoholes but the relatively small size of the Fermi surface limits the number of phonon modes that may scatter off electrons. This effect is manifested in the energy dependence of the imaginary part of the electron self energy of the surface state which shows a decay to higher binding energies in contrast to the monotonic increase proportional to E$^2$ in the Fermi liquid theory due to electron-electron interaction.
Furthermore, the effect of the surface impurities of Chapter 5 on the quasiparticle life- times is investigated. We find that Fe impurities have a much stronger influence on the lifetimes as compared to Ag. Moreover, we find that the influence is stronger independently of the sign of the doping. We argue that this observation suggests a minor contribution of the warping on increased scattering rates in contrast to current belief. This is additionally confirmed by the observation that the scattering rates increase further with increasing silver amount while the doping stays constant and by the fact that clean Bi2Se3 and Bi2Te3 show very similar scattering rates regardless of the much stronger warping in Bi2Te3.
In the last chapter we report on a strong circular dichroism in the angle distribution of the photoemission signal of the surface state of Bi2Te3. We show that the color pattern obtained by calculating the difference between photoemission intensities measured with opposite photon helicity reflects the pattern expected for the spin polarization. However, we find a strong influence on strength and even sign of the effect when varying the photon energy. The sign change is qualitatively confirmed by means of one-step photoemission calculations conducted by our collaborators from the LMU München, while the calculated spin polarization is found to be independent of the excitation energy. Experiment and theory together unambiguously uncover the dichroism in these systems as a final state effect and the question in the title of the chapter has to be negated: Circular dichroism in the angle distribution is not a new spin sensitive technique.
The current thesis is focused on the properties of graphene supported by metallic substrates and specifically on the behaviour of electrons in such systems. Methods of scanning tunneling microscopy, electron diffraction and photoemission spectroscopy were applied to study the structural and electronic properties of graphene. The purpose of the first part of this work is to introduce the most relevant aspects of graphene physics and the methodical background of experimental techniques used in the current thesis.
The scientific part of this work starts with the extensive study by means of scanning tunneling microscopy of the nanostructures that appear in Au intercalated graphene on Ni(111). This study was aimed to explore the possible structural explanations of the Rashba-type spin splitting of ~100 meV experimentally observed in this system — much larger than predicted by theory. It was demonstrated that gold can be intercalated under graphene not only as a dense monolayer, but also in the form of well-periodic arrays of nanoclusters, a structure previously not reported. Such nanocluster arrays are able to decouple graphene from the strongly interacting Ni substrate and render it quasi-free-standing, as demonstrated by our DFT study. At the same time calculations confirm strong enhancement of the proximity-induced SOI in graphene supported by such nanoclusters in comparison to monolayer gold. This effect, attributed to the reduced graphene-Au distance in the case of clusters, provides a large Rashba-type spin splitting of ~60 meV.
The obtained results not only provide a possible mechanism of SOI enhancement in this particular system, but they can be also generalized for graphene on other strongly interacting substrates intercalated by nanostructures of heavy noble d metals.
Even more intriguing is the proximity of graphene to heavy sp-metals that were predicted to induce an intrinsic SOI and realize a spin Hall effect in graphene. Bismuth is the heaviest stable sp-metal and its compounds demonstrate a plethora of exciting physical phenomena. This was the motivation behind the next part of the current thesis, where structural and electronic properties of a previously unreported phase of Bi-intercalated graphene on Ir(111) were studied by means of scanning tunneling microscopy, spin- and angle-resolved photoemission spectroscopy and electron diffraction. Photoemission experiments revealed a remarkable, nearly ideal graphene band structure with strongly suppressed signatures of interaction between graphene and the Ir(111) substrate, moreover, the characteristic moiré pattern observed in graphene on Ir(111) by electron diffraction and scanning tunneling microscopy was strongly suppressed after intercalation. The whole set of experimental data evidences that Bi forms a dense intercalated layer that efficiently decouples graphene from the substrate. The interaction manifests itself only in the n-type charge doping (~0.4 eV) and a relatively small band gap at the Dirac point (~190 meV). The origin of this minor band gap is quite intriguing and in this work it was possible to exclude a wide range of mechanisms that could be responsible for it, such as induced intrinsic spin-orbit interaction, hybridization with the substrate states and corrugation of the graphene lattice. The main origin of the band gap was attributed to the A-B symmetry breaking and this conclusion found support in the careful analysis of the interference effects in photoemission that provided the band gap estimate of ~140 meV.
While the previous chapters were focused on adjusting the properties of graphene by proximity to heavy metals, graphene on its own is a great object to study various physical effects at crystal surfaces. The final part of this work is devoted to a study of surface scattering resonances by means of photoemission spectroscopy, where this effect manifests itself as a distinct modulation of photoemission intensity. Though scattering resonances were widely studied in the past by means of electron diffraction, studies about their observation in photoemission experiments started to appear only recently and they are very scarce.
For a comprehensive study of scattering resonances graphene was selected as a versatile model system with adjustable properties. After the theoretical and historical introduction to the topic of scattering resonances follows a detailed description of the unusual features observed in the photoemission spectra obtained in this work and finally the equivalence between these features and scattering resonances is proven. The obtained photoemission results are in a good qualitative agreement with the existing theory, as verified by our calculations in the framework of the interference model. This simple model gives a suitable explanation for the general experimental observations.
The possibilities of engineering the scattering resonances were also explored. A systematic study of graphene on a wide range of substrates revealed that the energy position of the resonances is in a direct relation to the magnitude of charge transfer between graphene and the substrate. Moreover, it was demonstrated that the scattering resonances in graphene on Ir(111) can be suppressed by nanopatterning either by a superlattice of Ir nanoclusters or by atomic hydrogen. These effects were attributed to strong local variations of tork function and/or destruction of long-range order of thephene lattice. The tunability of scattering resonances can be applied for optoelectronic devices based on graphene. Moreover, the results of this study expand the general understanding of the phenomenon of scattering resonances and are applicable to many other materials besides graphene.
Deep convection is an essential part of the circulation in the North Atlantic Ocean. It influences the northward heat transport achieved by the thermohaline circulation. Understanding its stability and variability is therefore necessary for assessing climatic changes in the area of the North Atlantic. This thesis aims at improving the conceptual understanding of the stability and variability of deep convection. Observational data from the Labrador Sea show phases with and without deep convection. A simple two-box model is fitted to these data. The results suggest that the Labrador Sea has two coexisting stable states, one with regular deep convection and one without deep convection. This bistability arises from a positive salinity feedback that is due to the net freshwater input into the surface layer. The convecting state can easily become unstable if the mean forcing shifts to warmer or less saline conditions. The weather-induced variability of the external forcing is included into the box model by adding a stochastic forcing term. It turns out that deep convection is then switched "on" and "off" frequently. The mean residence time in either state is a measure of its stochastic stability. The stochastic stability depends smoothly on the forcing parameters, in contrast to the deterministic (non-stochastic) stability which may change abruptly. The mean and the variance of the stochastic forcing both have an impact on the frequency of deep convection. For instance, a decline in convection frequency due to a surface freshening may be compensated for by an increased heat flux variability. With a further simplified box model some stochastic stability features are studied analytically. A new effect is described, called wandering monostability: even if deep convection is not a stable state due to changed forcing parameters, the stochastic forcing can still trigger convection events frequently. The analytical expressions explicitly show how wandering monostability and other effects depend on the model parameters. This dependence is always exponential for the mean residence times, but for the probability of long nonconvecting phases it is exponential only if this probability is small. It is to be expected that wandering monostability is relevant in other parts of the climate system as well. All in all, the results demonstrate that the stability of deep convection in the Labrador Sea reacts very sensitively to the forcing. The presence of variability is crucial for understanding this sensitivity. Small changes in the forcing can already significantly lower the frequency of deep convection events, which presumably strongly affects the regional climate. ----Anmerkung: Der Autor ist Träger des durch die Physikalische Gesellschaft zu Berlin vergebenen Carl-Ramsauer-Preises 2003 für die jeweils beste Dissertation der vier Universitäten Freie Universität Berlin, Humboldt-Universität zu Berlin, Technische Universität Berlin und Universität Potsdam.
Organic thin film transistors (TFT) are an attractive option for low cost electronic applications and may be used for active matrix displays and for RFID applications. To extend the range of applications there is a need to develop and optimise the performance of non-volatile memory devices that are compatible with the solution-processing fabrication procedures used in plastic electronics. A possible candidate is an organic TFT incorporating the ferroelectric co-polymer poly(vinylidenefluoride-trifluoroethylene)(P(VDF-TrFE)) as the gate insulator. Dielectric measurements have been carried out on all-organic metal-insulator-semiconductor structures with the ferroelectric polymer poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) as the gate insu-lator. The capacitance spectra of MIS devices, were measured under different biases, showing the effect of charge accumulation and depletion on the Maxwell-Wagner peak. The position and height of this peak clearly indicates the lack of stable depletion behavior and the decrease of mobility when increasing the depletion zone width, i.e. upon moving into the P3HT bulk. The lack of stable depletion was further investigated with capacitance-voltage (C-V) measurements. When the structure was driven into depletion, C-V plots showed a positive flat-band voltage shift, arising from the change in polarization state of the ferroelectric insulator. When biased into accumulation, the polarization was reversed. It is shown that the two polarization states are stable i.e. no depolarization occurs below the coercive field. However, negative charge trapped at the semiconductor-insulator interface during the depletion cycle masks the negative shift in flat-band voltage expected during the sweep to accumulation voltages. The measured output characteristics of the studied ferroelectric-field-effect transistors confirmed the results of the C-V plots. Furthermore, the results indicated a trapping of electrons at the positively charged surfaces of the ferroelectrically polarized P(VDF-TrFE) crystallites near the insulator/semiconductor in-terface during the first poling cycles. The study of the MIS structure by means of thermally stimulated current (TSC) revealed further evidence for the stability of the polarization under depletion voltages. It was shown, that the lack of stable depletion behavior is caused by the compensation of the orientational polarization by fixed electrons at the interface and not by the depolarization of the insulator, as proposed in several publications. The above results suggest a performance improvement of non-volatile memory devices by the optimization of the interface.
Amphiphilic molecules contain a hydrophilic headgroup and a hydrophobic tail. The headgroup is polar or ionic and likes water, the tail is typically an aliphatic chain that cannot be accommodated in a polar environment. The prevailing molecular asymmetry leads to a spontaneous adsorption of amphiphiles at the air/water or oil/water interfaces. As a result, the surface tension and the surface rheology is changed. Amphiphiles are important tools to deliberately modify the interfacial properties of liquid interfaces and enable new phenomena such as foams which cannot be formed in a pure liquid. In this thesis we investigate the static and dynamic properties of adsorption layers of soluble amphiphiles at the air/water interface, the so called Gibbs monolayers. The classical way for an investigation of these systems is based on a thermodynamic analysis of the equilibrium surface tension as a function of the bulk composition in the framework of Gibbs theory. However, thermodynamics does not provide any structural information and several recent publications challenge even fundamental text book concepts. The experimental investigation faces difficulties imposed by the low surface coverage and the presence of dissolved amphiphiles in the adjacent bulk phase. In this thesis we used a suite of techniques with the sensitivity to detect less than a monolayer of molecules at the air-water interface. Some of these techniques are extremely complex such as infrared visible sum frequency generation (IR-VIS SFG) spectroscopy or second harmonic generation (SHG). Others are traditional techniques, such as ellipsometry employed in new ways and pushed to new limits. Each technique probes selectively different parts of the interface and the combination provides a profound picture of the interfacial architecture. The first part of the thesis is dedicated to the distribution of ions at interfaces. Adsorption layers of ionic amphiphiles serve as model systems allowing to produce a defined surface charge. The charge of the monolayer is compensated by the counterions. As a result of a complex zoo of interactions there will be a defined distribution of ions at the interface, however, its experimental determination is a big scientific challenge. We could demonstrate that a combination of linear and nonlinear techniques gives direct insights in the prevailing ion distribution. Our investigations reveal specific ion effects which cannot be described by classical Poisson-Boltzmann mean field type theories. Adsorption layer and bulk phase are in thermodynamic equilibrium, however, it is important to stress that there is a constant molecular exchange between adsorbed and dissolved species. This exchange process is a key element for the understanding of some of the thermodynamic properties. An excellent way to study Gibbs monolayers is to follow the relaxation from a non-equilibrium to an equilibrium state. Upon compression amphiphiles must leave the adsorption layer and dissolve in the adjacent bulk phase. Upon expansion amphiphiles must adsorb at the interface to restore the equilibrium coverage. Obviously the frequency of the expansion and compression cycles must match the molecular exchange processes. At too low frequencies the equilibrium is maintained at all times. If the frequency is too fast the system behaves as a monolayer of insoluble surfactants. In this thesis we describe an unique variant of an oscillating bubble technique that measures precisely the real and imaginary part of the complex dilational modulus E in a frequency range up to 500 Hz. The extension of about two decades in the time domain in comparison to the conventional method of an oscillating drop is a tremendous achievement. The imaginary part of the complex dilational modulus E is a consequence of a dissipative process which is interpreted as an intrinsic surface dilational viscosity. The IR-VIS SFG spectra of the interfacial water provide a molecular interpretation of the underlying dissipative process.