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Stream water and groundwater are important fresh water resources but their water quality is deteriorated by harmful solutes introduced by human activities. The interface between stream water and the subsurface water is an important zone for retention, transformation and attenuation of these solutes. Streambed structures enhance these processes by increased water and solute exchange across this interface, denoted as hyporheic exchange.
This thesis investigates the influence of hydrological and morphological factors on hyporheic water and solute exchange as well as redox-reactions in fluvial streambed structures on the intermediate scale (10–30m). For this purpose, a three-dimensional numerical modeling approach for coupling stream water flow with porous media flow is used. Multiple steady state stream water flow scenarios over different generic pool-riffle morphologies and a natural in-stream gravel bar are simulated by a computational fluid dynamics code that provides the hydraulic head distribution at the streambed. These heads are subsequently used as the top boundary condition of a reactive transport groundwater model of the subsurface beneath the streambed. Ambient groundwater that naturally interacts with the stream water is considered in scenarios of different magnitudes of downwelling stream water (losing case) and upwelling groundwater (gaining case). Also, the neutral case, where stream stage and groundwater levels are balanced is considered. Transport of oxygen, nitrate and dissolved organic carbon and their reaction by aerobic respiration and denitrification are modeled.
The results show that stream stage and discharge primarily induce hyporheic exchange flux and solute transport with implications for specific residence times and reactions at both the fully and partially submerged structures. Gaining and losing conditions significantly diminish the extent of the hyporheic zone, the water exchange flux, and shorten residence times for both the fully and partially submerged structures. With increasing magnitude of gaining or losing conditions, these metrics exponentially decrease.
Stream water solutes are transported mainly advectively into the hyporheic zone and hence their influx corresponds directly to the infiltrating water flux. Aerobic respiration takes place in the shallow streambed sediments, coinciding to large parts with the extent of the hyporheic exchange flow. Denitrification occurs mainly as a “reactive fringe” surrounding the aerobic zone, where oxygen concentration is low and still a sufficient amount of stream water carbon source is available. The solute consumption rates and the efficiency of the aerobic and anaerobic reactions depend primarily on the available reactive areas and the residence times, which are both controlled by the interplay between hydraulic head distribution at the streambed and the gradients between stream stage and ambient groundwater. Highest solute consumption rates can be expected under neutral conditions, where highest solute flux, longest residence times and largest extent of the hyporheic exchange occur. The results of this thesis show that streambed structures on the intermediate scale have a significant potential to contribute to a net solute turnover that can support a healthy status of the aquatic ecosystem.
The Barberton Greenstone Belt (BGB) in the northwestern part of South Africa belongs to the few well-preserved remnants of Archean crust. Over the last centuries, the BGB has been intensively studied at surface with detailed mapping of its surfacial geological units and tectonic features. Nevertheless, the deeper structure of the BGB remains poorly understood. Various tectonic evolution models have been developed based on geo-chronological and structural data. These theories are highly controversial and centre on the question whether plate tectonics - as geoscientists understand them today - was already evolving on the Early Earth or whether vertical mass movements driven by the higher temperature of the Earth in Archean times governed continent development.
To get a step closer to answering the questions regarding the internal structure and formation of the BGB, magnetotelluric (MT) field experiments were conducted as part of the German-South African research initiative Inkaba yeAfrica. Five-component MT data (three magnetic and two electric channels) were collected at ~200 sites aligned along six profiles crossing the southern part of the BGB. Tectonic features like (fossil) faults and shear zones are often mineralized and therefore can have high electrical conductivities. Hence, by obtaining an image of the conductivity distribution of the subsurface from MT measurements can provide useful information on tectonic processes.
Unfortunately, the BGB MT data set is heavily affected by man-made electromagnetic noise caused, e.g. by powerlines and electric fences. Aperiodic spikes in the magnetic and corresponding offsets in the electric field components impair the data quality particularly at periods >1 s which are required to image deep electrical structures. Application of common methods for noise reduction like delay filtering and remote reference processing, only worked well for periods <1 s. Within the framework of this thesis two new filtering approaches were developed to handle the severe noise in long period data and obtain reliable processing results. The first algorithm is based on the Wiener filter in combination with a spike detection algorithm. Comparison of data variances of a local site with those of a reference site allows the identification of disturbed time series windows for each recorded channel at the local site. Using the data of the reference site, a Wiener filter algorithm is applied to predict physically meaningful data to replace the disturbed windows. While spikes in the magnetic channels are easily recognized and replaced, steps in the electric channels are more difficult to detect depending on their offset. Therefore, I have implemented a novel approach based on time series differentiation, noise removal and subsequent integration to overcome this obstacle. A second filtering approach where spikes and steps in the time series are identified using a comparison of the short and long time average of the data was also implemented as part of my thesis. For this filtering approach the noise in the form of spikes and offsets in the data is treated by an interpolation of the affected data samples. The new developments resulted in a substantial data improvement and allowed to gain one to two decades of data (up to 10 or 100 s).
The re-processed MT data were used to image the electrical conductivity distribution of the BGB by 2D and 3D inversion. Inversion models are in good agreement with the surface geology delineating the highly resistive rocks of the BGB from surrounding more conductive geological units. Fault zones appear as conductive structures and can be traced to depths of 5 to 10 km. 2D models suggest a continuation of the faults further south across the boundary of the BGB. Based on the shallow tectonic structures (fault system) within the BGB compared to deeply rooted resistive batholiths in the area, tectonic models including both vertical mass transport and in parts present-day style plate tectonics seem to be most likely for the evolution of the BGB.
The origin of cosmic rays was the subject of several studies for over a century. The investigations done within this dissertation are one small step to shed some more light on this mystery.
Locating the sources of cosmic rays is not trivial due to the interstellar magnetic field. However, the Hillas criterion allows us to arrive at the conclusion that supernova remnants are our main suspect for the origin of galactic cosmic rays. The mechanism by which they are accelerating particles is found within the field of shock physics as diffusive shock acceleration. To allow particles to enter this process also known as Fermi acceleration pre-acceleration processes like shock surfing acceleration and shock drift acceleration are necessary. Investigating the processes happening in the plasma shocks of supernova remnants is possible by utilising a simplified model which can be simulated on a computer using Particle-in-Cell simulations.
We developed a new and clean setup to simulate the formation of a double shock, i.e., consisting of a forward and a reverse shock and a contact discontinuity, by the collision of two counter-streaming plasmas, in which a magnetic field can be woven into. In a previous work, we investigated the processes at unmagnetised and at magnetised parallel shocks, whereas in the current work, we move our investigation on to magnetised perpendicular shocks.
Due to a much stronger confinement of the particles to the collision region the perpendicular shock develops much faster than the parallel shock. On the other hand, this leads to much weaker turbulence. We are able to find indications for shock surfing acceleration and shock drift acceleration happening at the two shocks leading to populations of pre-accelerated particles that are suitable as a seed population to be injected into further diffusive shock acceleration to be accelerated to even higher energies. We observe the development of filamentary structures in the shock ramp of the forward shock, but not at the reverse shock. This leads to the conclusion that the development of such structures in the shock ramp of quasi-perpendicular collisionless shocks might not necessarily be determined by the existence of a critical sonic Mach number but by a critical shock speed.
The results of the investigations done within this dissertation might be useful for further studies of oblique shocks and for studies using hybrid or magnetohydrodynamic simulations. Together with more sophisticated observational methods, these studies will help to bring us closer to an answer as to how particles can be accelerated in supernova remnants and eventually become cosmic rays that can be detected on Earth.
Assumed comparable environmental conditions of early Mars and early Earth in 3.7 Ga ago – at a time when first fossil records of life on Earth could be found – suggest the possibility of life emerging on both planets in parallel. As conditions changed, the hypothetical life on Mars either became extinct or was able to adapt and might still exist in biological niches. The controversial discussed detection of methane on Mars led to the assumption, that it must have a recent origin – either abiotic through active volcanism or chemical processes, or through biogenic production. Spatial and seasonal variations in the detected methane concentrations and correlations between the presence of water vapor and geological features such as subsurface hydrogen, which are occurring together with locally increased detected concentrations of methane, gave fuel to the hypothesis of a possible biological source of the methane on Mars.
Therefore the phylogenetically old methanogenic archaea, which have evolved under early Earth conditions, are often used as model-organisms in astrobiological studies to investigate the potential of life to exist in possible extraterrestrial habitats on our neighboring planet. In this thesis methanogenic archaea originating from two extreme environments on Earth were investigated to test their ability to be active under simulated Mars analog conditions. These extreme environments – the Siberian permafrost-affected soil and the chemoautotrophically based terrestrial ecosystem of Movile cave, Romania – are regarded as analogs for possible Martian (subsurface) habitats. Two novel species of methanogenic archaea isolated from these environments were described within the frame of this thesis.
It could be shown that concentrations up to 1 wt% of Mars regolith analogs added to the growth media had a positive influence on the methane production rates of the tested methanogenic archaea, whereas higher concentrations resulted in decreasing rates. Nevertheless it was possible for the organisms to metabolize when incubated on water-saturated soil matrixes made of Mars regolith analogs without any additional nutrients. Long-term desiccation resistance of more than 400 days was proven with reincubation and indirect counting of viable cells through a combined treatment with propidium monoazide (to inactivate DNA of destroyed cells) and quantitative PCR. Phyllosilicate rich regolith analogs seem to be the best soil mixtures for the tested methanogenic archaea to be active under Mars analog conditions. Furthermore, in a simulation chamber experiment the activity of the permafrost methanogen strain Methanosarcina soligelidi SMA-21 under Mars subsurface analog conditions could be proven. Through real-time wavelength modulation spectroscopy measurements the increase in the methane concentration at temperatures down to -5 °C could be detected.
The results presented in this thesis contribute to the understanding of the activity potential of methanogenic archaea under Mars analog conditions and therefore provide insights to the possible habitability of present-day Mars (near) subsurface environments. Thus, it contributes also to the data interpretation of future life detection missions on that planet. For example the ExoMars mission of the European Space Agency (ESA) and Roscosmos which is planned to be launched in 2018 and is aiming to drill in the Martian subsurface.
In the last decade, the number and dimensions of catastrophic flooding events in the Niger River Basin (NRB) have markedly increased. Despite the devastating impact of the floods on the population and the mainly agriculturally based economy of the riverine nations, awareness of the hazards in policy and science is still low. The urgency of this topic and the existing research deficits are the motivation for the present dissertation.
The thesis is an initial detailed assessment of the increasing flood risk in the NRB. The research strategy is based on four questions regarding (1) features of the change in flood risk, (2) reasons for the change in the flood regime, (3) expected changes of the flood regime given climate and land use changes, and (4) recommendations from previous analysis for reducing the flood risk in the NRB.
The question examining the features of change in the flood regime is answered by means of statistical analysis. Trend, correlation, changepoint, and variance analyses show that, in addition to the factors exposure and vulnerability, the hazard itself has also increased significantly in the NRB, in accordance with the decadal climate pattern of West Africa. The northern arid and semi-arid parts of the NRB are those most affected by the changes.
As potential reasons for the increase in flood magnitudes, climate and land use changes are attributed by means of a hypothesis-testing framework. Two different approaches, based on either data analysis or simulation, lead to similar results, showing that the influence of climatic changes is generally larger compared to that of land use changes. Only in the dry areas of the NRB is the influence of land use changes comparable to that of climatic alterations.
Future changes of the flood regime are evaluated using modelling results. First ensembles of statistically and dynamically downscaled climate models based on different emission scenarios are analyzed. The models agree with a distinct increase in temperature. The precipitation signal, however, is not coherent. The climate scenarios are used to drive an eco-hydrological model. The influence of climatic changes on the flood regime is uncertain due to the unclear precipitation signal. Still, in general, higher flood peaks are expected. In a next step, effects of land use changes are integrated into the model. Different scenarios show that regreening might help to reduce flood peaks. In contrast, an expansion of agriculture might enhance the flood peaks in the NRB. Similarly to the analysis of observed changes in the flood regime, the impacts of climate- and land use changes for the future scenarios are also most severe in the dry areas of the NRB.
In order to answer the final research question, the results of the above analysis are integrated into a range of recommendations for science and policy on how to reduce flood risk in the NRB. The main recommendations include a stronger consideration of the enormous natural climate variability in the NRB and a focus on so called “no-regret” adaptation strategies which account for high uncertainty, as well as a stronger consideration of regional differences. Regarding the prevention and mitigation of catastrophic flooding, the most vulnerable and sensitive areas in the basin, the arid and semi-arid Sahelian and Sudano-Sahelian regions, should be prioritized. Eventually, an active, science-based and science-guided flood policy is recommended. The enormous population growth in the NRB in connection with the expected deterioration of environmental and climatic conditions is likely to enhance the region´s vulnerability to flooding. A smart and sustainable flood policy can help mitigate these negative impacts of flooding on the development of riverine societies in West Africa.
Spectral fingerprinting
(2015)
Current research on runoff and erosion processes, as well as an increasing demand for sustainable watershed management emphasize the need for an improved understanding of sediment dynamics. This involves the accurate assessment of erosion rates and sediment transfer, yield and origin. A variety of methods exist to capture these processes at the catchment scale. Among these, sediment fingerprinting, a technique to trace back the origin of sediment, has attracted increasing attention by the scientific community in recent years. It is a two-step procedure, based on the fundamental assumptions that potential sources of sediment can be reliably discriminated based on a set of characteristic ‘fingerprint’ properties, and that a comparison of source and sediment fingerprints allows to quantify the relative contribution of each source.
This thesis aims at further assessing the potential of spectroscopy to assist and improve the sediment fingerprinting technique. Specifically, this work focuses on (1) whether potential sediment sources can be reliably identified based on spectral features (‘fingerprints’), whether (2) these spectral fingerprints permit the quantification of relative source contribution, and whether (3) in situ derived source information is sufficient for this purpose. Furthermore, sediment fingerprinting using spectral information is applied in a study catchment to (4) identify major sources and observe how relative source contributions change between and within individual flood events. And finally, (5) spectral fingerprinting results are compared and combined with simultaneous sediment flux measurements to study sediment origin, transport and storage behaviour.
For the sediment fingerprinting approach, soil samples were collected from potential sediment sources within the Isábena catchment, a meso-scale basin in the central Spanish Pyrenees. Undisturbed samples of the upper soil layer were measured in situ using an ASD spectroradiometer and subsequently sampled for measurements in the laboratory. Suspended sediment was sampled automatically by means of ISCO samplers at the catchment as well as at the five major subcatchment outlets during flood events, and stored fine sediment from the channel bed was collected from 14 cross-sections along the main river. Artificial mixtures of known contributions were produced from source soil samples. Then, all source, sediment and mixture samples were dried and spectrally measured in the laboratory. Subsequently, colour coefficients and physically based features with relation to organic carbon, iron oxide, clay content and carbonate, were calculated from all in situ and laboratory spectra. Spectral parameters passing a number of prerequisite tests were submitted to principal component analyses to study natural clustering of samples, discriminant function analyses to observe source differentiation accuracy, and a mixing model for source contribution assessment. In addition, annual as well as flood event based suspended sediment fluxes from the catchment and its subcatchments were calculated from rainfall, water discharge and suspended sediment concentration measurements using rating curves and Quantile Regression Forests. Results of sediment flux monitoring were interpreted individually with respect to storage behaviour, compared to fingerprinting source ascriptions and combined with fingerprinting to assess their joint explanatory potential.
In response to the key questions of this work, (1) three source types (land use) and five spatial sources (subcatchments) could be reliably discriminated based on spectral fingerprints. The artificial mixture experiment revealed that while (2) laboratory parameters permitted source contribution assessment, (3) the use of in situ derived information was insufficient. Apparently, high discrimination accuracy does not necessarily imply good quantification results. When applied to suspended sediment samples of the catchment outlet, the spectral fingerprinting approach was able to (4) quantify the major sediment sources: badlands and the Villacarli subcatchment, respectively, were identified as main contributors, which is consistent with field observations and previous studies. Thereby, source contribution was found to vary both, within and between individual flood events. Also sediment flux was found to vary considerably, annually as well as seasonally and on flood event base. Storage was confirmed to play an important role in the sediment dynamics of the studied catchment, whereas floods with lower total sediment yield tend to deposit and floods with higher yield rather remove material from the channel bed. Finally, a comparison of flux measurements with fingerprinting results highlighted the fact that (5) immediate transport from sources to the catchment outlet cannot be assumed. A combination of the two methods revealed different aspects of sediment dynamics that none of the techniques could have uncovered individually.
In summary, spectral properties provide a fast, non-destructive, and cost-efficient means to discriminate and quantify sediment sources, whereas, unfortunately, straight-forward in situ collected source information is insufficient for the approach. Mixture modelling using artificial mixtures permits valuable insights into the capabilities and limitations of the method and similar experiments are strongly recommended to be performed in the future. Furthermore, a combination of techniques such as e.g. (spectral) sediment fingerprinting and sediment flux monitoring can provide comprehensive understanding of sediment dynamics.
Water resources from Central Asia’s mountain regions have a high relevance for the water supply of the water scarce lowlands. A good understanding of the water cycle in these mountain regions is therefore needed to develop water management strategies. Hydrological modeling helps to improve our knowledge of the regional water cycle, and it can be used to gain a better understanding of past changes or estimate future hydrologic changes in view of projected changes in climate. However, due to the scarcity of hydrometeorological data, hydrological modeling for mountain regions in Central Asia involves large uncertainties.
Addressing this problem, the first aim of this thesis was to develop hydrological modeling approaches that can increase the credibility of hydrological models in data sparse mountain regions. This was achieved by using additional data from remote sensing and atmospheric modeling. It was investigated whether spatial patterns from downscaled reanalysis data can be used for the interpolation of station-based precipitation data. This approach was compared to other precipitation estimates using a hydrologic evaluation based on hydrological modeling and a comparison of simulated and observed discharge, which demonstrated a generally good performance of this method. The study further investigated the value of satellite-derived snow cover data for model calibration. Trade-offs of good model performance in terms of discharge and snow cover were explicitly evaluated using a multiobjective optimization algorithm, and the results were contrasted with single-objective calibration and Monte Carlo simulations. The study clearly shows that the additional use of snow cover data improved the internal consistency of the hydrological model. In this context, it was further investigated for the first time how many snow cover scenes were required for hydrological model calibration.
The second aim of this thesis was the application of the hydrological model in order to investigate the causes of observed streamflow increases in two headwater catchments of the Tarim River over the recent decades. This simulation-based approach for trend attribution was complemented by a data-based approach. The hydrological model was calibrated to discharge and glacier mass balance data and considered changes in glacier geometry over time. The results show that in the catchment with a lower glacierization, increasing precipitation and temperature both contributed to the streamflow increases, while in the catchment with a stronger glacierization, increasing temperatures were identified as the dominant driver.
Organic bulk heterojunction (BHJ) solar cells based on polymer:fullerene blends are a promising alternative for a low-cost solar energy conversion. Despite significant improvements of the power conversion efficiency in recent years, the fundamental working principles of these devices are yet not fully understood. In general, the current output of organic solar cells is determined by the generation of free charge carriers upon light absorption and their transport to the electrodes in competition to the loss of charge carriers due to recombination.
The object of this thesis is to provide a comprehensive understanding of the dynamic processes and physical parameters determining the performance. A new approach for analyzing the characteristic current-voltage output was developed comprising the experimental determination of the efficiencies of charge carrier generation, recombination and transport, combined with numerical device simulations.
Central issues at the beginning of this work were the influence of an electric field on the free carrier generation process and the contribution of generation, recombination and transport to the current-voltage characteristics. An elegant way to directly measure the field dependence of the free carrier generation is the Time Delayed Collection Field (TDCF) method. In TDCF charge carriers are generated by a short laser pulse and subsequently extracted by a defined rectangular voltage pulse. A new setup was established with an improved time resolution compared to former reports in literature. It was found that charge generation is in general independent of the electric field, in contrast to the current view in literature and opposed to the expectations of the Braun-Onsager model that was commonly used to describe the charge generation process. Even in cases where the charge generation was found to be field-dependend, numerical modelling showed that this field-dependence is in general not capable to account for the voltage dependence of the photocurrent. This highlights the importance of efficient charge extraction in competition to non-geminate recombination, which is the second objective of the thesis.
Therefore, two different techniques were combined to characterize the dynamics and efficiency of non-geminate recombination under device-relevant conditions. One new approach is to perform TDCF measurements with increasing delay between generation and extraction of charges. Thus, TDCF was used for the first time to measure charge carrier generation, recombination and transport with the same experimental setup. This excludes experimental errors due to different measurement and preparation conditions and demonstrates the strength of this technique. An analytic model for the description of TDCF transients was developed and revealed the experimental conditions for which reliable results can be obtained. In particular, it turned out that the $RC$ time of the setup which is mainly given by the sample geometry has a significant influence on the shape of the transients which has to be considered for correct data analysis.
Secondly, a complementary method was applied to characterize charge carrier recombination under steady state bias and illumination, i.e. under realistic operating conditions. This approach relies on the precise determination of the steady state carrier densities established in the active layer. It turned out that current techniques were not sufficient to measure carrier densities with the necessary accuracy. Therefore, a new technique {Bias Assisted Charge Extraction} (BACE) was developed. Here, the charge carriers photogenerated under steady state illumination are extracted by applying a high reverse bias. The accelerated extraction compared to conventional charge extraction minimizes losses through non-geminate recombination and trapping during extraction. By performing numerical device simulations under steady state, conditions were established under which quantitative information on the dynamics can be retrieved from BACE measurements.
The applied experimental techniques allowed to sensitively analyse and quantify geminate and non-geminate recombination losses along with charge transport in organic solar cells. A full analysis was exemplarily demonstrated for two prominent polymer-fullerene blends.
The model system P3HT:PCBM spincast from chloroform (as prepared) exhibits poor power conversion efficiencies (PCE) on the order of 0.5%, mainly caused by low fill factors (FF) and currents. It could be shown that the performance of these devices is limited by the hole transport and large bimolecular recombination (BMR) losses, while geminate recombination losses are insignificant. The low polymer crystallinity and poor interconnection between the polymer and fullerene domains leads to a hole mobility of the order of 10^-7 cm^2/Vs which is several orders of magnitude lower than the electron mobility in these devices. The concomitant build up of space charge hinders extraction of both electrons and holes and promotes bimolecular recombination losses.
Thermal annealing of P3HT:PCBM blends directly after spin coating improves crystallinity and interconnection of the polymer and the fullerene phase and results in comparatively high electron and hole mobilities in the order of 10^-3 cm^2/Vs and 10^-4 cm^2/Vs, respectively. In addition, a coarsening of the domain sizes leads to a reduction of the BMR by one order of magnitude. High charge carrier mobilities and low recombination losses result in comparatively high FF (>65%) and short circuit current (J_SC ≈ 10 mA/cm^2). The overall device performance (PCE ≈ 4%) is only limited by a rather low spectral overlap of absorption and solar emission and a small V_OC, given by the energetics of the P3HT.
From this point of view the combination of the low bandgap polymer PTB7 with PCBM is a promising approach. In BHJ solar cells, this polymer leads to a higher V_OC due to optimized energetics with PCBM. However, the J_SC in these (unoptimized) devices is similar to the J_SC in the optimized blend with P3HT and the FF is rather low (≈ 50%). It turned out that the unoptimized PTB7:PCBM blends suffer from high BMR, a low electron mobility of the order of 10^-5 cm^2/Vs and geminate recombination losses due to field dependent charge carrier generation.
The use of the solvent additive DIO optimizes the blend morphology, mainly by suppressing the formation of very large fullerene domains and by forming a more uniform structure of well interconnected donor and acceptor domains of the order of a few nanometers. Our analysis shows that this results in an increase of the electron mobility by about one order of magnitude (3 x 10^-4 cm^2/Vs), while BMR and geminate recombination losses are significantly reduced. In total these effects improve the J_SC (≈ 17 mA/cm^2) and the FF (> 70%). In 2012 this polymer/fullerene combination resulted in a record PCE for a single junction OSC of 9.2%.
Remarkably, the numerical device simulations revealed that the specific shape of the J-V characteristics depends very sensitively to the variation of not only one, but all dynamic parameters. On the one hand this proves that the experimentally determined parameters, if leading to a good match between simulated and measured J-V curves, are realistic and reliable. On the other hand it also emphasizes the importance to consider all involved dynamic quantities, namely charge carrier generation, geminate and non-geminate recombination as well as electron and hole mobilities. The measurement or investigation of only a subset of these parameters as frequently found in literature will lead to an incomplete picture and possibly to misleading conclusions.
Importantly, the comparison of the numerical device simulation employing the measured parameters and the experimental $J-V$ characteristics allows to identify loss channels and limitations of OSC. For example, it turned out that inefficient extraction of charge carriers is a criticical limitation factor that is often disobeyed. However, efficient and fast transport of charges becomes more and more important with the development of new low bandgap materials with very high internal quantum efficiencies. Likewise, due to moderate charge carrier mobilities, the active layer thicknesses of current high-performance devices are usually limited to around 100 nm. However, larger layer thicknesses would be more favourable with respect to higher current output and robustness of production. Newly designed donor materials should therefore at best show a high tendency to form crystalline structures, as observed in P3HT, combined with the optimized energetics and quantum efficiency of, for example, PTB7.
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.
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.