@phdthesis{Šustr2020, author = {Šustr, David}, title = {Molecular diffusion in polyelectrolyte multilayers}, doi = {10.25932/publishup-48903}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-489038}, school = {Universit{\"a}t Potsdam}, pages = {106}, year = {2020}, abstract = {Research on novel and advanced biomaterials is an indispensable step towards their applications in desirable fields such as tissue engineering, regenerative medicine, cell culture, or biotechnology. The work presented here focuses on such a promising material: polyelectrolyte multilayer (PEM) composed of hyaluronic acid (HA) and poly(L-lysine) (PLL). This gel-like polymer surface coating is able to accumulate (bio-)molecules such as proteins or drugs and release them in a controlled manner. It serves as a mimic of the extracellular matrix (ECM) in composition and intrinsic properties. These qualities make the HA/PLL multilayers a promising candidate for multiple bio-applications such as those mentioned above. The work presented aims at the development of a straightforward approach for assessment of multi-fractional diffusion in multilayers (first part) and at control of local molecular transport into or from the multilayers by laser light trigger (second part). The mechanism of the loading and release is governed by the interaction of bioactives with the multilayer constituents and by the diffusion phenomenon overall. The diffusion of a molecule in HA/PLL multilayers shows multiple fractions of different diffusion rate. Approaches, that are able to assess the mobility of molecules in such a complex system, are limited. This shortcoming motivated the design of a novel evaluation tool presented here. The tool employs a simulation-based approach for evaluation of the data acquired by fluorescence recovery after photobleaching (FRAP) method. In this approach, possible fluorescence recovery scenarios are primarily simulated and afterwards compared with the data acquired while optimizing parameters of a model until a sufficient match is achieved. Fluorescent latex particles of different sizes and fluorescein in an aqueous medium are utilized as test samples validating the analysis results. The diffusion of protein cytochrome c in HA/PLL multilayers is evaluated as well. This tool significantly broadens the possibilities of analysis of spatiotemporal FRAP data, which originate from multi-fractional diffusion, while striving to be widely applicable. This tool has the potential to elucidate the mechanisms of molecular transport and empower rational engineering of the drug release systems. The second part of the work focuses on the fabrication of such a spatiotemporarily-controlled drug release system employing the HA/PLL multilayer. This release system comprises different layers of various functionalities that together form a sandwich structure. The bottom layer, which serves as a reservoir, is formed by HA/PLL PEM deposited on a planar glass substrate. On top of the PEM, a layer of so-called hybrids is deposited. The hybrids consist of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) -based hydrogel microparticles with surface-attached gold nanorods. The layer of hybrids is intended to serve as a gate that controls the local molecular transport through the PEM-solution-interface. The possibility of stimulating the molecular transport by near-infrared (NIR) laser irradiation is being explored. From several tested approaches for the deposition of hybrids onto the PEM surface, the drying-based approach was identified as optimal. Experiments, that examine the functionality of the fabricated sandwich at elevated temperature, document the reversible volume phase transition of the PEM-attached hybrids while sustaining the sandwich stability. Further, the gold nanorods were shown to effectively absorb light radiation in the tissue- and cell-friendly NIR spectral region while transducing the energy of light into heat. The rapid and reversible shrinkage of the PEM-attached hybrids was thereby achieved. Finally, dextran was employed as a model transport molecule. It loads into the PEM reservoir in a few seconds with the partition constant of 2.4, while it spontaneously releases in a slower, sustained manner. The local laser irradiation of the sandwich, which contains the fluorescein isothiocyanate tagged dextran, leads to a gradual reduction of fluorescence intensity in the irradiated region. The release system fabricated employs renowned photoresponsivity of the hybrids in an innovative setting. The results of the research are a step towards a spatially-controlled on-demand drug release system that paves the way to spatiotemporally controlled drug release. The approaches developed in this work have the potential to elucidate the molecular dynamics in ECM and to foster engineering of multilayers with properties tuned to mimic the ECM. The work aims at spatiotemporal control over the diffusion of bioactives and their presentation to the cells.}, language = {en} } @phdthesis{Zorn2020, author = {Zorn, Edgar Ulrich}, title = {Monitoring lava dome growth and deformation with photogrammetric methods and modelling}, doi = {10.25932/publishup-48360}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-483600}, school = {Universit{\"a}t Potsdam}, pages = {IX, 167}, year = {2020}, abstract = {Lava domes are severely hazardous, mound-shaped extrusions of highly viscous lava and commonly erupt at many active stratovolcanoes around the world. Due to gradual growth and flank oversteepening, such lava domes regularly experience partial or full collapses, resulting in destructive and far-reaching pyroclastic density currents. They are also associated with cyclic explosive activity as the complex interplay of cooling, degassing, and solidification of dome lavas regularly causes gas pressurizations on the dome or the underlying volcano conduit. Lava dome extrusions can last from days to decades, further highlighting the need for accurate and reliable monitoring data. This thesis aims to improve our understanding of lava dome processes and to contribute to the monitoring and prediction of hazards posed by these domes. The recent rise and sophistication of photogrammetric techniques allows for the extraction of observational data in unprecedented detail and creates ideal tools for accomplishing this purpose. Here, I study natural lava dome extrusions as well as laboratory-based analogue models of lava dome extrusions and employ photogrammetric monitoring by Structure-from-Motion (SfM) and Particle-Image-Velocimetry (PIV) techniques. I primarily use aerial photography data obtained by helicopter, airplanes, Unoccupied Aircraft Systems (UAS) or ground-based timelapse cameras. Firstly, by combining a long time-series of overflight data at Volc{\´a}n de Colima, M{\´e}xico, with seismic and satellite radar data, I construct a detailed timeline of lava dome and crater evolution. Using numerical model, the impact of the extrusion on dome morphology and loading stress is further evaluated and an impact on the growth direction is identified, bearing important implications for the location of collapse hazards. Secondly, sequential overflight surveys at the Santiaguito lava dome, Guatemala, reveal surface motion data in high detail. I quantify the growth of the lava dome and the movement of a lava flow, showing complex motions that occur on different timescales and I provide insight into rock properties relevant for hazard assessment inferred purely by photogrammetric processing of remote sensing data. Lastly, I recreate artificial lava dome and spine growth using analogue modelling under controlled conditions, providing new insights into lava extrusion processes and structures as well as the conditions in which they form. These findings demonstrate the capabilities of photogrammetric data analyses to successfully monitor lava dome growth and evolution while highlighting the advantages of complementary modelling methods to explain the observed phenomena. The results presented herein further bear important new insights and implications for the hazards posed by lava domes.}, language = {en} } @phdthesis{Ziemann2020, author = {Ziemann, Vanessa}, title = {Toxische Effekte von Arsenolipiden in humanen Kulturzellen und Caenorhabditis elegans}, school = {Universit{\"a}t Potsdam}, pages = {112}, year = {2020}, language = {de} } @phdthesis{Zhelavskaya2020, author = {Zhelavskaya, Irina}, title = {Modeling of the Plasmasphere Dynamics}, doi = {10.25932/publishup-48243}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-482433}, school = {Universit{\"a}t Potsdam}, pages = {xlii, 256}, year = {2020}, abstract = {The plasmasphere is a dynamic region of cold, dense plasma surrounding the Earth. Its shape and size are highly susceptible to variations in solar and geomagnetic conditions. Having an accurate model of plasma density in the plasmasphere is important for GNSS navigation and for predicting hazardous effects of radiation in space on spacecraft. The distribution of cold plasma and its dynamic dependence on solar wind and geomagnetic conditions remain, however, poorly quantified. Existing empirical models of plasma density tend to be oversimplified as they are based on statistical averages over static parameters. Understanding the global dynamics of the plasmasphere using observations from space remains a challenge, as existing density measurements are sparse and limited to locations where satellites can provide in-situ observations. In this dissertation, we demonstrate how such sparse electron density measurements can be used to reconstruct the global electron density distribution in the plasmasphere and capture its dynamic dependence on solar wind and geomagnetic conditions. First, we develop an automated algorithm to determine the electron density from in-situ measurements of the electric field on the Van Allen Probes spacecraft. In particular, we design a neural network to infer the upper hybrid resonance frequency from the dynamic spectrograms obtained with the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrumentation suite, which is then used to calculate the electron number density. The developed Neural-network-based Upper hybrid Resonance Determination (NURD) algorithm is applied to more than four years of EMFISIS measurements to produce the publicly available electron density data set. We utilize the obtained electron density data set to develop a new global model of plasma density by employing a neural network-based modeling approach. In addition to the location, the model takes the time history of geomagnetic indices and location as inputs, and produces electron density in the equatorial plane as an output. It is extensively validated using in-situ density measurements from the Van Allen Probes mission, and also by comparing the predicted global evolution of the plasmasphere with the global IMAGE EUV images of He+ distribution. The model successfully reproduces erosion of the plasmasphere on the night side as well as plume formation and evolution, and agrees well with data. The performance of neural networks strongly depends on the availability of training data, which is limited during intervals of high geomagnetic activity. In order to provide reliable density predictions during such intervals, we can employ physics-based modeling. We develop a new approach for optimally combining the neural network- and physics-based models of the plasmasphere by means of data assimilation. The developed approach utilizes advantages of both neural network- and physics-based modeling and produces reliable global plasma density reconstructions for quiet, disturbed, and extreme geomagnetic conditions. Finally, we extend the developed machine learning-based tools and apply them to another important problem in the field of space weather, the prediction of the geomagnetic index Kp. The Kp index is one of the most widely used indicators for space weather alerts and serves as input to various models, such as for the thermosphere, the radiation belts and the plasmasphere. It is therefore crucial to predict the Kp index accurately. Previous work in this area has mostly employed artificial neural networks to nowcast and make short-term predictions of Kp, basing their inferences on the recent history of Kp and solar wind measurements at L1. We analyze how the performance of neural networks compares to other machine learning algorithms for nowcasting and forecasting Kp for up to 12 hours ahead. Additionally, we investigate several machine learning and information theory methods for selecting the optimal inputs to a predictive model of Kp. The developed tools for feature selection can also be applied to other problems in space physics in order to reduce the input dimensionality and identify the most important drivers. Research outlined in this dissertation clearly demonstrates that machine learning tools can be used to develop empirical models from sparse data and also can be used to understand the underlying physical processes. Combining machine learning, physics-based modeling and data assimilation allows us to develop novel methods benefiting from these different approaches.}, language = {en} } @phdthesis{Zhang2020, author = {Zhang, Jianrui}, title = {Completely water-based emulsions as compartmentalized systems via pickering stabilization}, doi = {10.25932/publishup-47654}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-476542}, school = {Universit{\"a}t Potsdam}, pages = {II, 119}, year = {2020}, abstract = {Completely water-based systems are of interest for the development of novel material for various reasons: On one hand, they provide benign environment for biological systems and on the other hand they facilitate effective molecular transport in a membrane-free environment. In order to investigate the general potential of aqueous two-phase systems (ATPSs) for biomaterials and compartmentalized systems, various solid particles were applied to stabilize all-aqueous emulsion droplets. The target ATPS to be investigated should be prepared via mixing of two aqueous solutions of water-soluble polymers, which turn biphasic when exceeding a critical polymer concentration. Hydrophilic polymers with a wide range of molar mass such as dextran/poly(ethylene glycol) (PEG) can therefore be applied. Solid particles adsorbed at the interfaces can be exceptionally efficient stabilizers forming so-called Pickering emulsions, and nanoparticles can bridge the correlation length of polymer solutions and are thereby the best option for water-in-water emulsions. The first approach towards the investigation of ATPS was conducted with all aqueous dextran-PEG emulsions in the presence of poly(dopamine) particles (PDP) in Chapter 4. The water-in-water emulsions were formed with a PEG/dextran system via utilizing PDP as stabilizers. Studies of the formed emulsions were performed via laser scanning confocal microscope (CLSM), optical microscope (OM), cryo-scanning electron microscope (SEM) and tensiometry. The stable emulsions (at least 16 weeks) were demulsified easily via dilution or surfactant addition. Furthermore, the solid PDP at the water-water interface were crosslinked in order to inhibit demulsification of the Pickering emulsion. Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to visualize the morphology of PDP before and after crosslinking. PDP stabilized water-in-water emulsions were utilized in the following Chapter 5 to form supramolecular compartmentalized hydrogels. Here, hydrogels were prepared in pre-formed water-in-water emulsions and gelled via α-cyclodextrin-PEG (α-CD-PEG) inclusion complex formation. Studies of the formed complexes were performed via X-ray powder diffraction (XRD) and the mechanical properties of the hydrogels were measured with oscillatory shear rheology. In order to verify the compartmentalized state and its triggered decomposition, hydrogels and emulsions were assessed via OM, SEM and CLSM. The last chapter broadens the investigations from the previous two systems by utilizing various carbon nitrides (CN) as different stabilizers in ATPS. CN introduces another way to trigger demulsification, namely irradiation with visible light. Therefore, emulsification and demulsification with various triggers were probed. The investigated all aqueous multi-phase systems will act as model for future fabrication of biocompatible materials, cell micropatterning as well as separation of compartmentalized systems.}, language = {en} } @phdthesis{Zeckra2020, author = {Zeckra, Martin}, title = {Seismological and seismotectonic analysis of the northwestern Argentine Central Andean foreland}, doi = {10.25932/publishup-47324}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-473240}, school = {Universit{\"a}t Potsdam}, pages = {vii, 120}, year = {2020}, abstract = {After a severe M W 5.7 earthquake on October 17, 2015 in El Galp{\´o}n in the province of Salta NW Argentina, I installed a local seismological network around the estimated epicenter. The network covered an area characterized by inherited Cretaceous normal faults and neotectonic faults with unknown recurrence intervals, some of which may have been reactivated normal faults. The 13 three-component seismic stations recorded data continuously for 15 months. The 2015 earthquake took place in the Santa B{\´a}rbara System of the Andean foreland, at about 17km depth. This region is the easternmost morphostructural region of the central Andes. As a part of the broken foreland, it is bounded to the north by the Subandes fold-and-thrust belt and the Sierras Pampeanas to the south; to the east lies the Chaco-Paran{\´a} basin. A multi-stage morphotectonic evolution with thick-skinned basement uplift and coeval thin-skinned deformation in the intermontane basins is suggested for the study area. The release of stresses associated with the foreland deformation can result in strong earthquakes, as the study area is known for recurrent and historical, destructive earthquakes. The available continuous record reaches back in time, when the strongest event in 1692 (magnitude 7 or intensity IX) destroyed the city of Esteco. Destructive earthquakes and surface deformation are thus a hallmark of this part of the Andean foreland. With state-of-the-art Python packages (e.g. pyrocko, ObsPy), a semi-automatic approach is followed to analyze the collected continuous data of the seismological network. The resulting 1435 hypocenter locations consist of three different groups: 1.) local crustal earthquakes (nearly half of the events belong to this group), 2.) interplate activity, of regional distance in the slab of the Nazca-plate, and 3.) very deep earthquakes at about 600km depth. My major interest focused on the first event class. Those crustal events are partly aftershock events of the El Galp{\´o}n earthquake and a second earthquake, in the south of the same fault. Further events can be considered as background seismicity of other faults within the study area. Strikingly, the seismogenic zone encompass the whole crust and propagates brittle deformation down, close to the Moho. From the collected seismological data, a local seismic velocity model is estimated, using VELEST. After the execution of various stability tests, the robust minimum 1D-velocity model implies guiding values for the composition of the local, subsurface structure of the crust. Afterwards, performing a hypocenter relocation enables the assignment of individual earthquakes to aftershock clusters or extended seismotectonic structures. This allows the mapping of previously unknown seismogenic faults. Finally, focal mechanisms are modeled for events with acurately located hypocenters, using the newly derived local velocity model. A compressive regime is attested by the majority of focal mechanisms, while the strike direction of the individual seismogenic structures is in agreement with the overall north - south orientation of the Central Andes, its mountain front, and individual mountain ranges in the southern Santa-B{\´a}rbara-System.}, language = {en} } @phdthesis{Zaruba2020, author = {Zaruba, Nicole}, title = {Die Entwicklung von Lehrer{\"u}berzeugungen im Potsdamer Praxissemester}, school = {Universit{\"a}t Potsdam}, pages = {viii, 195}, year = {2020}, language = {de} } @phdthesis{Youakim2020, author = {Youakim, Kris}, title = {Galactic archaeology with metal-poor stars from the Pristine survey}, doi = {10.25932/publishup-47431}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-474314}, school = {Universit{\"a}t Potsdam}, pages = {iv, 151}, year = {2020}, abstract = {The Milky Way is a spiral galaxy consisting of a disc of gas, dust and stars embedded in a halo of dark matter. Within this dark matter halo there is also a diffuse population of stars called the stellar halo, that has been accreting stars for billions of years from smaller galaxies that get pulled in and disrupted by the large gravitational potential of the Milky Way. As they are disrupted, these galaxies leave behind long streams of stars that can take billions of years to mix with the rest of the stars in the halo. Furthermore, the amount of heavy elements (metallicity) of the stars in these galaxies reflects the rate of chemical enrichment that occurred in them, since the Universe has been slowly enriched in heavy elements (e.g. iron) through successive generations of stars which produce them in their cores and supernovae explosions. Therefore, stars that contain small amounts of heavy elements (metal-poor stars) either formed at early times before the Universe was significantly enriched, or in isolated environments. The aim of this thesis is to develop a better understanding of the substructure content and chemistry of the Galactic stellar halo, in order to gain further insight into the formation and evolution of the Milky Way. The Pristine survey uses a narrow-band filter which specifically targets the Ca II H \& K spectral absorption lines to provide photometric metallicities for a large number of stars down to the extremely metal-poor (EMP) regime, making it a very powerful data set for Galactic archaeology studies. In Chapter 2, we quantify the efficiency of the survey using a preliminary spectroscopic follow-up sample of ~ 200 stars. We also use this sample to establish a set of selection criteria to improve the success rate of selecting EMP candidates for follow-up spectroscopy. In Chapter 3, we extend this work and present the full catalogue of ~ 1000 stars from a three year long medium resolution spectroscopic follow-up effort conducted as part of the Pristine survey. From this sample, we compute success rates of 56\% and 23\% for recovering stars with [Fe/H] < -2.5 and [Fe/H] < -3.0, respectively. This demonstrates a high efficiency for finding EMP stars as compared to previous searches with success rates of 3-4\%. In Chapter 4, we select a sample of ~ 80000 halo stars using colour and magnitude cuts to select a main sequence turnoff population in the distance range 6 < dʘ < 20 kpc. We then use the spectroscopic follow-up sample presented in Chapter 3 to statistically rescale the Pristine photometric metallicities of this sample, and present the resulting corrected metallicity distribution function (MDF) of the halo. The slope at the metal-poor end is significantly shallower than previous spectroscopic efforts have shown, suggesting that there may be more metal-poor stars with [Fe/H] < -2.5 in the halo than previously thought. This sample also shows evidence that the MDF of the halo may not be bimodal as was proposed by previous works, and that the lack of globular clusters in the Milky Way may be the result of a physical truncation of the MDF rather than just statistical under-sampling. Chapter 5 showcases the unexpected capability of the Pristine filter for separating blue horizontal branch (BHB) stars from Blue Straggler (BS) stars. We demonstrate a purity of 93\% and completeness of 91\% for identifying BHB stars, a substantial improvement over previous works. We then use this highly pure and complete sample of BHB stars to trace the halo density profile out to d > 100 kpc, and the Sagittarius stream substructure out to ~ 130 kpc. In Chapter 6 we use the photometric metallicities from the Pristine survey to perform a clustering analysis of the halo as a function of metallicity. Separating the Pristine sample into four metallicity bins of [Fe/H] < -2, -2 < [Fe/H] < -1.5, -1.5 < [Fe/H] < -1 and -0.9 < [Fe/H] < -0.8, we compute the two-point correlation function to measure the amount of clustering on scales of < 5 deg. For a smooth comparison sample we make a mock Pristine data set generated using the Galaxia code based on the Besan{\c{c}}on model of the Galaxy. We find enhanced clustering on small scales (< 0.5 deg) for some regions of the Galaxy for the most metal-poor bin ([Fe/H] < -2), while in others we see large scale signals that correspond to known substructures in those directions. This confirms that the substructure content of the halo is highly anisotropic and diverse in different Galactic environments. We discuss the difficulties of removing systematic clustering signals from the data and the limitations of disentangling weak clustering signals from real substructures and residual systematic structure in the data. Taken together, the work presented in this thesis approaches the problem of better understanding the halo of our Galaxy from multiple angles. Firstly, presenting a sizeable sample of EMP stars and improving the selection efficiency of EMP stars for the Pristine survey, paving the way for the further discovery of metal-poor stars to be used as probes to early chemical evolution. Secondly, improving the selection of BHB distance tracers to map out the halo to large distances, and finally, using the large samples of metal-poor stars to derive the MDF of the inner halo and analyse the substructure content at different metallicities. The results of this thesis therefore expand our understanding of the physical and chemical properties of the Milky Way stellar halo, and provide insight into the processes involved in its formation and evolution.}, language = {en} } @phdthesis{Yang2020, author = {Yang, Xiaoqiang}, title = {Spatial and temporal analyses of catchment and in-stream nitrate dynamics}, doi = {10.25932/publishup-47702}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-477029}, school = {Universit{\"a}t Potsdam}, pages = {VIII, 146}, year = {2020}, abstract = {Water quality in river systems is of growing concern due to rising anthropogenic pressures and climate change. Mitigation efforts have been placed under the guidelines of different governance conventions during last decades (e.g., the Water Framework Directive in Europe). Despite significant improvement through relatively straightforward measures, the environmental status has likely reached a plateau. A higher spatiotemporal accuracy of catchment nitrate modeling is, therefore, needed to identify critical source areas of diffuse nutrient pollution (especially for nitrate) and to further guide implementation of spatially differentiated, cost-effective mitigation measures. On the other hand, the emerging high-frequency sensor monitoring upgrades the monitoring resolution to the time scales of biogeochemical processes and enables more flexible monitoring deployments under varying conditions. The newly available information offers new prospects in understanding nitrate spatiotemporal dynamics. Formulating such advanced process understanding into catchment models is critical for model further development and environmental status evaluation. This dissertation is targeting on a comprehensive analysis of catchment and in-stream nitrate dynamics and is aiming to derive new insights into their spatial and temporal variabilities through the new fully distributed model development and the new high-frequency data. Firstly, a new fully distributed, process-based catchment nitrate model (the mHM-Nitrate model) is developed based on the mesoscale Hydrological Model (mHM) platform. Nitrate process descriptions are adopted from the Hydrological Predictions for the Environment (HYPE), with considerable improved implementations. With the multiscale grid-based discretization, mHM-Nitrate balances the spatial representation and the modeling complexity. The model has been thoughtfully evaluated in the Selke catchment (456 km2), central Germany, which is characterized by heterogeneous physiographic conditions. Results show that the model captures well the long-term discharge and nitrate dynamics at three nested gauging stations. Using daily nitrate-N observations, the model is also validated in capturing short-term fluctuations due to changes in runoff partitioning and spatial contribution during flooding events. By comparing the model simulations with the values reported in the literature, the model is capable of providing detailed and reliable spatial information of nitrate concentrations and fluxes. Therefore, the model can be taken as a promising tool for environmental scientists in advancing environmental modeling research, as well as for stakeholders in supporting their decision-making, especially for spatially differentiated mitigation measures. Secondly, a parsimonious approach of regionalizing the in-stream autotrophic nitrate uptake is proposed using high-frequency data and further integrated into the new mHM-Nitrate model. The new regionalization approach considers the potential uptake rate (as a general parameter) and effects of above-canopy light and riparian shading (represented by global radiation and leaf area index data, respectively). Multi-parameter sensors have been continuously deployed in a forest upstream reach and an agricultural downstream reach of the Selke River. Using the continuous high-frequency data in both streams, daily autotrophic uptake rates (2011-2015) are calculated and used to validate the regionalization approach. The performance and spatial transferability of the approach is validated in terms of well-capturing the distinct seasonal patterns and value ranges in both forest and agricultural streams. Integrating the approach into the mHM-Nitrate model allows spatiotemporal variability of in-stream nitrate transport and uptake to be investigated throughout the river network. Thirdly, to further assess the spatial variability of catchment nitrate dynamics, for the first time the fully distributed parameterization is investigated through sensitivity analysis. Sensitivity results show that parameters of soil denitrification, in-stream denitrification and in-stream uptake processes are the most sensitive parameters throughout the Selke catchment, while they all show high spatial variability, where hot-spots of parameter sensitivity can be explicitly identified. The Spearman rank correlation is further analyzed between sensitivity indices and multiple catchment factors. The correlation identifies that the controlling factors vary spatially, reflecting heterogeneous catchment responses in the Selke catchment. These insights are, therefore, informative in informing future parameter regionalization schemes for catchment water quality models. In addition, the spatial distributions of parameter sensitivity are also influenced by the gauging information that is being used for sensitivity evaluation. Therefore, an appropriate monitoring scheme is highly recommended to truly reflect the catchment responses.}, language = {en} } @phdthesis{Wolff2020, author = {Wolff, Christian Michael}, title = {Identification and reduction of losses in perovskite solar cells}, doi = {10.25932/publishup-47930}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-479301}, school = {Universit{\"a}t Potsdam}, pages = {x, 158}, year = {2020}, abstract = {Perovskite solar cells have become one of the most studied systems in the quest for new, cheap and efficient solar cell materials. Within a decade device efficiencies have risen to >25\% in single-junction and >29\% in tandem devices on top of silicon. This rapid improvement was in many ways fortunate, as e. g. the energy levels of commonly used halide perovskites are compatible with already existing materials from other photovoltaic technologies such as dye-sensitized or organic solar cells. Despite this rapid success, fundamental working principles must be understood to allow concerted further improvements. This thesis focuses on a comprehensive understanding of recombination processes in functioning devices. First the impact the energy level alignment between the perovskite and the electron transport layer based on fullerenes is investigated. This controversial topic is comprehensively addressed and recombination is mitigated through reducing the energy difference between the perovskite conduction band minimum and the LUMO of the fullerene. Additionally, an insulating blocking layer is introduced, which is even more effective in reducing this recombination, without compromising carrier collection and thus efficiency. With the rapid efficiency development (certified efficiencies have broken through the 20\% ceiling) and thousands of researchers working on perovskite-based optoelectronic devices, reliable protocols on how to reach these efficiencies are lacking. Having established robust methods for >20\% devices, while keeping track of possible pitfalls, a detailed description of the fabrication of perovskite solar cells at the highest efficiency level (>20\%) is provided. The fabrication of low-temperature p-i-n structured devices is described, commenting on important factors such as practical experience, processing atmosphere \& temperature, material purity and solution age. Analogous to reliable fabrication methods, a method to identify recombination losses is needed to further improve efficiencies. Thus, absolute photoluminescence is identified as a direct way to quantify the Quasi-Fermi level splitting of the perovskite absorber (1.21eV) and interfacial recombination losses the transport layers impose, reducing the latter to ~1.1eV. Implementing very thin interlayers at both the p- and n-interface (PFN-P2 and LiF, respectively), these losses are suppressed, enabling a VOC of up to 1.17eV. Optimizing the device dimensions and the bandgap, 20\% devices with 1cm2 active area are demonstrated. Another important consideration is the solar cells' stability if subjected to field-relevant stressors during operation. In particular these are heat, light, bias or a combination thereof. Perovskite layers - especially those incorporating organic cations - have been shown to degrade if subjected to these stressors. Keeping in mind that several interlayers have been successfully used to mitigate recombination losses, a family of perfluorinated self-assembled monolayers (X-PFCn, where X denotes I/Br and n = 7-12) are introduced as interlayers at the n-interface. Indeed, they reduce interfacial recombination losses enabling device efficiencies up to 21.3\%. Even more importantly they improve the stability of the devices. The solar cells with IPFC10 are stable over 3000h stored in the ambient and withstand a harsh 250h of MPP at 85◦C without appreciable efficiency losses. To advance further and improve device efficiencies, a sound understanding of the photophysics of a device is imperative. Many experimental observations in recent years have however drawn an inconclusive picture, often suffering from technical of physical impediments, disguising e. g. capacitive discharge as recombination dynamics. To circumvent these obstacles, fully operational, highly efficient perovskites solar cells are investigated by a combination of multiple optical and optoelectronic probes, allowing to draw a conclusive picture of the recombination dynamics in operation. Supported by drift-diffusion simulations, the device recombination dynamics can be fully described by a combination of first-, second- and third-order recombination and JV curves as well as luminescence efficiencies over multiple illumination intensities are well described within the model. On this basis steady state carrier densities, effective recombination constants, densities-of-states and effective masses are calculated, putting the devices at the brink of the radiative regime. Moreover, a comprehensive review of recombination in state-of-the-art devices is given, highlighting the importance of interfaces in nonradiative recombination. Different strategies to assess these are discussed, before emphasizing successful strategies to reduce interfacial recombination and pointing towards the necessary steps to further improve device efficiency and stability. Overall, the main findings represent an advancement in understanding loss mechanisms in highly efficient solar cells. Different reliable optoelectronic techniques are used and interfacial losses are found to be of grave importance for both efficiency and stability. Addressing the interfaces, several interlayers are introduced, which mitigate recombination losses and degradation.}, language = {en} }