464 search hits
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Soil erosion and conservation potential of row crop farming in mountainous landscapes of South Korea
(2013)
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Sebastian Arnhold
- Soils play an essential role for mankind because they provide fundamental ecosystem services required for human life, primarily for the production of food by providing the environment for plant growth. However, soils worldwide became highly threatened by human induced degradation, especially as a consequence of accelerated erosion by water during recent decades. In consideration of climate change and an increasing food demand of a rising population, there is an urgent need to conserve the soil resources by implementing effective erosion control measures for agricultural production. The effective implementation of those measures strongly depends on the specific conditions of particular regions and requires the analysis of the existing farming systems and their capability for erosion control.
Objective of this thesis is the analysis of the major agricultural practices applied for row crop cultivation in mountainous watersheds of South Korea with respect to water erosion and the identification of their conservation potential. Our first two studies analyze the subsurface flow processes, the runoff patterns, and the associated erosion rates of the widely applied plastic covered ridge-furrow system (plastic mulch), and our third study investigates the impact of herbicide applications on erosion associated with conventional and organic farming. To analyze the flow processes induced by the plastic mulch cultivation, we conducted four irrigation experiments on potato fields that represent a smooth surface, uncovered ridges, and plastic covered ridges with and without a developed crop canopy. With an automatic sprinkler, we irrigated small plots with a dye tracer solution of Brilliant Blue and potassium iodide, collected surface runoff, and excavated soil profiles to visualize the subsurface flow patterns, which were subsequently analyzed by image index functions. We found that the ridge-furrow system, especially when ridges are covered with plastic, decreased infiltration and generated high amounts of surface runoff, whereas a developed crop canopy increased infiltration due to interception and stem flow. The analyses of the subsurface flow patterns show that the plastic covered ridge-furrow system induces preferential infiltration in furrows and planting holes due to its topography and the impermeable covers, but that the impact on flow processes in the soils is relatively small compared to the impact on runoff generation. To identify the patterns of overland flow and the erosion rates associated with the plastic mulch system, we installed runoff collectors to monitor runoff and sediment transport of two potato fields with concave and convex topographies, and we applied the EROSION 3D model to compare the plastic covered ridge-furrow system to uncovered ridges and a smooth surface. We found that plastic mulch cultivation considerably increases soil erosion compared to uncovered ridges as a consequence of high amounts of surface runoff. Our results show that the ridge-furrow system concentrated overland flow on the concave field, resulting in severe gully erosion, but prevented flow accumulation and reduced erosion on the convex field, which demonstrates that the effect of this cultivation strategy is primarily controlled by the field topography and its orientation. To analyze the effects of conventional and organic farming on water erosion, we measured multiple vegetation parameters of crops and weeds of conventional and organic farms cultivating bean, potato, radish, and cabbage, and we simulated long-term soil loss rates with the Revised Universal Soil Loss Equation (RUSLE). We found that organic farming reduced erosion for radish, as a result of an increased weed biomass due to the absence of herbicides, but that it increased erosion for potato due to lower crop coverage, presumably as a consequence of crop-weed competition or herbivory associated with the absence of agricultural chemicals. Although we demonstrated that a developed weed cover in the furrows can potentially decrease the erosion risk for row crops, our results show that the average annual erosion rates of both farming systems exceed by far any tolerable soil loss.
In consideration of the generally high soil loss found in our studies, we conclude that the applied farming practices are not capable for effective erosion control and soil conservation in this region. However, based on our findings, we could identify possible modifications of those practices that can help to reduce the risk of erosion in the future. We recommend perforated plastic covers for ridges to reduce runoff generation, and the orientation of the ridge-furrow system along the contours or towards field edges to prevent flow accumulation and gully formation. Additionally, we suggest residue mulching of furrows to protect the soil surface from overland flow, and the cultivation of winter cover crops after harvest to maintain a better soil cover throughout the year.
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Flow and transport processes as affected by tillage management under monsoonal conditions in South Korea
(2013)
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Marianne Ruidisch
- A sustainable agriculture, which provides enough yields to satisfy the food demand and minimizes the impacts on ecosystem services such as provision of high water quality, is challenging especially in monsoon regions. In this thesis, plastic mulched ridge cultivation (RTpm) under monsoonal conditions and its impact on flow processes and nitrate transport was investigated.
On hillslopes, we monitored surface and subsurface flow processes in four plastic mulched potato fields using a network of tensiometers, FDR sensors, runoff collectors and flow dividers as well as Brilliant Blue FCF tracer experiments. The obtained datasets were used to calibrate the process-based models HYDRUS 2/3D and EROSION 3D in order to quantify drainage water fluxes, surface runoff and erosion rates of RTpm compared to ridge tillage without coverage (RT) and conventional flat tillage (CT). In a flat terrain, N fate under fertilizer rates at 50, 150, 250 and 350 kg NO3− ha−1 was investigated in a plastic mulched radish field using suction lysimeters, tensiometers and a 15N tracer experiment. We used datasets of nitrate concentrations and matric potentials to calibrate a water flow and solute transport model using the numerical code HydroGeoSphere.
RTpm affects soil water dynamics dominantly during dry periods, when ridge soil was drier compared to furrow soil caused by the protective plastic coverage and root water uptake in ridges. Hence, pressure head gradients induced lateral flow from furrows to ridges. Under monsoonal conditions, soil was fully saturated and down slope lateral flow occurred in the coarse textured topsoil. The dye tracer experiments showed that matrix flow dominated in the sandy topsoil. Lateral funnel flow above the tillage pan was the prominent preferential flow path. Unexpectedly, macropore flow in deeper soil horizons was not detected. The field and modeling studies revealed that surface runoff was substantially increased under RTpm compared to RT and CT. However, the field topography primarily controlled surface runoff and erosion rates. The concavity of the field led to flow accumulation and high erosion losses in the center of the field, while a convex shape resulted in less soil erosion.
NO3− leaching was found to be the prominent pathway especially during the early season. Furthermore, the biomass production did not significantly differ between NO3− fertilizer rates of 150 to 350 kg ha−1. Hence, we recommend NO3− fertilizer application of 150 kg ha−1, a better fertilizer placement and split applications. We simulated whether the given recommendations on fertilizer best management practices (FBMPs) decreased NO3− leaching amounts. Compared to RT under conventional fertilization in ridges and furrows, the simulations showed that NO3− leaching can be considerably reduced up to 82% by combining RTpm, fertilizer placement only in ridges and split applications with a total fertilizer NO3− amount of 150 kg ha−1.
Based on these findings, the impact of RTpm on flow and transport processes has to be evaluated differently depending on terrain complexity. In a flat terrain, where surface runoff processes are absent or minimal, RTpm has several advantages. Beside functions such as weed control, and earlier plant emergence due to higher temperatures, plastic mulching decreases drainage water and NO3− leaching. Thus, RTpm enhances nutrient retention below the plastic mulch and reduces NO3− groundwater contamination risk. On slopes, where precipitation contributes substantially to surface runoff, RTpm even increases runoff, soil erosion and surface leaching of agrochemicals into aquatic systems.
This thesis provides several recommendations, aiming to minimize environmental impacts and to decrease costs of fertilizer and herbicide inputs. To reduce surface runoff and soil erosion at sloped fields, we suggest applying perforated plastic mulch and a ridge configuration following contours of the field. Furthermore, we recommend omitting application of herbicides in furrows to allow weed growth, which slows down runoff processes. These suggestions would increase infiltration and subsurface flow processes automatically become more important. However, absent preferential flow to deeper soil layers indicated a low groundwater contamination risk. Since funnel flow above the tillage pan was found to be the most important preferential flow path, we propose the establishment of riparian buffer zones. This would also help to reduce the discharge of sediments and fertilizers via surface runoff into the streams. Finally, FBMPs such as fertilizer placement only in ridges and split applications were found to decrease nitrate leaching considerably. Hence, we suggest applying FBMPs with impermeable plastic mulch in flat terrain, while on hill slopes FBMPs should be applied with perforated plastic mulch. To reduce the leaching and erosion risk after harvest when the plastic mulched ridges are removed, we recommend cultivating cover crops.
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The origins of olivine fabric transitions and their effects on seismic anisotropy in the upper mantle
(2012)
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Sushant Shekhar
- Convecting mantle plays a central role in the thermal and geochemical evolution of the Earth. It provides the principal force responsible for major geological features such as mountains and ocean basins. Plate tectonics and its violent consequences such as earthquakes and volcanoes are all manifestations of the dynamics of the convective mantle. Shearing forces generated by mantle convection leads to lattice preferred orientation (LPO) of the major upper mantle mineral phases. LPO that develops in this way is thought to be the principal cause behind seismic anisotropy in the upper mantle, which can consequently be used to chart convective flow of the mantle.
Strong changes in seismic anisotropy occur in the top 300 km of the upper mantle where olivine is the principal mineral. In this study a solid media high pressure deformation apparatus, called the deformation-DIA or D-DIA, has been used to deform aggregates of San Carlos olivine in simple shear geometry at pressures between 3 and 8.5 GPa and temperatures from 1300-1500°C. As part of this project a high pressure and temperature solid-media cubic assembly was developed to facilitate these experiment that employed alumina pistons cut at 45° to shear the sample but minimized cold deformation of the sample by employing initially porous alumina in the sample column. Once stable high pressures and temperature were reached the cubic assembly was deformed by compressing two vertically oriented anvils of the D-DIA, while the four horizontally oriented anvils were maintained at a constant loading force. This assembly shortening led to shearing of the olivine sample. Recovered samples were analyzed for fabric development employing electron backscattered diffraction (EBSD) and microstructure was observed using transmission electron microscopy (TEM).
Experiments were performed at each pressure and temperature as a function of strain rate and H2O content. In dry olivine deformation experiments performed at slower strain rates an A-type fabric dominated at all pressures and temperatures, implying deformation by dislocation glide through the (010)[100] slip system. At higher strain rates evidence for the B-type fabric was observed, suggesting increased activity of the (010)[001] slip system at higher stresses. Recrystallization grains size and dislocation densities were used to estimate stresses in the samples and a good correlation was observed between strain rate and estimated flow stresses. Dry experiments from 8.5 GPa and 1500°C exhibited no LPO, which may be an indication for deformation through diffusion accommodated grain boundary sliding at these conditions. No indication was found that pressure influences the dominant slip system in olivine, in contrast to previous studies. It is considered that previously reported incidences of pressure effects can in fact be attributed to the development of higher stresses in experiments performed at higher pressures.
Fabrics in H2O bearing olivine deformed at similar conditions revealed the overriding dominance of the C-type fabric, developed through action of the (100)[001] slip system. Variations in pressure, temperature and strain rate had little influence on this fabric development. TEM observations confirmed the presence of dislocations with slip systems consistent with the development of the macroscopic fabrics. Viscoplastic self consistent modeling was employed to understand the development of fabric in the samples and to estimate the relative contributions of variations slip systems to the developed fabrics.
These results are used to construct an olivine fabric map which is found to be consistent with some previous studies at lower pressures. It is argued that the decrease in seismic anisotropy observed in the top 300 km of the upper mantle cannot originate from a pressure induced change in the dominant olivine deformation fabric. Instead it is argued that changes in the H2O content of olivine with depth cause a shift in the dominant fabric from A-type to C-type, with a possible excursion through the E-type fabric, dominant slip system (001)[100], which was, however, not observed in this study. Modeling is used to show that this variation in fabric with depth can cause the observed weakening the seismic anisotropy in the upper mantle if the olivine H2O content increases from below 100 ppm at 50 km to 250 ppm at 300 km. Rather than implying an increased in the H2O content of the mantle with depth, however, it is argued that this change in olivine H2O content can be caused by changes in the H2O olivine-pyroxene partition coefficients with depth, for a fixed bulk mantle H2O content of 200 ppm.
Similar deformation experiments performed on a peridotite assemblage at 8.5 GPa and 1300°C indicate identical olivine fabrics to those observed in monomineralic experiments at the same conditions. Fabrics for diopside and enstatite were found to be similar to those found in previously performed lower pressure experiments.
Experiments on a piezoelectric single crystal of GaPO4 were performed in the D-DIA and 6-ram MAVO press at high pressures in order to measure charge on the crystal developed through the application of deviatoric stresses. Electrical charges were measured through the use of an operational amplifier. Experiments performed at room temperature using a developed cubic assembly were successful in measuring quantifiable electrical charges resulting from the advancement of the deformation anvils by as little as 0.5 µm. Although the piezoelectric constant for this material is not yet calibrated at high pressures, stresses were estimated from the measured charges and measureable values were in the range 4-350 MPa.
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Rhizodeposition and its effects on C fluxes in the soil
(2013)
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Johanna Pausch
- Organic compounds released from living roots (rhizodeposits) are easily available sources of energy for microorganisms strongly affecting soil organic matter (SOM) dynamics. Although, rhizodeposition is a key driver of microbially mediated processes in the soils, it still remains the most uncertain component of the terrestrial carbon (C) cycle.
The input of C through rhizodeposition occurs in temporal and spatial hotspots. The objective of Study 1 was to determine the dynamics of hotspots of recently assimilated C in ryegrass roots. Shoots were 14CO2 pulse labeled and the allocation patterns at increasing time intervals were visualized by phosphor imaging. We could show a quick translocation of assimilated C to the roots. 14C hotspots were detected at the root tips already 6 hours after labeling. The hotspots remained active for at least 2 days. Eleven days after assimilation the hotspots at the tips had disappeared, and the 14C distribution was much more even than after 6 hours and 2 days.
Through the availability of rhizodeposits, hotspots create preferred habitats for microbes. Rhizodeposits are an important source of C and energy for microorganisms stimulating their growth and activity. Thereby, roots can influence the rate of native SOM decomposition in the rhizosphere. This rhizosphere priming effect (RPE) was reported to be plant-species specific. Therefore, we hypothesized that also plant inter-species interactions affect the RPE.
In Study 2, we used continuous 13CO2 labeling to investigate the RPE of monocultures and mixtures of typical agricultural crops. The RPE was consistently positive for all cultures with an increase of 43% - 136% above the unplanted soil. Of particular interest was the result that plant inter-species interactions between sunflower and wheat significantly reduced the RPE in contrast to mixtures which included soybean as a legume. It was argued that the RPE of the sunflower-wheat mixture was reduced through a more severe competition for nitrogen (N), whereas, due to the N-rich rhizodeposits of the legume and its lower demand for soil mineral N the RPE of the legume containing mixtures remained unaffected.
Besides potential plant-specific differences in the quality and quantity of rhizodeposits, also photosynthesis could control root exudation because of the fast transport of recently assimilated C to belowground pools. Taking both factors into account, in Studies 3 and 4 the effect of limited photosynthesis on the distribution of recently assimilated C, of stored C and of N was investigated. Based on 13C, 14C and 15N labeling of a legume and a non-legume we could demonstrate that high C and N demands of regrowing shoots after clipping led to a remobilization of stored C and N to the shoots. Additionally, recently assimilated C was retained in the regrowing shoots.
Shading, in contrast, did not induce a remobilization of stored C, since recently assimilated C obviously covered the demand of the shoots with lower growth rates. For both treatments lower amounts of recently assimilated C were observed in the belowground pools emphasizing the importance of the tight coupling of assimilation and belowground processes. Furthermore, different responses of clipping and shading of the legume and the non-legume could be detected for root-derived CO2.
The quantitative importance of rhizodeposition at field scale was determined in Study 5. We proposed a new approach for an improved quantification of rhizodeposition under field conditions taking into account the decomposed fraction of rhizodeposits. Based on a 14CO2 pulse labeling experiment under controlled conditions a rhizodeposition-to-root ratio was calculated and was applied to the root biomass of the field. The root biomass C of maize, sampled in July 2009, was 298±64 kg C ha-1. Gross rhizodeposition was 166±53 kg C ha-1.
With aging of SOM, the availability of C for microbial decomposition declines. In Study 6 the availability of younger relative to older C sources was assessed. The natural isotope abundances of 13C and 12C of SOM and CO2 were analyzed after a C3 to C4 vegetation change. The contribution of younger C, originating from the belowground C input by maize in the previous year, and that of older C sources, derived from the former C3 vegetation, to SOM and CO2 was determined. Comparing the proportions of younger and older C in SOM with that in CO2, we found that younger C was 7 times more available for microbial decomposition than older C pools.
In summary, this thesis extends the understanding of factors affecting rhizodeposition and of processes occurring at the soil-root interface. Furthermore, it presents a new method to quantify gross rhizodeposition at field scale. Although, we could gain insight in temporal changes of the availability of C pools for microbes, the ecological importance of C fluxes in the rhizosphere requires future research on this topic with regard to spatial and temporal predictions.
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Comparisons of N2O and CH4 fluxes as affected by land use systems and climate in small catchments in Korea
(2013)
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Sina Berger
- In the course of global and climate change humankind has to face extreme weather events with increased intensity and frequency and it has to deal with feeding an increasing number of people which is accompanied by shortage of resources such as water. Since half of humankind directly depends on freshwater and other ecosystem services provided by mountainous areas, it is essential to study such complex terrains and how natural as well as agricultural systems react to climatic and other anthropogenic changes.
Emissions of greenhouse gases like Nitrous oxide (N2O) and Methane (CH4) are of global concern, too, because they are involved in global warming and therewith: climate change. Major sources of N2O are agriculturally managed soils, and very important sources of CH4 are rice paddies. Thus, it is of great importance to study intensively managed agricultural systems and the effects of the management practices on greenhouse gas emissions.
The major focus of this thesis is to quantify dry crop fields’ and forests’ N2O emissions as well as rice paddies’ N2O and CH4 emissions and to identify climatic as well as management related factors and underlying processes which are driving the N2O fluxes in a complex terrain.
A prolonged early summer drought in 2010 led to significant N2O consumption in soil of three different forest sites. The following above-average monsoon rainfall period indeed turned the N2O consumption into emission but could not turn the N2O balance of a forest on sandy-loam substrate from negative into a positive one, which means that for the first time a negative N2O balance was observed for a forest soil during the growing season. The N2O emissions of those forest sites were clearly driven by soil moisture and temperature and there appeared to be an effect of the substrate on N2O emissions as well, as it is increasingly often observed that sandy-loam soils show significant N2O consumption.
Plastic mulching – a worldwide used method in agriculture to increase crop production by enhancing soil temperature, creating more stable soil moisture conditions and restricting arable weed growth – turned out to have a mitigating effect on N2O emissions. DNDC (Denitrification and Decomposition) modeling results matched best with the measurement results when the maximum daily soil temperature and half of the daily precipitation was assumed to occur as dominating climate conditions underneath the impervious polyethylene (PE) film, suggesting that N2O production underneath the plastic cover was driven by soil moisture and temperature. N2O emissions from a non-fertilized soy bean field, which has Nitrogen fixation as an additional Nitrogen source, were similar to the N2O emissions from a radish field after application of an intermediate amount of N fertilizer of 200 kg ha-1.
Comparing N2O and CH4 emissions from rice paddies under different water management practices showed that intermittent irrigation (II) (no continuous flooding, no water logging)
had the least global warming potential (GWP) which was only 30% of the global warming potential (GWP) of a traditionally irrigated (TI) paddy (continuous flooding and water logging). Another practice of 2.5 months of continuous flooding, followed by midseason drainage and reflooding which created moist but non-water logged conditions (FDFM) lead to 66% of the traditionally irrigated paddies combined CH4 and N2O emissions. These results suggest that a trend towards less flooding has a great potential to mitigate greenhouse gas emissions from a sandy or sandy-loam substrate, respectively. Studying the three paddies’ subsoil conditions revealed that N2O production and consumption processes had mainly taken place between 25 and 50 cm soil depth judging by N2O concentrations and δ15N-N2O values along the soil profiles of all the investigated paddies as well as gene abundances of denitrifying and nitrifying bacteria of the FDFM paddy.
Apart from these important findings on N2O flux dynamics of three different land use systems, it is noticeable that the N2O emissions of the study region are in general very low which is very pleasing and implies that the area deals with global change challenges and associated intensive agriculture in a way that comparatively only small amounts of N2O degas. But this raises the question after the “why?” considering that large amounts of fertilizer are applied on the fields. This thesis does not have a final answer to that question but it discusses whether the sandy substrate may play a major role for the N dynamics of the whole area. There is evidence that NO3- - as the substrate for denitrification - leaches easily due to the soil conditions. To finally figure out why the N2O emissions are that low a more detailed investigation on the fate of NO3- would be desirable.
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Intuitive Human-Robot Interaction by Intention Recognition
(2013)
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Muhammad Awais
- For two humans to interact with each other to perform a common task, they need to know the expectation of each other during interaction. For example if we consider an example of a waiter and a guest. If the waiter tilts the bottle to offer a drink to the guest then he may expect two actions from the guest, i.e., either the guest will forward his glass to get it filled or he will take his glass backward for not accepting the drink. If the guest forwards his glass then the waiter expects that the guest will keep his glass at a certain point until he pours the liquid into the glass. Similarly if the guest takes its glass backward then he expects from the waiter not to pour the liquid into his glass. In any case of misunderstanding an accident can occur. It applies to almost all the instances of human-human interaction. The recognition of the intention plays a key role in human-human interaction. It is equally important in human-robot interaction.
With the increase of research in the field of robotics, the robots are and will be becoming more and more part of human life. For the robots to be the effective part of the human life they should be helpful to the human. For a robot to be helpful to the human he should act according to the human. In case if the robot tries to help the human without knowing the intention of the interacting human then the robot can be itself a problem rather than a solution to the problems. Therefore it is necessary for a robot to know the intention of the human with whom the robot is supposed to interact to facilitate him.
The aim of this work is to propose a solution to make the human robot interaction intuitive. For making the human-robot interaction intuitive the intention of the human should be known to the interacting robot. A probabilistic approach is introduced to recognize the human intention. The approach uses the finite state machines. Each finite state machine representing a unique human intention carries a probabilistic value that is called the weight of the finite state machine. That weight tells the robot about the current human intention.
Since it is not possible to embed all the possible intentions into the robot that the robot may need to recognize. Thus, there should be a measure that the robot can learn new human intentions. An approach is discussed for this purpose.
For the human-robot interaction to be intelligent the robot should be quick in his response towards the human intention. An approach is described that addresses the issue of quick (proactive) response of the robot. The proposed approach also discusses the scenario concerning the ambiguous human intention. An ambiguous intention is a human intention that apparently corresponds to more than one human intention.
There may be a scenario in which the human has a totally new intention that the robot does not know already and also has not learned that intention. In this case, apparently there is no human- robot interaction. In order to cope with this problem an approach is discussed that enables the robot to select an appropriate action to interact with the human.
An approach concerning the generalization of the human intention is also discussed. By generalizing the human intention, the robot can extend its response according to the human intention. The extension of the response means that the robot takes those actions that were not instructed to him to be taken concerning the human intention.
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Charge and excitation-energy transfer in time-dependent density functional theory
(2013)
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Dirk Hofmann-Mees
- Learning about and understanding the mechanisms and pathways of charge and excitation-energy transfer of natural molecular complexes is a promising approach for the tailored design of new artificial energy-converting materials. Therefore, next to extensive experimental investigations, a theoretical method that is able to reliably describe and predict these phenomena from first principles is of practical relevance. In principle, density functional theory (DFT) and time-dependent density functional theory (TDDFT) appear as natural choices to study the relevant sizable molecules on a first-principles scale at bearable computational cost. However, the application of standard local and semilocal density functional approximations suffers from well-known deficiencies, in particular, as far as the simulation of charge-transfer phenomena is concerned. The present thesis approaches charge and excitation-energy transfer with the objective of improving the predictive power and extending the range of applicability of (TD)DFT.
The deficiencies of standard density functional approximations have been related to self-interaction. Hence, one major aspect of this work is the extension of the self-interaction correction in Kohn-Sham DFT that is based on the generalized optimized effective potential to TDDFT using a real-time propagation approach. The multiplicative Kohn-Sham potential allows for a transparent analysis of the exchange-correlation potential during time evolution. It reveals frequency-dependent field-counteracting behavior and step structures that appear in dynamic charge-transfer situations. The latter are important for the proper description of charge transfer. Self-interaction correction allows to access many cases that are difficult for standard TDDFT ranging from chain-like systems over excitonic excitations in semiconductor nanoclusters to short- and long-range charge-transfer excitations. At the same time, it does not spoil the reasonable accuracy that already (semi)local functionals exhibit for local excitations. Moreover, the TDDFT perspective on self-interaction correction sheds new light also on the ground-state formalism. Complex degrees of freedom in the energy-minimizing transformation of the generalized optimized effective potential approach yield smoother orbital densities that appear more reasonable when inserted into approximate functionals in the self-interaction correction formalism. This work provides new insight into the use of different functional approximations. Last but not least, the influence of spin-symmetry breaking and step structures of the potential on the preference to transfer integer units of the elementary electric charge between largely separated donor and acceptor moieties is illustrated when static external electric fields are applied. This work has been reported in three publications and one submitted manuscript.
In the field of excitation-energy transfer, recent discoveries of quantum coherence effects shed new light on the mechanisms behind energy-transfer rates. The latter are affected by a number of different properties of the isolated molecules, but involve also effects due to the environment of the system. This thesis addresses excitation-energy transfer phenomena from two perspectives. First, I use real-time propagation TDDFT to investigate the intermolecular coupling strength and the coupling mechanism between single fragments of supermolecular setups. These investigations base on standard closed quantum system TDDFT and exploit the coherent oscillation of excitation energy between separated molecules after the initial excitation process. Second, I use open quantum system ideas in the framework of TDDFT to study the influence of the system’s environment on the energy-transfer time scales and pathways in a circular arrangement of molecules using an effective energy-dissipation mechanism. The first part of these results is published. The second part is presented in this thesis and includes work in progress.
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Polyelectrolyte Coatings with Internal Hierarchy
(2013)
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Julia Gensel
- The results presented in this thesis are focused on the surface modification by polyelectrolytes and polyelectrolyte copolymers. The internal structural hierarchy originate thereby from the self-assembly processes at different length scales. To generate different levels of hierarchy, the coatings were constructed by using either the layer-by-layer (LbL) deposition method (lateral chemical structure), the adsorption of supramolecular aggregates (lateral topographycal structure), or the combination of both. Using these techniques, one can control the properties of the coatings by varying the chemical structure of the polyelectrolytes, for instance, their charge density, thus providing a convenient way for their functionalization and the ability to tune properties of the surface. Therefore, we were working with systems which have variable charge densities. With this approach, we were able to produce thin and ultrathin nanostructured films with tunable properties and functionality.
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Synthesis and Combinatorial Optimization of Novel Star-Shaped Resist Materials for Lithographic Applications
(2012)
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Florian Wieberger
- Gordon Earle Moore predicted in the mid-1960s the cost-efficient doubling of transistors’ number on integrated circuits every two years – known as Moore’s Law. Leading companies orientates by the development of integrated circuits on this Moore’s Law and contributed to this prediction to come true up to the present. In so doing, the semiconductor industry drafts every two years aims to fulfill this prediction summarized in the so-called International Technology Roadmap for Semiconductors (ITRS). The ITRS lists guidelines for cost-effective progresses in performance of integrated circuits, e.g. design of integrated circuits, advancements of exposure tools and exposure techniques, and closely correlated resist materials. This thesis deals with the development of new resist materials and their combinatorial investigation concerning the performance in lithographic patterning.
The lithographic patterning procedure is a sequence of multiple processing steps and thus this procedure involves many processing variables interacting strongly with each other. For understanding and comprehensive investigation of such multi-variable dependent systems the development and implementation of combinatorial approaches were in the focus of this thesis. Furthermore this thesis is focused on the synthesis of new tailored resist materials for lithographic patterning. Star topology was the selected polymer architecture of this new resist material realized via the core-first atom transfer radical polymerization (ATRP) technique. The lithographic performance of electron beam lithography patterning was investigated for the resulting randomly distributed star terpolymers and star block copolymers by combinatorial libraries in view of features’ quality.
The first chapter deals with developed, adapted, and improved combinatorial techniques for thin film investigations in general and utilized for lithographic patterning investigations in particular. The lithographic patterning procedure of chemically amplified resist systems consists of various steps: film preparation, post apply bake (PAB) to remove residual solvent, exposure, post exposure bake (PEB) to activate the catalytic reaction, and development. For this rather complex process variable gradients were developed and adapted for each processing step to investigate and optimize the performance of especially new resist systems. For the film preparation a method was developed to prepare an internal material composition gradient. This was realized by a gradient extrudate prepared using two individual controllable syringe pumps and subsequent doctor-blading. The material composition gradient was verified by high performance liquid chromatography. The second (PAB) and also the fourth (PEB) processing step are both annealing processes of the resist film although they serve different purposes. For the investigation of such annealing processes temperature gradients were prepared adjustable in temperature range and temperature slope. This adjustability is ensured by the active heating and the active cooling source and also by the gap and the type of metal plate. For the third step exposure methods were developed to realize defined exposure dose gradients in very small areas of the resist film. Different exposure dose gradients were designed for photolithography as well as for electron beam lithography. For the latter case this dose gradient was programmed in the pattern design using the software which controls the electron beam during the exposure process. The dose gradient for photolithography investigations was realized by a special designed shadow mask. For the last processing step development a preliminary screening of the dissolubility conditions of the resist film was established utilizing quartz crystal microbalances. Based on this measured dissolubility behavior the time frame was set for development time gradients performed by a stepwise or continuously immersion of the resist films. Lastly two to three variable gradients were combined to binary or ternary combinatorial libraries, respectively. The ternary combinatorial libraries allow the investigation of three variables of the lithographic patterning process in one experiment. Thus it is possible to optimize a resist material system fast and efficiently in respect to resist performance.
In the second chapter a star-shaped teroligomer is reported as new high potential resist type for lithographic patterning purposes. The polymerization was carried out via the core-first ATRP route using a functionalized saccharose with eight initiating sites as core. Four star-shaped teroligomers were synthesized with varying target arm lengths. In addition a saccharose molecule was synthesized with an average number of 3.5 initiating sites and thus a star oligomer was realized with a reduced arm number but an identical core and similar arm length. As reference resist material a linear model oligomer was synthesized using ethyl 2-bromoisobutyrate as initiator. For all polymers narrow monomodal distributions were detected with polydispersity index values of lower than 1.1. Based on calibration polymerizations runs the monomer feed of the three used monomers was adapted to achieve targeted monomer incorporations for all teroligomers. The targeted monomer incorporation was copied from a currently industrially used linear teroligomer. One star oligomer was selected as proof of principle for the utilization of the star architecture for lithographic purposes. This new resist material was combinatorial investigated in a ternary library and thus optimized in one experiment concerning exposure dose, PEB temperature, and development time. The optimized patterns with a feature size of 100 nm and an excellent line edge roughness (LER) value of 3.1 nm were observed.
The last chapter of this thesis demonstrates the straight forward advancement of the star-shaped resist material reported in chapter two. The statistical monomer incorporation was exchanged by the introduction of the tailored star block copolymer architecture. This architecture was synthesized for the first time via the core-first ATRP route by full conversion of a first polar monomer and in-situ polymerization of additionally added nonpolar monomer. The successful syntheses were indicated by contact angle measurements showing increased hydrophobicity of star block copolymers in contrast to random star copolymers with the same monomer incorporation. The star block copolymers exhibited also enhanced dissolubility behavior characterized by quartz crystal microbalance measurements. Furthermore they demonstrated an up to eight times increased sensitivity at their lithographic application in contrast to the synthesized reference linear copolymer. The most promising star block copolymer was selected to investigate its lithographic performance. The optimization was performed in a ternary combinatorial library based on the gradient variables exposure dose and feature size, PEB temperature, and development time. The optimized pattern of clear lines and a feature size of 66 nm was observed with a LER value of 6 nm.
To conclude, different tailored star-shaped terpolymers were synthesized using the ATRP core-first route and successfully applied in the lithographic patterning process for the first time. In addition the combinatorial optimization offers the absolutely promising potential of utilizing these star shaped resist materials by the demonstrated brilliant LER values, the achieved extremely high sensitivity, and the fast and efficient development of clear 66 nm lines.
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Single-Particle Orbit Tracking - Setup, Characterisation and Application
(2013)
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Dominique Ernst
- In this thesis, the development and experimental realisation of an optical setup which records the 2-dimensional trajectories of single fluorescently labeled polystyrene beads, either 20nm or 50nm in diameter, with a high spatial and temporal resolution is introduced. Combining single molecule fluorescence techniques with a new method called single-particle orbit tracking the spatial position of the beads could be determined with an accuracy of less than 10nm at a time resolution of 4 ms. The idea is to manipulate the excitation light spatially and temporally to locate a particle. In order to do so, special optics which deflect a laser beam and guide it on a circular path were used. Subsequently, this rotating beam is projected by a microscope into the sample with the diffusing particles. Due to the spatially and periodically modulated excitation light, the emission signal of the bead is modulated with the frequency of the rotation of the laser focus. The amplitude of the modulated emission signal depends on the position of the particle within the excitation orbit. An ingeniously developed algorithm calculates the position of the particle with respect to the centre of the orbit by demodulating the emission signal and restores the particle back to the orbit centre. Applying this method successively, the trajectory of the diffusing bead can be reconstructed. Besides the experimental realisation, the characterisation of the setup in terms of the spatial and temporal accuracy as well as the experimental shortcomings that influences the measured trajectories and hence, the interpretation of the data, were also the main topics of this work. For this purpose a reference sample of 20nm sized beads in glycerol was used. The accuracies were studied mainly by computer simulations and the artifacts by experiments. The technical details of the setup and the characterisation results were published (publication P1).
The recorded trajectories were analysed with various methods, among which the commonly used mean squared displacement (MSD) yields the results with highest information. The diffusion coefficient as well as the diffusion behaviour could be quantified. With this method the obtainable accuracy in measuring the diffusion coefficient by the acquisition of single-particle trajectories was studied as a function of the length of the trajectories and as a function of the number of fitting points that were used for a linear fit to the experimentally determined MSD-curves. As expected, the relative error of the determined diffusion coefficient gets better for longer trajectories. Further, an optimal number of fitting points for the linear approximation to the MSD-curves was found, which yields the most exact values for the diffusion coefficients and which is independent of the trajectory length. For the first time, experimental results on that issue were compared with theoretical predictions, where a good agreement was found. These findings were published (publication P2). By the use of the Stokes-Einstein relation the diffusion coefficients could further be converted to particle radii. A closer examination of these radii emphasises the influence of the afore mentioned number of fitting points. For the optimal value, significantly precise radii could be determined.
Finally, an application of the new setup is presented. In cooperation with the chair of experimental physics I (group of Prof. Dr. M. Weiss) of the University of Bayreuth, the diffusion behaviour of single nanoparticles in a complex fluid was studied. Background hereto is the investigation of biochemical reactions in a biological cell, whose kinetic is given by the diffusion of the corresponding reaction partners. Due to the high crowding of the cell compartments the diffusion is hindered. The diffusion behaviour in these systems is called anomalous and more exactly subdiffusive. Several theoretical models have been developed to explain this phenomenon, but yet without experimental verifications. Here, the diffusion of 50nm sized polymer beads in the model system dextran (a highly branched biopolysaccaride) is investigated experimentally with high spatial and temporal resolution. The data were analysed in the group of the cooperation partner which yields a very good agreement with the model of “fractional Brownian motion”. These results were also published (publication P3).
