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Dieser Artikel adressiert zwei bisher nur wenig untersuchte Aspekte der Führungsforschung: Führungsverhalten im öffentlichen Sektor und Faktoren die Führungsverhalten beeinflussen. Mittels einer Fallstudie in der Bundesagentur für Arbeit werden explorativ Hypothesen über Einflussfaktoren des Führungsverhaltens aufgestellt. Die Studie kommt zu der Erkenntnis, dass eine oftmals angenommene Führungslücke im öffentlichen Sektor nicht bestätigt werden kann. Für das ausgeprägte Führungsverhalten, das in der Fallstudie beobachtet wurde, wird als Determinante die besondere Ausgestaltung des Managementsystems der Bundesagentur für Arbeit verantwortlich gemacht. Dazu gehört unter anderem das Performance Management System sowie die Führungskräfteauswahl und -entwicklung. Die Arbeit schließt mit Empfehlungen für weitere Forschungsansätze auf dem Gebiet der Führungsforschung im öffentlichen Sektor.
Virtualized cloud data centers provide on-demand resources, enable agile resource provisioning, and host heterogeneous applications with different resource requirements. These data centers consume enormous amounts of energy, increasing operational expenses, inducing high thermal inside data centers, and raising carbon dioxide emissions. The increase in energy consumption can result from ineffective resource management that causes inefficient resource utilization. This dissertation presents detailed models and novel techniques and algorithms for virtual resource management in cloud data centers. The proposed techniques take into account Service Level Agreements (SLAs) and workload heterogeneity in terms of memory access demand and communication patterns of web applications and High Performance Computing (HPC) applications. To evaluate our proposed techniques, we use simulation and real workload traces of web applications and HPC applications and compare our techniques against the other recently proposed techniques using several performance metrics. The major contributions of this dissertation are the following: proactive resource provisioning technique based on robust optimization to increase the hosts' availability for hosting new VMs while minimizing the idle energy consumption. Additionally, this technique mitigates undesirable changes in the power state of the hosts by which the hosts' reliability can be enhanced in avoiding failure during a power state change. The proposed technique exploits the range-based prediction algorithm for implementing robust optimization, taking into consideration the uncertainty of demand. An adaptive range-based prediction for predicting workload with high fluctuations in the short-term. The range prediction is implemented in two ways: standard deviation and median absolute deviation. The range is changed based on an adaptive confidence window to cope with the workload fluctuations. A robust VM consolidation for efficient energy and performance management to achieve equilibrium between energy and performance trade-offs. Our technique reduces the number of VM migrations compared to recently proposed techniques. This also contributes to a reduction in energy consumption by the network infrastructure. Additionally, our technique reduces SLA violations and the number of power state changes. A generic model for the network of a data center to simulate the communication delay and its impact on VM performance, as well as network energy consumption. In addition, a generic model for a memory-bus of a server, including latency and energy consumption models for different memory frequencies. This allows simulating the memory delay and its influence on VM performance, as well as memory energy consumption. Communication-aware and energy-efficient consolidation for parallel applications to enable the dynamic discovery of communication patterns and reschedule VMs using migration based on the determined communication patterns. A novel dynamic pattern discovery technique is implemented, based on signal processing of network utilization of VMs instead of using the information from the hosts' virtual switches or initiation from VMs. The result shows that our proposed approach reduces the network's average utilization, achieves energy savings due to reducing the number of active switches, and provides better VM performance compared to CPU-based placement. Memory-aware VM consolidation for independent VMs, which exploits the diversity of VMs' memory access to balance memory-bus utilization of hosts. The proposed technique, Memory-bus Load Balancing (MLB), reactively redistributes VMs according to their utilization of a memory-bus using VM migration to improve the performance of the overall system. Furthermore, Dynamic Voltage and Frequency Scaling (DVFS) of the memory and the proposed MLB technique are combined to achieve better energy savings.
The toxicologically most relevant mercury (Hg) species for human exposure is methylmercury (MeHg). Thiomersal is a common preservative used in some vaccine formulations. The aim of this study is to get further mechanistic insight into the yet not fully understood neurotoxic modes of action of organic Hg species. Mercury species investigated include MeHgCl and thiomersal. Additionally HgCl2 was studied, since in the brain mercuric Hg can be formed by dealkylation of the organic species. As a cellular system astrocytes were used. In vivo astrocytes provide the environment necessary for neuronal function. In the present study, cytotoxic effects of the respective mercuricals increased with rising alkylation level and correlated with their cellular bioavailability. Further experiments revealed for all species at subcytotoxic concentrations no induction of DNA strand breaks, whereas all species massively increased H2O2-induced DNA strand breaks. This co- genotoxic effect is likely due to a disturbance of the cellular DNA damage response. Thus, at nanomolar, sub-cytotoxic concentrations, all three mercury species strongly disturbed poly(ADP-ribosyl)ation, a signalling reaction induced by DNA strand breaks. Interestingly, the molecular mechanism behind this inhibition seems to be different for the species. Since chronic PARP-1 inhibition is also discussed to sacrifice neurogenesis and learning abilities, further experiments on neurons and in vivo studies could be helpful to clarify whether the inhibition of poly(ADP-ribosyl) ation contributes to organic Hg induced neurotoxicity.
One of the most significant current discussions in Astrophysics relates to the origin of high-energy cosmic rays. According to our current knowledge, the abundance distribution of the elements in cosmic rays at their point of origin indicates, within plausible error limits, that they were initially formed by nuclear processes in the interiors of stars. It is also believed that their energy distribution up to 1018 eV has Galactic origins. But even though the knowledge about potential sources of cosmic rays is quite poor above „ 1015 eV, that is the “knee” of the cosmic-ray spectrum, up to the knee there seems to be a wide consensus that supernova remnants are the most likely candidates. Evidence of this comes from observations of non-thermal X-ray radiation, requiring synchrotron electrons with energies up to 1014 eV, exactly in the remnant of supernovae. To date, however, there is not conclusive evidence that they produce nuclei, the dominant component of cosmic rays, in addition to electrons. In light of this dearth of evidence, γ-ray observations from supernova remnants can offer the most promising direct way to confirm whether or not these astrophysical objects are indeed the main source of cosmic-ray nuclei below the knee. Recent observations with space- and ground-based observatories have established shell-type supernova remnants as GeV-to- TeV γ-ray sources. The interpretation of these observations is however complicated by the different radiation processes, leptonic and hadronic, that can produce similar fluxes in this energy band rendering ambiguous the nature of the emission itself. The aim of this work is to develop a deeper understanding of these radiation processes from a particular shell-type supernova remnant, namely RX J1713.7–3946, using observations of the LAT instrument onboard the Fermi Gamma-Ray Space Telescope. Furthermore, to obtain accurate spectra and morphology maps of the emission associated with this supernova remnant, an improved model of the diffuse Galactic γ-ray emission background is developed. The analyses of RX J1713.7–3946 carried out with this improved background show that the hard Fermi-LAT spectrum cannot be ascribed to the hadronic emission, leading thus to the conclusion that the leptonic scenario is instead the most natural picture for the high-energy γ-ray emission of RX J1713.7–3946. The leptonic scenario however does not rule out the possibility that cosmic-ray nuclei are accelerated in this supernova remnant, but it suggests that the ambient density may not be high enough to produce a significant hadronic γ-ray emission. Further investigations involving other supernova remnants using the improved back- ground developed in this work could allow compelling population studies, and hence prove or disprove the origin of Galactic cosmic-ray nuclei in these astrophysical objects. A break- through regarding the identification of the radiation mechanisms could be lastly achieved with a new generation of instruments such as CTA.
Large-scale floodplain sediment dynamics in the Mekong Delta : present state and future prospects
(2014)
The Mekong Delta (MD) sustains the livelihood and food security of millions of people in Vietnam and Cambodia. It is known as the “rice bowl” of South East Asia and has one of the world’s most productive fisheries. Sediment dynamics play a major role for the high productivity of agriculture and fishery in the delta. However, the MD is threatened by climate change, sea level rise and unsustainable development activities in the Mekong Basin. But despite its importance and the expected threats, the understanding of the present and future sediment dynamics in the MD is very limited. This is a consequence of its large extent, the intricate system of rivers, channels and floodplains and the scarcity of observations. Thus this thesis aimed at (1) the quantification of suspended sediment dynamics and associated sediment-nutrient deposition in floodplains of the MD, and (2) assessed the impacts of likely future boundary changes on the sediment dynamics in the MD. The applied methodology combines field experiments and numerical simulation to quantify and predict the sediment dynamics in the entire delta in a spatially explicit manner. The experimental part consists of a comprehensive procedure to monitor quantity and spatial variability of sediment and associated nutrient deposition for large and complex river floodplains, including an uncertainty analysis. The measurement campaign applied 450 sediment mat traps in 19 floodplains over the MD for a complete flood season. The data also supports quantification of nutrient deposition in floodplains based on laboratory analysis of nutrient fractions of trapped sedimentation.The main findings are that the distribution of grain size and nutrient fractions of suspended sediment are homogeneous over the Vietnamese floodplains. But the sediment deposition within and between ring dike floodplains shows very high spatial variability due to a high level of human inference. The experimental findings provide the essential data for setting up and calibration of a large-scale sediment transport model for the MD. For the simulation studies a large scale hydrodynamic model was developed in order to quantify large-scale floodplain sediment dynamics. The complex river-channel-floodplain system of the MD is described by a quasi-2D model linking a hydrodynamic and a cohesive sediment transport model. The floodplains are described as quasi-2D presentations linked to rivers and channels modeled in 1D by using control structures. The model setup, based on the experimental findings, ignored erosion and re-suspension processes due to a very high degree of human interference during the flood season. A two-stage calibration with six objective functions was developed in order to calibrate both the hydrodynamic and sediment transport modules. The objective functions include hydraulic and sediment transport parameters in main rivers, channels and floodplains. The model results show, for the first time, the tempo-spatial distribution of sediment and associated nutrient deposition rates in the whole MD. The patterns of sediment transport and deposition are quantified for different sub-systems. The main factors influencing spatial sediment dynamics are the network of rivers, channels and dike-rings, sluice gate operations, magnitude of the floods and tidal influences. The superposition of these factors leads to high spatial variability of the sediment transport and deposition, in particular in the Vietnamese floodplains. Depending on the flood magnitude, annual sediment loads reaching the coast vary from 48% to 60% of the sediment load at Kratie, the upper boundary of the MD. Deposited sediment varies from 19% to 23% of the annual load at Kratie in Cambodian floodplains, and from 1% to 6% in the compartmented and diked floodplains in Vietnam. Annual deposited nutrients (N, P, K), which are associated to the sediment deposition, provide on average more than 50% of mineral fertilizers typically applied for rice crops in non-flooded ring dike compartments in Vietnam. This large-scale quantification provides a basis for estimating the benefits of the annual Mekong floods for agriculture and fishery, for assessing the impacts of future changes on the delta system, and further studies on coastal deposition/erosion. For the estimation of future prospects a sensitivity-based approach is applied to assess the response of floodplain hydraulics and sediment dynamics to the changes in the delta boundaries including hydropower development, climate change in the Mekong River Basin and effective sea level rise. The developed sediment model is used to simulate the mean sediment transport and sediment deposition in the whole delta system for the baseline (2000-2010) and future (2050-2060) periods. For each driver we derive a plausible range of future changes and discretize it into five levels, resulting in altogether 216 possible factor combinations. Our results thus cover all plausible future pathways of sediment dynamics in the delta based on current knowledge. The uncertainty of the range of the resulting impacts can be decreased in case more information on these drivers becomes available. Our results indicate that the hydropower development dominates the changes in sediment dynamics of the Mekong Delta, while sea level rise has the smallest effect. The floodplains of Vietnamese Mekong Delta are much more sensitive to the changes compared to the other subsystems of the delta. In terms of median changes of the three combined drivers, the inundation extent is predicted to increase slightly, but the overall floodplain sedimentation would be reduced by approximately 40%, while the sediment load to the Sea would diminish to half of the current rates. These findings provide new and valuable information on the possible impacts of future development on the delta, and indicate the most vulnerable areas. Thus, the presented results are a significant contribution to the ongoing international discussion on the hydropower development in the Mekong basin and its impact on the Mekong delta.
Entwicklung von Strategien zur Attraktivitätssteigerung von Fortbildungen im Gesundheitsmanagement
(2014)
Die Herausforderungen des 21. Jahrhunderts bewirken sowohl im Bundesministerium der Finanzen BMF als auch im französischen Wirtschafts- und Finanzministerium MINEFI, der Gesunderhaltung der Beschäftigten besondere Aufmerksamkeit zu schenken. Beide Verwaltungen sehen dabei die Referatsleiter/innen (RL) in der Pflicht und bieten deshalb Fortbildungen im Gesundheitsmanagement an. Das Interesse der RL für dieses Angebot ist bisher gering. Die vorliegende Masterarbeit untersucht die Ursachen für das in der deutschen und französischen Finanzverwaltung unterschiedlich geringe Interesse und kommt zu dem Schluss, dass die Hemmnisse im MINEFI stärker durch soziokulturelle und institutionelle Faktoren (republikanische Elitenbildung und Positionsmacht der jeweiligen Hierarchiestufe) bedingt sind, während im BMF institutionelle und persönlichkeitsspezifische Gründe zusammentreffen. Die Behördenkultur beider Ministerien fokussiert die Arbeitsergebnisse der RL und lässt ihr Verhältnis zu den Referatsangehörigen weitestgehend außer Acht. Eine Attraktivitätssteigerung des Fortbildungsangebots im Gesundheitsmanagement setzt in beiden Verwaltungen voraus, Marketingstrategien innerhalb der Behörde zu etablieren, die die Wertigkeit des Gesundheitsmanagements im Organisationsgefüge erhöhen und dadurch die RL stärker motivieren. Dieser Change-Prozess erfordert Ausdauer und Geduld.
This work is devoted to the convergence analysis of a modified Runge-Kutta-type iterative regularization method for solving nonlinear ill-posed problems under a priori and a posteriori stopping rules. The convergence rate results of the proposed method can be obtained under Hölder-type source-wise condition if the Fréchet derivative is properly scaled and locally Lipschitz continuous. Numerical results are achieved by using the Levenberg-Marquardt and Radau methods.
Organische Halbleiter besitzen neue, bemerkenswerte Materialeigenschaften, die sie für die grundlegende Forschung wie auch aktuelle technologische Entwicklung (bsw. org. Leuchtdioden, org. Solarzellen) interessant werden lassen. Aufgrund der starken konformative Freiheit der konjugierten Polymerketten führt die Vielzahl der möglichen Anordnungen und die schwache intermolekulare Wechselwirkung für gewöhnlich zu geringer struktureller Ordnung im Festkörper. Die Morphologie hat gleichzeitig direkten Einfluss auf die elektronische Struktur der organischen Halbleiter, welches sich meistens in einer deutlichen Reduktion der Ladungsträgerbeweglichkeit gegenüber den anorganischen Verwandten zeigt. So stellt die Beweglichkeit der Ladungen im Halbleiter einen der limitierenden Faktoren für die Leistungsfähigkeit bzw. den Wirkungsgrad von funktionellen organischen Bauteilen dar. Im Jahr 2009 wurde ein neues auf Naphthalindiimid und Bithiophen basierendes Dornor/Akzeptor Copolymer vorgestellt [P(NDI2OD‑T2)], welches sich durch seine außergewöhnlich hohe Ladungsträgermobilität auszeichnet. In dieser Arbeit wird die Ladungsträgermobilität in P(NDI2OD‑T2) bestimmt, und der Transport durch eine geringe energetischer Unordnung charakterisiert. Obwohl dieses Material zunächst als amorph beschrieben wurde zeigt eine detaillierte Analyse der optischen Eigenschaften von P(NDI2OD‑T2), dass bereits in Lösung geordnete Vorstufen supramolekularer Strukturen (Aggregate) existieren. Quantenchemische Berechnungen belegen die beobachteten spektralen Änderungen. Mithilfe der NMR-Spektroskopie kann die Bildung der Aggregate unabhängig von optischer Spektroskopie bestätigt werden. Die Analytische Ultrazentrifugation an P(NDI2OD‑T2) Lösungen legt nahe, dass sich die Aggregation innerhalb der einzelnen Ketten unter Reduktion des hydrodynamischen Radius vollzieht. Die Ausbildung supramolekularen Strukturen nimmt auch eine signifikante Rolle bei der Filmbildung ein und verhindert gleichzeitig die Herstellung amorpher P(NDI2OD‑T2) Filme. Durch chemische Modifikation der P(NDI2OD‑T2)-Kette und verschiedener Prozessierungs-Methoden wurde eine Änderung des Kristallinitätsgrades und gleichzeitig der Orientierung der kristallinen Domänen erreicht und mittels Röntgenbeugung quantifiziert. In hochauflösenden Elektronenmikroskopie-Messungen werden die Netzebenen und deren Einbettung in die semikristallinen Strukturen direkt abgebildet. Aus der Kombination der verschiedenen Methoden erschließt sich ein Gesamtbild der Nah- und Fernordnung in P(NDI2OD‑T2). Über die Messung der Elektronenmobilität dieser Schichten wird die Anisotropie des Ladungstransports in den kristallographischen Raumrichtungen von P(NDI2OD‑T2) charakterisiert und die Bedeutung der intramolekularen Wechselwirkung für effizienten Ladungstransport herausgearbeitet. Gleichzeitig wird deutlich, wie die Verwendung von größeren und planaren funktionellen Gruppen zu höheren Ladungsträgermobilitäten führt, welche im Vergleich zu klassischen semikristallinen Polymeren weniger sensitiv auf die strukturelle Unordnung im Film sind.
A dramatic efficiency improvement of bulk heterojunction solar cells based on electron-donating conjugated polymers in combination with soluble fullerene derivatives has been achieved over the past years. Certified and reported power conversion efficiencies now reach over 9% for single junctions and exceed the 10% benchmark for tandem solar cells. This trend brightens the vision of organic photovoltaics becoming competitive with inorganic solar cells including the realization of low-cost and large-area organic photovoltaics. For the best performing organic materials systems, the yield of charge generation can be very efficient. However, a detailed understanding of the free charge carrier generation mechanisms at the donor acceptor interface and the energy loss associated with it needs to be established. Moreover, organic solar cells are limited by the competition between charge extraction and free charge recombination, accounting for further efficiency losses. A conclusive picture and the development of precise methodologies for investigating the fundamental processes in organic solar cells are crucial for future material design, efficiency optimization, and the implementation of organic solar cells into commercial products.
In order to advance the development of organic photovoltaics, my thesis focuses on the comprehensive understanding of charge generation, recombination and extraction in organic bulk heterojunction solar cells summarized in 6 chapters on the cumulative basis of 7 individual publications.
The general motivation guiding this work was the realization of an efficient hybrid inorganic/organic tandem solar cell with sub-cells made from amorphous hydrogenated silicon and organic bulk heterojunctions. To realize this project aim, the focus was directed to the low band-gap copolymer PCPDTBT and its derivatives, resulting in the examination of the charge carrier dynamics in PCPDTBT:PC70BM blends in relation to by the blend morphology. The phase separation in this blend can be controlled by the processing additive diiodooctane, enhancing domain purity and size. The quantitative investigation of the free charge formation was realized by utilizing and improving the time delayed collection field technique. Interestingly, a pronounced field dependence of the free carrier generation for all blends is found, with the field dependence being stronger without the additive. Also, the bimolecular recombination coefficient for both blends is rather high and increases with decreasing internal field which we suggest to be caused by a negative field dependence of mobility. The additive speeds up charge extraction which is rationalized by the threefold increase in mobility.
By fluorine attachment within the electron deficient subunit of PCPDTBT, a new polymer F-PCPDTBT is designed. This new material is characterized by a stronger tendency to aggregate as compared to non-fluorinated PCPDTBT. Our measurements show that for F-PCPDTBT:PCBM blends the charge carrier generation becomes more efficient and the field-dependence of free charge carrier generation is weakened. The stronger tendency to aggregate induced by the fluorination also leads to increased polymer rich domains, accompanied in a threefold reduction in the non-geminate recombination coefficient at conditions of open circuit. The size of the polymer domains is nicely correlated to the field-dependence of charge generation and the Langevin reduction factor, which highlights the importance of the domain size and domain purity for efficient charge carrier generation. In total, fluorination of PCPDTBT causes the PCE to increase from 3.6 to 6.1% due to enhanced fill factor, short circuit current and open circuit voltage. Further optimization of the blend ratio, active layer thickness, and polymer molecular weight resulted in 6.6% efficiency for F-PCPDTBT:PC70BM solar cells.
Interestingly, the double fluorinated version 2F-PCPDTBT exhibited poorer FF despite a further reduction of geminate and non-geminate recombination losses. To further analyze this finding, a new technique is developed that measures the effective extraction mobility under charge carrier densities and electrical fields comparable to solar cell operation conditions. This method involves the bias enhanced charge extraction technique. With the knowledge of the carrier density under different electrical field and illumination conditions, a conclusive picture of the changes in charge carrier dynamics leading to differences in the fill factor upon fluorination of PCPDTBT is attained. The more efficient charge generation and reduced recombination with fluorination is counterbalanced by a decreased extraction mobility. Thus, the highest fill factor of 60% and efficiency of 6.6% is reached for F-PCPDTBT blends, while 2F-PCPDTBT blends have only moderate fill factors of 54% caused by the lower effective extraction mobility, limiting the efficiency to 6.5%.
To understand the details of the charge generation mechanism and the related losses, we evaluated the yield and field-dependence of free charge generation using time delayed collection field in combination with sensitive measurements of the external quantum efficiency and absorption coefficients for a variety of blends. Importantly, both the yield and field-dependence of free charge generation is found to be unaffected by excitation energy, including direct charge transfer excitation below the optical band gap. To access the non-detectable absorption at energies of the relaxed charge transfer emission, the absorption was reconstructed from the CT emission, induced via the recombination of thermalized charges in electroluminescence. For a variety of blends, the quantum yield at energies of charge transfer emission was identical to excitations with energies well above the optical band-gap. Thus, the generation proceeds via the split-up of the thermalized charge transfer states in working solar cells. Further measurements were conducted on blends with fine-tuned energy levels and similar blend morphologies by using different fullerene derivatives. A direct correlation between the efficiency of free carrier generation and the energy difference of the relaxed charge transfer state relative to the energy of the charge separated state is found. These findings open up new guidelines for future material design as new high efficiency materials require a minimum energetic offset between charge transfer and the charge separated state while keeping the HOMO level (and LUMO level) difference between donor and acceptor as small as possible.
Donor-acceptor (D-A) copolymers have revolutionized the field of organic electronics over the last decade. Comprised of a electron rich and an electron deficient molecular unit, these copolymers facilitate the systematic modification of the material's optoelectronic properties. The ability to tune the optical band gap and to optimize the molecular frontier orbitals as well as the manifold of structural sites that enable chemical modifications has created a tremendous variety of copolymer structures. Today, these materials reach or even exceed the performance of amorphous inorganic semiconductors. Most impressively, the charge carrier mobility of D-A copolymers has been pushed to the technologically important value of 10 cm^{2}V^{-1}s^{-1}. Furthermore, owed to their enormous variability they are the material of choice for the donor component in organic solar cells, which have recently surpassed the efficiency threshold of 10%. Because of the great number of available D-A copolymers and due to their fast chemical evolution, there is a significant lack of understanding of the fundamental physical properties of these materials. Furthermore, the complex chemical and electronic structure of D-A copolymers in combination with their semi-crystalline morphology impede a straightforward identification of the microscopic origin of their superior performance. In this thesis, two aspects of prototype D-A copolymers were analysed. These are the investigation of electron transport in several copolymers and the application of low band gap copolymers as acceptor component in organic solar cells. In the first part, the investigation of a series of chemically modified fluorene-based copolymers is presented. The charge carrier mobility varies strongly between the different derivatives, although only moderate structural changes on the copolymers structure were made. Furthermore, rather unusual photocurrent transients were observed for one of the copolymers. Numerical simulations of the experimental results reveal that this behavior arises from a severe trapping of electrons in an exponential distribution of trap states. Based on the comparison of simulation and experiment, the general impact of charge carrier trapping on the shape of photo-CELIV and time-of-flight transients is discussed. In addition, the high performance naphthalenediimide (NDI)-based copolymer P(NDI2OD-T2) was characterized. It is shown that the copolymer posses one of the highest electron mobilities reported so far, which makes it attractive to be used as the electron accepting component in organic photovoltaic cells.\par Solar cells were prepared from two NDI-containing copolymers, blended with the hole transporting polymer P3HT. I demonstrate that the use of appropriate, high boiling point solvents can significantly increase the power conversion efficiency of these devices. Spectroscopic studies reveal that the pre-aggregation of the copolymers is suppressed in these solvents, which has a strong impact on the blend morphology. Finally, a systematic study of P3HT:P(NDI2OD-T2) blends is presented, which quantifies the processes that limit the efficiency of devices. The major loss channel for excited states was determined by transient and steady state spectroscopic investigations: the majority of initially generated electron-hole pairs is annihilated by an ultrafast geminate recombination process. Furthermore, exciton self-trapping in P(NDI2OD-T2) domains account for an additional reduction of the efficiency. The correlation of the photocurrent to microscopic morphology parameters was used to disclose the factors that limit the charge generation efficiency. Our results suggest that the orientation of the donor and acceptor crystallites relative to each other represents the main factor that determines the free charge carrier yield in this material system. This provides an explanation for the overall low efficiencies that are generally observed in all-polymer solar cells.
Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to Mw ≈ 50 kg mol−1 and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32–45%) in all-polymer solar cells compared to NDI-based materials (15–30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.
Permafrost, defined as ground that is frozen for at least two consecutive years, is a distinct feature of the terrestrial unglaciated Arctic. It covers approximately one quarter of the land area of the Northern Hemisphere (23,000,000 km²). Arctic landscapes, especially those underlain by permafrost, are threatened by climate warming and may degrade in different ways, including active layer deepening, thermal erosion, and development of rapid thaw features. In Siberian and Alaskan late Pleistocene ice-rich Yedoma permafrost, rapid and deep thaw processes (called thermokarst) can mobilize deep organic carbon (below 3 m depth) by surface subsidence due to loss of ground ice. Increased permafrost thaw could cause a feedback loop of global significance if its stored frozen organic carbon is reintroduced into the active carbon cycle as greenhouse gases, which accelerate warming and inducing more permafrost thaw and carbon release. To assess this concern, the major objective of the thesis was to enhance the understanding of the origin of Yedoma as well as to assess the associated organic carbon pool size and carbon quality (concerning degradability). The key research questions were:
- How did Yedoma deposits accumulate?
- How much organic carbon is stored in the Yedoma region?
- What is the susceptibility of the Yedoma region's carbon for future decomposition?
To address these three research questions, an interdisciplinary approach, including detailed field studies and sampling in Siberia and Alaska as well as methods of sedimentology, organic biogeochemistry, remote sensing, statistical analyses, and computational modeling were applied. To provide a panarctic context, this thesis additionally includes results both from a newly compiled northern circumpolar carbon database and from a model assessment of carbon fluxes in a warming Arctic.
The Yedoma samples show a homogeneous grain-size composition. All samples were poorly sorted with a multi-modal grain-size distribution, indicating various (re-) transport processes. This contradicts the popular pure loess deposition hypothesis for the origin of Yedoma permafrost. The absence of large-scale grinding processes via glaciers and ice sheets in northeast Siberian lowlands, processes which are necessary to create loess as material source, suggests the polygenetic origin of Yedoma deposits.
Based on the largest available data set of the key parameters, including organic carbon content, bulk density, ground ice content, and deposit volume (thickness and coverage) from Siberian and Alaskan study sites, this thesis further shows that deep frozen organic carbon in the Yedoma region consists of two distinct major reservoirs, Yedoma deposits and thermokarst deposits (formed in thaw-lake basins). Yedoma deposits contain ~80 Gt and thermokarst deposits ~130 Gt organic carbon, or a total of ~210 Gt. Depending on the approach used for calculating uncertainty, the range for the total Yedoma region carbon store is ±75 % and ±20 % for conservative single and multiple bootstrapping calculations, respectively. Despite the fact that these findings reduce the Yedoma region carbon pool by nearly a factor of two compared to previous estimates, this frozen organic carbon is still capable of inducing a permafrost carbon feedback to climate warming. The complete northern circumpolar permafrost region contains between 1100 and 1500 Gt organic carbon, of which ~60 % is perennially frozen and decoupled from the short-term carbon cycle.
When thawed and reintroduced into the active carbon cycle, the organic matter qualities become relevant. Furthermore, results from investigations into Yedoma and thermokarst organic matter quality studies showed that Yedoma and thermokarst organic matter exhibit no depth-dependent quality trend. This is evidence that after freezing, the ancient organic matter is preserved in a state of constant quality. The applied alkane and fatty-acid-based biomarker proxies including the carbon-preference and the higher-land-plant-fatty-acid indices show a broad range of organic matter quality and thus no significantly different qualities of the organic matter stored in thermokarst deposits compared to Yedoma deposits. This lack of quality differences shows that the organic matter biodegradability depends on different decomposition trajectories and the previous decomposition/incorporation history. Finally, the fate of the organic matter has been assessed by implementing deep carbon pools and thermokarst processes in a permafrost carbon model. Under various warming scenarios for the northern circumpolar permafrost region, model results show a carbon release from permafrost regions of up to ~140 Gt and ~310 Gt by the years 2100 and 2300, respectively. The additional warming caused by the carbon release from newly-thawed permafrost contributes 0.03 to 0.14°C by the year 2100. The model simulations predict that a further increase by the 23rd century will add 0.4°C to global mean surface air temperatures.
In conclusion, Yedoma deposit formation during the late Pleistocene was dominated by water-related (alluvial/fluvial/lacustrine) as well as aeolian processes under periglacial conditions. The circumarctic permafrost region, including the Yedoma region, contains a substantial amount of currently frozen organic carbon. The carbon of the Yedoma region is well-preserved and therefore available for decomposition after thaw. A missing quality-depth trend shows that permafrost preserves the quality of ancient organic matter. When the organic matter is mobilized by deep degradation processes, the northern permafrost region may add up to 0.4°C to the global warming by the year 2300.