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International adjudication is currently under assault, encouraging a number of States to withdraw, or to consider withdrawing, from treaties providing for international dispute settlement. This Working Paper argues that the act of treaty withdrawal is not merely as the unilateral executive exercise of the individual sovereign prerogative of a State. International law places checks upon the exercise of withdrawal, recognising that it is an act that of its nature affects the interests of other States parties, which have a collective interest in constraining withdrawal. National courts have a complementary function in restraining unilateral withdrawal in order to support the domestic constitution. The arguments advanced against international adjudication in the name of popular democracy at the national level can serve as a cloak for the exercise of executive power unrestrained by law. The submission by States of their disputes to peaceful settlement through international adjudication is central, not incidental, to the successful operation of the international legal system.
The identification of vulnerabilities in IT infrastructures is a crucial problem in enhancing the security, because many incidents resulted from already known vulnerabilities, which could have been resolved. Thus, the initial identification of vulnerabilities has to be used to directly resolve the related weaknesses and mitigate attack possibilities. The nature of vulnerability information requires a collection and normalization of the information prior to any utilization, because the information is widely distributed in different sources with their unique formats. Therefore, the comprehensive vulnerability model was defined and different sources have been integrated into one database. Furthermore, different analytic approaches have been designed and implemented into the HPI-VDB, which directly benefit from the comprehensive vulnerability model and especially from the logical preconditions and postconditions.
Firstly, different approaches to detect vulnerabilities in both IT systems of average users and corporate networks of large companies are presented. Therefore, the approaches mainly focus on the identification of all installed applications, since it is a fundamental step in the detection. This detection is realized differently depending on the target use-case. Thus, the experience of the user, as well as the layout and possibilities of the target infrastructure are considered. Furthermore, a passive lightweight detection approach was invented that utilizes existing information on corporate networks to identify applications.
In addition, two different approaches to represent the results using attack graphs are illustrated in the comparison between traditional attack graphs and a simplistic graph version, which was integrated into the database as well. The implementation of those use-cases for vulnerability information especially considers the usability. Beside the analytic approaches, the high data quality of the vulnerability information had to be achieved and guaranteed. The different problems of receiving incomplete or unreliable information for the vulnerabilities are addressed with different correction mechanisms. The corrections can be carried out with correlation or lookup mechanisms in reliable sources or identifier dictionaries. Furthermore, a machine learning based verification procedure was presented that allows an automatic derivation of important characteristics from the textual description of the vulnerabilities.
Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells
(2019)
Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell’s cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C.
A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts.
Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8%.
Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9% relative to 26.5% absolute. The results also reveal general guidelines for further performance gains of the technology.
Hyperspectral remote sensing of the spatial and temporal heterogeneity of low Arctic vegetation
(2019)
Arctic tundra ecosystems are experiencing warming twice the global average and Arctic vegetation is responding in complex and heterogeneous ways. Shifting productivity, growth, species composition, and phenology at local and regional scales have implications for ecosystem functioning as well as the global carbon and energy balance. Optical remote sensing is an effective tool for monitoring ecosystem functioning in this remote biome. However, limited field-based spectral characterization of the spatial and temporal heterogeneity limits the accuracy of quantitative optical remote sensing at landscape scales. To address this research gap and support current and future satellite missions, three central research questions were posed:
• Does canopy-level spectral variability differ between dominant low Arctic vegetation communities and does this variability change between major phenological phases?
• How does canopy-level vegetation colour images recorded with high and low spectral resolution devices relate to phenological changes in leaf-level photosynthetic pigment concentrations?
• How does spatial aggregation of high spectral resolution data from the ground to satellite scale influence low Arctic tundra vegetation signatures and thereby what is the potential of upcoming hyperspectral spaceborne systems for low Arctic vegetation characterization?
To answer these questions a unique and detailed database was assembled. Field-based canopy-level spectral reflectance measurements, nadir digital photographs, and photosynthetic pigment concentrations of dominant low Arctic vegetation communities were acquired at three major phenological phases representing early, peak and late season. Data were collected in 2015 and 2016 in the Toolik Lake Research Natural Area located in north central Alaska on the North Slope of the Brooks Range. In addition to field data an aerial AISA hyperspectral image was acquired in the late season of 2016. Simulations of broadband Sentinel-2 and hyperspectral Environmental and Mapping Analysis Program (EnMAP) satellite reflectance spectra from ground-based reflectance spectra as well as simulations of EnMAP imagery from aerial hyperspectral imagery were also obtained.
Results showed that canopy-level spectral variability within and between vegetation communities differed by phenological phase. The late season was identified as the most discriminative for identifying many dominant vegetation communities using both ground-based and simulated hyperspectral reflectance spectra. This was due to an overall reduction in spectral variability and comparable or greater differences in spectral reflectance between vegetation communities in the visible near infrared spectrum.
Red, green, and blue (RGB) indices extracted from nadir digital photographs and pigment-driven vegetation indices extracted from ground-based spectral measurements showed strong significant relationships. RGB indices also showed moderate relationships with chlorophyll and carotenoid pigment concentrations. The observed relationships with the broadband RGB channels of the digital camera indicate that vegetation colour strongly influences the response of pigment-driven spectral indices and digital cameras can track the seasonal development and degradation of photosynthetic pigments.
Spatial aggregation of hyperspectral data from the ground to airborne, to simulated satel-lite scale was influenced by non-photosynthetic components as demonstrated by the distinct shift of the red edge to shorter wavelengths. Correspondence between spectral reflectance at the three scales was highest in the red spectrum and lowest in the near infra-red. By artificially mixing litter spectra at different proportions to ground-based spectra, correspondence with aerial and satellite spectra increased. Greater proportions of litter were required to achieve correspondence at the satellite scale.
Overall this thesis found that integrating multiple temporal, spectral, and spatial data is necessary to monitor the complexity and heterogeneity of Arctic tundra ecosystems. The identification of spectrally similar vegetation communities can be optimized using non-peak season hyperspectral data leading to more detailed identification of vegetation communities. The results also highlight the power of vegetation colour to link ground-based and satellite data. Finally, a detailed characterization non-photosynthetic ecosystem components is crucial for accurate interpretation of vegetation signals at landscape scales.
The size structure of autotroph communities – the relative abundance of small vs. large individuals – shapes the functioning of ecosystems. Whether common mechanisms underpin the size structure of unicellular and multicellular autotrophs is, however, unknown. Using a global data compilation, we show that individual body masses in tree and phytoplankton communities follow power-law distributions and that the average exponents of these individual size distributions (ISD) differ. Phytoplankton communities are characterized by an average ISD exponent consistent with three-quarter-power scaling of metabolism with body
mass and equivalence in energy use among mass classes. Tree communities deviate from this pattern in a manner consistent with equivalence in energy use among diameter size classes. Our findings suggest that whilst universal metabolic constraints ultimately underlie the emergent size structure of autotroph communities, divergent aspects of body size (volumetric vs. linear dimensions) shape the ecological outcome of metabolic scaling in forest vs. pelagic ecosystems.
Carbonate-rich silicate and carbonate melts play a crucial role in deep Earth magmatic processes and their melt structure is a key parameter, as it controls physical and chemical properties. Carbonate-rich melts can be strongly enriched in geochemically important trace elements. The structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses, which are usually employed for structural investigations. This thesis investigates the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations as well as in silicate and carbonate melts. The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano, Tanzania.
The local environments of the three elements yttrium (Y), lanthanum (La) and strontium (Sr) were investigated in synthesized glasses and melts using X-ray absorption fine structure (XAFS) spectroscopy. Especially extended X-ray absorption fine structure spectroscopy (EXAFS) provides element specific information on local structure, such as bond lengths, coordination numbers and the degree of disorder. To cope with the enhanced structural disorder present in glasses and melts, EXAFS analysis was based on fitting approaches using an asymmetric distribution function as well as a correlation model according to bond valence theory. Firstly, silicate glasses quenched from high pressure/temperature melts with up to 7.6 wt % CO2 were investigated. In strongly and extremely peralkaline glasses the local structure of Y is unaffected by the CO2 content (with oxygen bond lengths of ~ 2.29 Å). Contrary, the bond lengths for Sr-O and La-O increase with increasing CO2 content in the strongly peralkaline glasses from ~ 2.53 to ~ 2.57 Å and from ~ 2.52 to ~ 2.54 Å, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 Å and 2.54 Å, respectively). Furthermore, silicate and unquenchable carbonate melts were investigated in-situ at high pressure/temperature conditions (2.2 to 2.6 GPa, 1200 to 1500 °C) using a Paris-Edinburgh press. A novel design of the pressure medium assembly for this press was developed, which features increased mechanical stability as well as enhanced transmittance at relevant energies to allow for low content element EXAFS in transmission. Compared to glasses the bond lengths of Y-O, La-O and Sr-O are elongated by up to + 3 % in the melt and exhibit higher asymmetric pair distributions. For all investigated silicate melt compositions Y-O bond lengths were found constant at ~ 2.37 Å, while in the carbonate melt the Y-O length increases slightly to 2.41 Å. The La-O bond lengths in turn, increase systematically over the whole silicate – carbonate melt joint from 2.55 to 2.60 Å. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 Å from pure silicate to silicate-bearing carbonate composition with constant elevated bond length within the carbonate region.
For comparison and deeper insight, glass and melt structures of Y and Sr bearing sodium-rich silicate to carbonate compositions were simulated in an explorative ab initio molecular dynamics (MD) study. The simulations confirm observed patterns of CO2-dependent local changes around Y and Sr and additionally provide further insights into detailed incorporation mechanisms of the trace elements and CO2. Principle findings include that in sodium-rich silicate compositions carbon either is mainly incorporated as a free carbonate-group or shares one oxygen with a network former (Si or [4]Al) to form a non-bridging carbonate. Of minor importance are bridging carbonates between two network formers. Here, a clear preference for two [4]Al as adjacent network formers occurs, compared to what a statistical distribution would suggest. In C-bearing silicate melts minor amounts of molecular CO2 are present, which is almost totally dissolved as carbonate in the quenched glasses.
The combination of experiment and simulation provides extraordinary insights into glass and melt structures. The new data is interpreted on the basis of bond valence theory and is used to deduce potential mechanisms for structural incorporation of investigated elements, which allow for prediction on their partitioning behavior in natural melts. Furthermore, it provides unique insights into the dissolution mechanisms of CO2 in silicate melts and into the carbonate melt structure. For the latter, a structural model is suggested, which is based on planar CO3-groups linking 7- to 9-fold cation polyhedra, in accordance to structural units as found in the Na-Ca carbonate nyerereite. Ultimately, the outcome of this study contributes to rationalize the unique physical properties and geological phenomena related to carbonated silicate-carbonate melts.
The paper aims to lay out a framework for evaluating value shifts in the international legal order for the purposes of a forthcoming book. In view of current contestations it asks whether we are observing yet another period of norm change (Wandel) or even a more fundamental transformation of international law – a metamorphosis (Verwandlung). For this purpose it suggests to look into the mechanisms of how norms change from the perspective of legal and political science and also to approximate a reference point where change turns into metamorphosis. It submits that such a point may be reached where specific legally protected values are indeed changing (change of legal values) or where the very idea of protecting certain values through law is renounced (delegalizing of values). The paper discusses the benefits of such an interdisciplinary exchange and tries to identify differences and commonalities among both disciplinary perspectives.
Over the past decade, society has witnessed an increasing expansion of service economies as manufacturing (i.e., product-oriented) companies break free from their product-based business model and move toward more service-oriented value creation as a result of several economic, technological, and social changes. As they shift from products to (service) solutions, manufacturing companies pursue new strategic direction, inter alia, by extensively employing service business development activities.
The objective of this dissertation is to investigate the considerable (re-)emerging stream of service business development by providing vital insights for academia and management into important focus areas that have hardly, if at all, been (empirically) investigated in the existing literature before. Therefore, these findings can be vital to informing a differentiation in current and future marketing strategies in business practice.
First of all, this dissertation focuses on the extent to which service business development is transposed into business practice. Because scarce empirical-quantitative research has studied the current state of service business development across various industry and market sectors, this study analyzes a unique, manually collected dataset of 266 (product and service) business development activities. In so doing, this investigation contributes to literature by presenting a comprehensive, industry-wide status quo and trend report of service business development in practice.
Furthermore, given the surprisingly limited scientific attention paid to the question of how service business development is strategically configured and further applied to different environmental circumstances, this dissertation provides comprehensive theoretical and practical implications by analyzing in detail a sample of 137 service business developments of 66 product-oriented companies.
Lastly, manufacturers are recognizing that service-oriented value creation is moving toward a more collaborative process of co-creation as a promising measure to achieve competitive advantage, and even more as an appropriate response to complex business environments. Thus, an increasing number of companies around the world have recently introduced business models related to access-based services such as car-, scooter-, and bike-sharing systems. But despite the considerable advantages of access-based services as an alternative to ownership, these companies are now seeing that consumer adoption and (re-)usage rates remain insufficient. Owing to the lack of general and cross-national scientific knowledge, the purpose of this dissertation continues to explore which factors impede diffusion of related service business development activities from a consumer perspective and what kind of differences can be established between countries. Consequently, with a total of 1,443 participants, a cross-national survey was carried out in three countries, i.e., the United States, Germany, and China, to measure a vast number of different adoption barriers derived from a developed integrated framework that combines established theories within innovation and adoption behavior research.
We develop an amplitude spectral ratio method for event couples from clustered earthquakes to estimate seismic wave attenuation (Q-1) in the source volume. The method allows to study attenuation within the source region of earthquake swarms or aftershocks at depth, independent of wave path and attenuation between source region and surface station. We exploit the high-frequency slope of phase spectra using multitaper spectral estimates. The method is tested using simulated full wave-field seismograms affected by recorded noise and finite source rupture. The synthetic tests verify the approach and show that solutions are independent of focal mechanisms but also show that seismic noise may broaden the scatter of results. We apply the event couple spectral ratio method to northwest Bohemia, Czech Republic, a region characterized by the persistent occurrence of earthquake swarms in a confined source region at mid-crustal depth. Our method indicates a strong anomaly of high attenuation in the source region of the swarm with an averaged attenuation factor of Qp < 100. The application to S phases fails due to scattered P-phase energy interfering with S phases. The Qp anomaly supports the common hypothesis of highly fractured and fluid saturated rocks in the source region of the swarms in northwest Bohemia. However, high temperatures in a small volume around the swarms cannot be excluded to explain our observations.