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Wastewater treatment is crucial to environmental hygiene in urban environments. However, wastewater treatment plants (WWTPs) collect chemicals, organic matter, and microorganisms including pathogens and multi-resistant bacteria from various sources which may be potentially released into the environment via WWTP effluent. To better understand microbial dynamics in WWTPs, we characterized and compared the bacterial community of the inflow and effluent of a WWTP in Berlin, Germany using full-length 16S rRNA gene sequences, which allowed for species level determination in many cases and generally resolved bacterial taxa. Significantly distinct bacterial communities were identified in the wastewater inflow and effluent samples. Dominant operational taxonomic units (OTUs) varied both temporally and spatially. Disease associated bacterial groups were efficiently reduced in their relative abundance from the effluent by the WWTP treatment process, except for Legionella and Leptospira species which demonstrated an increase in relative proportion from inflow to effluent. This indicates that WWTPs, while effective against enteric bacteria, may enrich and release other potentially pathogenic bacteria into the environment. The taxonomic resolution of full-length 16S rRNA genes allows for improved characterization of potential pathogenic taxa and other harmful bacteria which is required to reliably assess health risk.
Microplastics (MP) constitute a widespread contaminant all over the globe. Rivers and wastewater treatment plants (WWTP) transport annually several million tons of MP into freshwaters, estuaries and oceans, where they provide increasing artificial surfaces for microbial colonization. As knowledge on MP-attached communities is insufficient for brackish ecosystems, we conducted exposure experiments in the coastal Baltic Sea, an in-flowing river and a WWTP within the drainage basin. While reporting on prokaryotic and fungal communities from the same set-up previously, we focus here on the entire eukaryotic communities. Using high-throughput 18S rRNA gene sequencing, we analyzed the eukaryotes colonizing on two types of MP, polyethylene and polystyrene, and compared them to the ones in the surrounding water and on a natural surface (wood). More than 500 different taxa across almost all kingdoms of the eukaryotic tree of life were identified on MP, dominated by Alveolata, Metazoa, and Chloroplastida. The eukaryotic community composition on MP was significantly distinct from wood and the surrounding water, with overall lower diversity and the potentially harmful dinoflagellate Pfiesteria being enriched on MP. Co-occurrence networks, which include prokaryotic and eukaryotic taxa, hint at possibilities for dynamic microbial interactions on MP. This first report on total eukaryotic communities on MP in brackish environments highlights the complexity of MP-associated biofilms, potentially leading to altered microbial activities and hence changes in ecosystem functions.
Salinity is a significant factor for structuring microbial communities, but little is known for aquatic fungi, particularly in the pelagic zone of brackish ecosystems. In this study, we explored the diversity and composition of fungal communities following a progressive salinity decline (from 34 to 3 PSU) along three transects of ca. 2000 km in the Baltic Sea, the world’s largest estuary. Based on 18S rRNA gene sequence analysis, we detected clear changes in fungal community composition along the salinity gradient and found significant differences in composition of fungal communities established above and below a critical value of 8 PSU. At salinities below this threshold, fungal communities resembled those from freshwater environments, with a greater abundance of Chytridiomycota, particularly of the orders Rhizophydiales, Lobulomycetales, and
Gromochytriales. At salinities above 8 PSU, communities were more similar to those from marine environments and, depending on the season, were dominated by a strain of the LKM11 group (Cryptomycota) or by members of Ascomycota and Basidiomycota. Our results highlight salinity as an important environmental driver also for pelagic fungi, and thus should be taken into account to better understand fungal diversity and ecological function in the aquatic realm.
Die vorliegende Forschungsarbeit untersucht den Umgang mit Dilemmata von Topmanagern. Dilemmata sind ein alltägliches Geschäft im Topmanagement. Die entsprechenden Akteure sind daher immer wieder mit diesen konfrontiert und mit ihnen umzugehen, gehört gewissermaßen zu ihrer Berufsbeschreibung. Hinzu kommen Dilemmata im nicht direkt geschäftlichen Bereich, wie zum Beispiel jene zwischen Familien- und Arbeitszeit. Doch stellt dieses Feld ein kaum untersuchtes Forschungsgebiet dar. Während Dilemmata in anderen Bereichen eine zunehmende Aufmerksamkeit erfuhren, wurden deren Besonderheiten im Topmanagement genauso wenig differenziert betrachtet wie zugehörige Umgangsweisen. Theorie und Praxis stellen bezüglich Dilemmata von Topmanagern vor allem einen Gegensatz dar, beziehungsweise fehlt es an einer theoretischen Fundierung der Empirie. Diesem Umstand wird mittels dieser Studie begegnet. Auf der Grundlage einer differenzierten und breiten Erfassung von Theorien zu Dilemmata, so diese auch noch nicht auf Topmanager bezogen wurden, und einer empirischen Erhebung, die im Mittelpunkt dieser Arbeit stehen, soll das Feld Dilemmata von Topmanagern der Forschung geöffnet werden. Empirische Grundlage sind vor allem narrative Interviews mit Topmanagern über ihre Dilemmata-Wahrnehmung, ausgemachte Ursachen, Umgangsweisen und Resultate. Dies erlaubt es, Topmanagertypen sowie Dilemmata-Arten, mit denen sie konfrontiert sind oder waren, analytisch herauszuarbeiten. Angesichts der Praxisrelevanz von Dilemmata von Topmanagern wird jedoch nicht nur ein theoretisches Modell zu dieser Thematik erarbeitet, es werden auch Reflexionen auf die Praxis in Form von Handlungsempfehlungen vorgenommen. Schließlich gilt es, die allgemeine Theorie zu Dilemmata, ohne konkreten Bezug zu Topmanagern, mit den theoretischen Erkenntnissen dieser Studie auf empirischer Basis zu kontrastieren. Dabei wird im Rahmen der empirischen Erfassung und Auswertung dem Ansatz der Grounded-Theory-Methodologie gefolgt.
Water stable isotope ratios of tropical precipitation predominantly reflect moisture source and precipitation intensity. Trees can incorporate the isotopic signals into annual tree-ring cellulose records, permitting reconstruction of the temporal changes of hydroclimate over decades to millennia. This is especially valuable in the Himalayas where the understanding of monsoon dynamics is limited by the lack of a dense and representative observational network. We have analyzed tree ring delta O-18 records from two distinct physiographic sites along the upper Kali Gandaki valley in the central Nepal Himalayas, representing the wet High-Himalayas and the Trans-Himalayan dryland to the north. Empirical correlations and regression analyses were compared to an in-situ calibrated oxygen isotope fractionation model, exploring the relationships between tree ring delta O-18 and seasonal-mean variability of hydroclimatic forcing at the different locations. For this purpose, gridded precipitation data from the Asian rain gauge dataset APHRODITE, as well as high resolution onsite observations (relative humidity, air temperature, delta O-18 of precipitation and radial tree growth) were used. We found that two distinct sets of meteorological values, reflecting pre-monsoon and monsoon conditions, are needed to reproduce the measured tree ring delta O-18 values from the High-Himalayan site, but that a single set of monsoonal values performs best for the Trans-Himalayan site. We conclude that Trans-Himalayan trees capture long-term changes in strength of the Indian summer monsoon. In contrast, High-Himalayan tree ring delta(18)Orecords a more complex hydro-climatic signal reflecting both pre-monsoon and monsoon seasons with very contrasting isotopic signatures of precipitation. This difference in the two hydroclimatic proxy records offers an opportunity to reconstruct first-order hydroclimate conditions, such as local precipitation rates, and to gain new insights into monsoon timing and seasonal water source determination across the Himalayan orographic region. (C) 2019 Elsevier B.V. All rights reserved.
We demonstrate full control of acoustic and thermal periodic deformations at solid surfaces down to subnanosecond time scales and few-micrometer length scales via independent variation of the temporal and spatial phase of two optical transient grating (TG) excitations. For this purpose, we introduce an experimental setup that exerts control of the spatial phase of subsequent time-delayed TG excitations depending on their polarization state. Specific exemplary coherent control cases are discussed theoretically and corresponding experimental data are presented in which time-resolved x-ray reflectivity measures the spatiotemporal surface distortion of nanolayered heterostructures. Finally, we discuss examples where the application of our method may enable the control of functional material properties via tailored spatiotemporal strain fields.
We measure the transient strain profile in a nanoscale multilayer system composed of yttrium, holmium, and niobium after laser excitation using ultrafast x-ray diffraction. The strain propagation through each layer is determined by transient changes in the material-specific Bragg angles. We experimentally derive the exponentially decreasing stress profile driving the strain wave and show that it closely matches the optical penetration depth. Below the Neel temperature of Ho, the optical excitation triggers negative thermal expansion, which is induced by a quasi-instantaneous contractive stress and a second contractive stress contribution increasing on a 12-ps timescale. These two timescales were recently measured for the spin disordering in Ho [Rettig et al., Phys. Rev. Lett. 116, 257202 (2016)]. As a consequence, we observe an unconventional bipolar strain pulse with an inverted sign traveling through the heterostructure.
Thermal treatment of hexaazatriphenylene-hexacarbonitrile (HAT-CN) in the temperature range from 500 degrees C to 700 degrees C leads to precise control over the degree of condensation, and thus atomic construction and porosity of the resulting C2N-type materials. Depending on the condensation temperature of HAT-CN, nitrogen contents of more than 30 at% can be reached. In general, these carbons show adsorption properties which are comparable to those known for zeolites but their pore size can be adjusted over a wider range. At condensation temperatures of 525 degrees C and below, the uptake of nitrogen gas remains negligible due to size exclusion, but the internal pores are large and polarizing enough that CO2 can still adsorb on part of the internal surface. This leads to surprisingly high CO2 adsorption capacities and isosteric heat of adsorption of up to 52 kJ mol(-1). Theoretical calculations show that this high binding enthalpy arises from collective stabilization effects from the nitrogen atoms in the C2N layers surrounding the carbon atom in the CO2 molecule and from the electron acceptor properties of the carbon atoms from C2N which are in close proximity to the oxygen atoms in CO2. A true CO2 molecular sieving effect is achieved for the first time in such a metal-free organic material with zeolite-like properties, showing an IAST CO2/N-2 selectivity of up to 121 at 298 K and a N-2/CO2 ratio of 90/10 without notable changes in the CO2 adsorption properities over 80 cycles.
Oxidation of particulate organic carbon (POC) during fluvial transit releases CO2 to the atmosphere and can influence global climate. Field data show large POC oxidation fluxes in lowland rivers; however, it is unclear if POC losses occur predominantly during in-river transport, where POC is in continual motion within an aerated environment, or during transient storage in floodplains, which may be anoxic. Determination of the locus of POC oxidation in lowland rivers is needed to develop process-based models to predict POC losses, constrain carbon budgets, and unravel links between climate and erosion. However, sediment exchange between rivers and floodplains makes differentiating POC oxidation during in-river transport from oxidation during floodplain storage difficult. Here, we isolated inriver POC oxidation using flume experiments transporting petrogenic and biospheric POC without floodplain storage. Our experiments showed solid phase POC losses of 0%-10% over similar to 10(3) km of fluvial transport, compared to similar to 7% to >50% losses observed in rivers over similar distances. The production of dissolved organic carbon (DOC) and dissolved rhenium (a proxy for petrogenic POC oxidation) was consistent with small POC lasses, and replicate experiments in static water tanks gave similar results. Our results show that fluvial sediment transport, particle abrasion, and turbulent mixing have a minimal role on POC oxidation, and they suggest that POC losses may accrue primarily in floodplain storage.
The large, shallow earthquakes at Northridge, California (1994), Chi-Chi, Taiwan (1999), and Wenchuan, China (2008), each triggered thousands of landslides. We have determined the position of these landslides along hillslopes, normalizing for statistical bias. The landslide patterns have a co-seismic signature, with clustering at ridge crests and slope toes. A cross-check against rainfall-induced landslide inventories seems to confirm that crest clustering is specific to seismic triggering as observed in previous studies. In our three study areas, the seismic ground motion parameters and lithologic and topographic features used do not seem to exert a primary control on the observed patterns of landslide clustering. However, we show that at the scale of the epicentral area, crest and toe clustering occur in areas with specific geological features. Toe clustering of seismically induced landslides tends to occur along regional major faults. Crest clustering is concentrated at sites where the lithology along hillslopes is approximately uniform, or made of alternating soft and hard strata, and without strong overprint of geological structures. Although earthquake-induced landslides locate higher on hillslopes in a statistically significant way, geological features strongly modulate the landslide position along the hillslopes. As a result the observation of landslide clustering on topographic ridges cannot be used as a definite indicator of the topographic amplification of ground shaking.
Right on track?
(2019)
Satellite telemetry is an increasingly utilized technology in wildlife research, and current devices can track individual animal movements at unprecedented spatial and temporal resolutions. However, as we enter the golden age of satellite telemetry, we need an in-depth understanding of the main technological, species-specific and environmental factors that determine the success and failure of satellite tracking devices across species and habitats. Here, we assess the relative influence of such factors on the ability of satellite telemetry units to provide the expected amount and quality of data by analyzing data from over 3,000 devices deployed on 62 terrestrial species in 167 projects worldwide. We evaluate the success rate in obtaining GPS fixes as well as in transferring these fixes to the user and we evaluate failure rates. Average fix success and data transfer rates were high and were generally better predicted by species and unit characteristics, while environmental characteristics influenced the variability of performance. However, 48% of the unit deployments ended prematurely, half of them due to technical failure. Nonetheless, this study shows that the performance of satellite telemetry applications has shown improvements over time, and based on our findings, we provide further recommendations for both users and manufacturers.
Thermokarst lake landscapes are permafrost regions, which are prone to rapid (on seasonal to decadal time scales) changes, affecting carbon and nitrogen cycles. However, there is a high degree of uncertainty related to the balance between carbon and nitrogen cycling and storage. We collected 12 permafrost soil cores from six drained thermokarst lake basins (DTLBs) along a chronosequence north of Teshekpuk Lake in northern Alaska and analyzed them for carbon and nitrogen contents. For comparison, we included three lacustrine cores from an adjacent thermokarst lake and one soil core from a non thermokarst affected remnant upland. This allowed to calculate the carbon and nitrogen stocks of the three primary landscape units (DTLB, lake, and upland), to reconstruct the landscape history, and to analyze the effect of thermokarst lake formation and drainage on carbon and nitrogen stocks. We show that carbon and nitrogen contents and the carbon-nitrogen ratio are considerably lower in sediments of extant lakes than in the DTLB or upland cores indicating degradation of carbon during thermokarst lake formation. However, we found similar amounts of total carbon and nitrogen stocks due to the higher density of lacustrine sediments caused by the lack of ground ice compared to DTLB sediments. In addition, the radiocarbon-based landscape chronology for the past 7,000years reveals five successive lake stages of partially, spatially overlapping DTLBs in the study region, reflecting the dynamic nature of ice-rich permafrost deposits. With this study, we highlight the importance to include these dynamic landscapes in future permafrost carbon feedback models. Plain Language Summary When permanently frozen soils (permafrost) contain ice-rich sediments, the thawing of this permafrost causes the surface to sink, which may result in lake formation. This process, the thaw of ice-rich permafrost and melting of ground ice leads to characteristic landforms-known as thermokarst. Once such a thaw process is initiated in ice-rich sediments, a thaw lake forms and grows by shoreline erosion, eventually expanding until a drainage pathway is encountered and the lake eventually drains, resulting in a drained thermokarst lake basin. In our study, we show that such a thermokarst-affected landscape north of Teshekpuk Lake in northern Alaska is shaped by repeated thaw lake formation and lake drainage events during the past 7,000years, highlighting the dynamic nature of these landscapes. These landscape-scale processes have a big effect on the carbon and nitrogen stored in permafrost soils. We show that large amounts of carbon (>45kg C/m(2)) and nitrogen (>2.6kg N/m(2)) are stored in unfrozen lake sediments and in frozen soil sediments. The findings are important when considering the potential effect that permafrost thaw has for the global climate through releasing carbon and nitrogen, which was frozen and therefore locked away for millennia, from the active carbon cycle.
Numerous preflight investigations were necessary prior to the exposure experiment BIOMEX on the International Space Station to test the basic potential of selected microorganisms to resist or even to be active under Mars-like conditions. In this study, methanogenic archaea, which are anaerobic chemolithotrophic microorganisms whose lifestyle would allow metabolism under the conditions on early and recent Mars, were analyzed. Some strains from Siberian permafrost environments have shown a particular resistance. In this investigation, we analyzed the response of three permafrost strains (Methanosarcina soligelidi SMA-21, Candidatus Methanosarcina SMA-17, Candidatus Methanobacterium SMA-27) and two related strains from non-permafrost environments (Methanosarcina mazei, Methanosarcina barkeri) to desiccation conditions (-80 degrees C for 315 days, martian regolith analog simulants S-MRS and P-MRS, a 128-day period of simulated Mars-like atmosphere). Exposure of the different methanogenic strains to increasing concentrations of magnesium perchlorate allowed for the study of their metabolic shutdown in a Mars-relevant perchlorate environment. Survival and metabolic recovery were analyzed by quantitative PCR, gas chromatography, and a new DNA-extraction method from viable cells embedded in S-MRS and P-MRS. All strains survived the two Mars-like desiccating scenarios and recovered to different extents. The permafrost strain SMA-27 showed an increased methanogenic activity by at least 10-fold after deep-freezing conditions. The methanogenic rates of all strains did not decrease significantly after 128 days S-MRS exposure, except for SMA-27, which decreased 10-fold. The activity of strains SMA-17 and SMA-27 decreased after 16 and 60 days P-MRS exposure. Non-permafrost strains showed constant survival and methane production when exposed to both desiccating scenarios. All strains showed unaltered methane production when exposed to the perchlorate concentration reported at the Phoenix landing site (2.4 mM) or even higher concentrations. We conclude that methanogens from (non-)permafrost environments are suitable candidates for potential life in the martian subsurface and therefore are worthy of study after space exposure experiments that approach Mars-like surface conditions.
In active mountain belts with steep terrain, bedrock landsliding is a major erosional agent. In the Himalayas, landsliding is driven by annual hydro-meteorological forcing due to the summer monsoon and by rarer, exceptional events, such as earthquakes. Independent methods yield erosion rate estimates that appear to increase with sampling time, suggesting that rare, high-magnitude erosion events dominate the erosional budget. Nevertheless, until now, neither the contribution of monsoon and earthquakes to landslide erosion nor the proportion of erosion due to rare, giant landslides have been quantified in the Himalayas. We address these challenges by combining and analysing earthquake- and monsoon-induced landslide inventories across different timescales. With time series of 5 m satellite images over four main valleys in central Nepal, we comprehensively mapped landslides caused by the monsoon from 2010 to 2018. We found no clear correlation between monsoon properties and landsliding and a similar mean landsliding rate for all valleys, except in 2015, where the valleys affected by the earthquake featured similar to 5-8 times more landsliding than the pre-earthquake mean rate. The longterm size-frequency distribution of monsoon-induced landsliding (MIL) was derived from these inventories and from an inventory of landslides larger than similar to 0.1 km(2) that occurred between 1972 and 2014. Using a published landslide inventory for the Gorkha 2015 earthquake, we derive the size-frequency distribution for earthquakeinduced landsliding (EQIL). These two distributions are dominated by infrequent, large and giant landslides but under-predict an estimated Holocene frequency of giant landslides (> 1 km(3)) which we derived from a literature compilation. This discrepancy can be resolved when modelling the effect of a full distribution of earthquakes of variable magnitude and when considering that a shallower earthquake may cause larger landslides. In this case, EQIL and MIL contribute about equally to a total long-term erosion of similar to 2 +/- 0.75 mm yr(-1) in agreement with most thermo-chronological data. Independently of the specific total and relative erosion rates, the heavy-tailed size-frequency distribution from MIL and EQIL and the very large maximal landslide size in the Himalayas indicate that mean landslide erosion rates increase with sampling time, as has been observed for independent erosion estimates. Further, we find that the sampling timescale required to adequately capture the frequency of the largest landslides, which is necessary for deriving long-term mean erosion rates, is often much longer than the averaging time of cosmogenic Be-10 methods. This observation presents a strong caveat when interpreting spatial or temporal variability in erosion rates from this method. Thus, in areas where a very large, rare landslide contributes heavily to long-term erosion (as the Himalayas), we recommend Be-10 sample in catchments with source areas > 10 000 km(2) to reduce the method mean bias to below similar to 20 % of the long-term erosion.
Editorial
(2019)
The sensitivity of fluvial systems to tectonic and climatic boundary conditions allows us to use the geomorphic and stratigraphic records as quantitative archives of past climatic and tectonic conditions. Thus, fluvial terraces that form on alluvial fans and floodplains as well as the rate of sediment export to oceanic and continental basins are commonly used to reconstruct paleoenvironments. However, we currently lack a systematic and quantitative understanding of the transient evolution of fluvial systems and their associated sediment storage and release in response to changes in base level, water input, and sediment input. Such knowledge is necessary to quantify past environmental change from terrace records or sedimentary deposits and to disentangle the multiple possible causes for terrace formation and sediment deposition. Here, we use a set of seven physical experiments to explore terrace formation and sediment export from a single, braided channel that is perturbed by changes in upstream water discharge or sediment supply, or through downstream base-level fall. Each perturbation differently affects (1) the geometry of terraces and channels, (2) the timing of terrace cutting, and (3) the transient response of sediment export from the basin. In general, an increase in water discharge leads to near-instantaneous channel incision across the entire fluvial system and consequent local terrace cutting, thus preserving the initial channel slope on terrace surfaces, and it also produces a transient increase in sediment export from the system. In contrast, a decreased upstream sediment-supply rate may result in longer lag times before terrace cutting, leading to terrace slopes that differ from the initial channel slope, and also lagged responses in sediment export. Finally, downstream base-level fall triggers the upstream propagation of a diffuse knickzone, forming terraces with upstream-decreasing ages. The slope of terraces triggered by base-level fall mimics that of the newly adjusted active channel, whereas slopes of terraces triggered by a decrease in upstream sediment discharge or an increase in upstream water discharge are steeper compared to the new equilibrium channel. By combining fillterrace records with constraints on sediment export, we can distinguish among environmental perturbations that would otherwise remain unresolved when using just one of these records.
Determining the relationship between genotype and phenotype is the key to understand the plasticity and robustness of phenotypes in nature. While the directly observable plant phenotypes (e.g. agronomic, yield and stress resistance traits) have been well-investigated, there is still a lack in our knowledge about the genetic basis of intermediate phenotypes, such as metabolic phenotypes. Dissecting the links between genotype and phenotype depends on suitable statistical models. The state-of-the-art models are developed for directly observable phenotypes, regardless the characteristics of intermediate phenotypes. This thesis aims to fill the gaps in understanding genetic architecture of intermediate phenotypes, and how they tie to composite traits, namely plant growth. The metabolite levels and reaction fluxes, as two aspects of metabolic phenotypes, are shaped by the interrelated chemical reactions formed in genome-scale metabolic network. Here, I attempt to answer the question: Can the knowledge of underlying genome-scale metabolic network improve the model performance for prediction of metabolic phenotypes and associated plant growth? To this end, two projects are investigated in this thesis. Firstly, we propose an approach that couples genomic selection with genome-scale metabolic network and metabolic profiles in Arabidopsis thaliana to predict growth. This project is the first integration of genomic data with fluxes predicted based on constraint-based modeling framework and data on biomass composition. We demonstrate that our approach leads to a considerable increase of prediction accuracy in comparison to the state-of-the-art methods in both within and across environment predictions. Therefore, our work paves the way for combining knowledge on metabolic mechanisms in the statistical approach underlying genomic selection to increase the efficiency of future plant breeding approaches. Secondly, we investigate how reliable is genomic selection for metabolite levels, and which single nucleotide polymorphisms (SNPs), obtained from different neighborhoods of a given metabolic network, contribute most to the accuracy of prediction. The results show that the local structure of first and second neighborhoods are not sufficient for predicting the genetic basis of metabolite levels in Zea mays. Furthermore, we find that the enzymatic SNPs can capture most the genetic variance and the contribution of non-enzymatic SNPs is in fact small. To comprehensively understand the genetic architecture of metabolic phenotypes, I extend my study to a local Arabidopsis thaliana population and their hybrids. We analyze the genetic architecture in primary and secondary metabolism as well as in growth. In comparison to primary metabolites, compounds from secondary metabolism were more variable and show more non-additive inheritance patterns which could be attributed to epistasis. Therefore, our study demonstrates that heterozygosity in local Arabidopsis thaliana population generates metabolic variation and may impact several tasks directly linked to metabolism. The studies in this thesis improve the knowledge of genetic architecture of metabolic phenotypes in both inbreed and hybrid population. The approaches I proposed to integrate genome-scale metabolic network with genomic data provide the opportunity to obtain mechanistic insights about the determinants of agronomically important polygenic traits.
The sensitivity of fluvial systems to tectonic and climatic boundary conditions allows us to use the geomorphic and stratigraphic records as quantitative archives of past climatic and tectonic conditions. Thus, fluvial terraces that form on alluvial fans and floodplains as well as the rate of sediment export to oceanic and continental basins are commonly used to reconstruct paleoenvironments. However, we currently lack a systematic and quantitative understanding of the transient evolution of fluvial systems and their associated sediment storage and release in response to changes in base level, water input, and sediment input. Such knowledge is necessary to quantify past environmental change from terrace records or sedimentary deposits and to disentangle the multiple possible causes for terrace formation and sediment deposition. Here, we use a set of seven physical experiments to explore terrace formation and sediment export from a single, braided channel that is perturbed by changes in upstream water discharge or sediment supply, or through downstream base-level fall. Each perturbation differently affects (1) the geometry of terraces and channels, (2) the timing of terrace cutting, and (3) the transient response of sediment export from the basin. In general, an increase in water discharge leads to near-instantaneous channel incision across the entire fluvial system and consequent local terrace cutting, thus preserving the initial channel slope on terrace surfaces, and it also produces a transient increase in sediment export from the system. In contrast, a decreased upstream sediment-supply rate may result in longer lag times before terrace cutting, leading to terrace slopes that differ from the initial channel slope, and also lagged responses in sediment export. Finally, downstream base-level fall triggers the upstream propagation of a diffuse knickzone, forming terraces with upstream-decreasing ages. The slope of terraces triggered by base-level fall mimics that of the newly adjusted active channel, whereas slopes of terraces triggered by a decrease in upstream sediment discharge or an increase in upstream water discharge are steeper compared to the new equilibrium channel. By combining fillterrace records with constraints on sediment export, we can distinguish among environmental perturbations that would otherwise remain unresolved when using just one of these records.
Plants have adapted to the diurnal light-dark cycle by establishing elaborate transcriptional programs that coordinate many metabolic, physiological, and developmental responses to the external environment. These transcriptional programs have been studied in only a few species, and their function and conservation across algae and plants is currently unknown. We performed a comparative transcriptome analysis of the diurnal cycle of nine members of Archaeplastida, and we observed that, despite large phylogenetic distances and dramatic differences in morphology and lifestyle, diurnal transcriptional programs of these organisms are similar. Expression of genes related to cell division and the majority of biological pathways depends on the time of day in unicellular algae but we did not observe such patterns at the tissue level in multicellular land plants. Hence, our study provides evidence for the universality of diurnal gene expression and elucidates its evolutionary history among different photosynthetic eukaryotes.
Groundwater travel time distributions (TTDs) provide a robust description of the subsurface mixing behavior and hydrological response of a subsurface system. Lagrangian particle tracking is often used to derive the groundwater TTDs. The reliability of this approach is subjected to the uncertainty of external forcings, internal hydraulic properties, and the interplay between them. Here, we evaluate the uncertainty of catchment groundwater TTDs in an agricultural catchment using a 3-D groundwater model with an overall focus on revealing the relationship between external forcing, internal hydraulic properties, and TTD predictions. Eight recharge realizations are sampled from a high-resolution dataset of land surface fluxes and states. Calibration-constrained hydraulic conductivity fields (Ks fields) are stochastically generated using the null-space Monte Carlo (NSMC) method for each recharge realization. The random walk particle tracking (RWPT) method is used to track the pathways of particles and compute travel times. Moreover, an analytical model under the random sampling (RS) assumption is fit against the numerical solutions, serving as a reference for the mixing behavior of the model domain. The StorAge Selection (SAS) function is used to interpret the results in terms of quantifying the systematic preference for discharging young/old water. The simulation results reveal the primary effect of recharge on the predicted mean travel time (MTT). The different realizations of calibration-constrained Ks fields moderately magnify or attenuate the predicted MTTs. The analytical model does not properly replicate the numerical solution, and it underestimates the mean travel time. Simulated SAS functions indicate an overall preference for young water for all realizations. The spatial pattern of recharge controls the shape and breadth of simulated TTDs and SAS functions by changing the spatial distribution of particles' pathways. In conclusion, overlooking the spatial nonuniformity and uncertainty of input (forcing) will result in biased travel time predictions. We also highlight the worth of reliable observations in reducing predictive uncertainty and the good interpretability of SAS functions in terms of understanding catchment transport processes.
Understanding the structure of reaction networks along with the underlying kinetics that lead to particular concentration readouts of the participating components is the first step toward optimization and control of (bio-)chemical processes. Yet, solutions to the problem of inferring the structure of reaction networks, i.e., characterizing the stoichiometry of the participating reactions provided concentration profiles of the participating components, remain elusive. Here, we present an approach to infer the stoichiometric subspace of a chemical reaction network from steady-state concentration data profiles obtained from a continuous isothermal reactor. The subsequent problem of finding reactions consistent with the observed subspace is cast as a series of mixed-integer linear programs whose solution generates potential reaction vectors together with a measure of their likelihood. We demonstrate the efficiency and applicability of the proposed approach using data obtained from synthetic reaction networks and from a well-established biological model for the Calvin-Benson cycle. Furthermore, we investigate the effect of missing information, in the form of unmeasured species or insufficient diversity within the data set, on the ability to accurately reconstruct the network reactions. The proposed framework is, in principle, applicable to many other reaction systems, thus providing future extensions to understanding reaction networks guiding chemical reactors and complex biological mixtures. (C) 2019 Author(s).
Plasticity in metabolism underpins local responses to nitrogen in Arabidopsis thaliana populations
(2019)
Nitrogen (N) is central for plant growth, and metabolic plasticity can provide a strategy to respond to changing N availability. We showed that two local A. thaliana populations exhibited differential plasticity in the compounds of photorespiratory and starch degradation pathways in response to three N conditions. Association of metabolite levels with growth-related and fitness traits indicated that controlled plasticity in these pathways could contribute to local adaptation and play a role in plant evolution.
IntroductionTo date, most studies of natural variation and metabolite quantitative trait loci (mQTL) in tomato have focused on fruit metabolism, leaving aside the identification of genomic regions involved in the regulation of leaf metabolism.ObjectiveThis study was conducted to identify leaf mQTL in tomato and to assess the association of leaf metabolites and physiological traits with the metabolite levels from other tissues.MethodsThe analysis of components of leaf metabolism was performed by phenotypying 76 tomato ILs with chromosome segments of the wild species Solanum pennellii in the genetic background of a cultivated tomato (S. lycopersicum) variety M82. The plants were cultivated in two different environments in independent years and samples were harvested from mature leaves of non-flowering plants at the middle of the light period. The non-targeted metabolite profiling was obtained by gas chromatography time-of-flight mass spectrometry (GC-TOF-MS). With the data set obtained in this study and already published metabolomics data from seed and fruit, we performed QTL mapping, heritability and correlation analyses.ResultsChanges in metabolite contents were evident in the ILs that are potentially important with respect to stress responses and plant physiology. By analyzing the obtained data, we identified 42 positive and 76 negative mQTL involved in carbon and nitrogen metabolism.ConclusionsOverall, these findings allowed the identification of S. lycopersicum genome regions involved in the regulation of leaf primary carbon and nitrogen metabolism, as well as the association of leaf metabolites with metabolites from seeds and fruits.
Diatoms outcompete other phytoplankton for nitrate, yet little is known about the mechanisms underpinning this ability. Genomes and genome-enabled studies have shown that diatoms possess unique features of nitrogen metabolism however, the implications for nutrient utilization and growth are poorly understood. Using a combination of transcriptomics, proteomics, metabolomics, fluxomics, and flux balance analysis to examine short-term shifts in nitrogen utilization in the model pennate diatom in Phaeodactylum tricornutum, we obtained a systems-level understanding of assimilation and intracellular distribution of nitrogen. Chloroplasts and mitochondria are energetically integrated at the critical intersection of carbon and nitrogen metabolism in diatoms. Pathways involved in this integration are organelle-localized GS-GOGAT cycles, aspartate and alanine systems for amino moiety exchange, and a split-organelle arginine biosynthesis pathway that clarifies the role of the diatom urea cycle. This unique configuration allows diatoms to efficiently adjust to changing nitrogen status, conferring an ecological advantage over other phytoplankton taxa.
Light and gravity are two key determinants in orientating plant stems for proper growth and development. The organization and dynamics of the actin cytoskeleton are essential for cell biology and critically regulated by actin-binding proteins. However, the role of actin cytoskeleton in shoot negative gravitropism remains controversial. In this work, we report that the actin-binding protein Rice Morphology Determinant (RMD) promotes reorganization of the actin cytoskeleton in rice (Oryza sativa) shoots. The changes in actin organization are associated with the ability of the rice shoots to respond to negative gravitropism. Here, light-grown rmd mutant shoots exhibited agravitropic phenotypes. By contrast, etiolated rmd shoots displayed normal negative shoot gravitropism. Furthermore, we show that RMD maintains an actin configuration that promotes statolith mobility in gravisensing endodermal cells, and for proper auxin distribution in light-grown, but not dark-grown, shoots. RMD gene expression is diurnally controlled and directly repressed by the phytochrome-interacting factor-like protein OsPIL16. Consequently, overexpression of OsPIL16 led to gravisensing and actin patterning defects that phenocopied the rmd mutant. Our findings outline a mechanism that links light signaling and gravity perception for straight shoot growth in rice.
Cotton (Gossypium hirsutum) fibres consist of single cells that grow in a highly polarized manner, assumed to be controlled by the cytoskeleton(1-3). However, how the cytoskeletal organization and dynamics underpin fibre development remains unexplored. Moreover, it is unclear whether cotton fibres expand via tip growth or diffuse growth(2-4). We generated stable transgenic cotton plants expressing fluorescent markers of the actin and microtubule cytoskeleton. Live-cell imaging revealed that elongating cotton fibres assemble a cortical filamentous actin network that extends along the cell axis to finally form actin strands with closed loops in the tapered fibre tip. Analyses of F-actin network properties indicate that cotton fibres have a unique actin organization that blends features of both diffuse and tip growth modes. Interestingly, typical actin organization and endosomal vesicle aggregation found in tip-growing cell apices were not observed in fibre tips. Instead, endomembrane compartments were evenly distributed along the elongating fibre cells and moved bi-directionally along the fibre shank to the fibre tip. Moreover, plus-end tracked microtubules transversely encircled elongating fibre shanks, reminiscent of diffusely growing cells. Collectively, our findings indicate that cotton fibres elongate via a unique tip-biased diffuse growth mode.
The improvement of process representations in hydrological models is often only driven by the modelers' knowledge and data availability. We present a comprehensive comparison between two hydrological models of different complexity that is developed to support (1) the understanding of the differences between model structures and (2) the identification of the observations needed for model assessment and improvement. The comparison is conducted on both space and time and by aggregating the outputs at different spatiotemporal scales. In the present study, mHM, a process‐based hydrological model, and ParFlow‐CLM, an integrated subsurface‐surface hydrological model, are used. The models are applied in a mesoscale catchment in Germany. Both models agree in the simulated river discharge at the outlet and the surface soil moisture dynamics, lending their supports for some model applications (drought monitoring). Different model sensitivities are, however, found when comparing evapotranspiration and soil moisture at different soil depths. The analysis supports the need of observations within the catchment for model assessment, but it indicates that different strategies should be considered for the different variables. Evapotranspiration measurements are needed at daily resolution across several locations, while highly resolved spatially distributed observations with lower temporal frequency are required for soil moisture. Finally, the results show the impact of the shallow groundwater system simulated by ParFlow‐CLM and the need to account for the related soil moisture redistribution. Our comparison strategy can be applied to other models types and environmental conditions to strengthen the dialog between modelers and experimentalists for improving process representations in Earth system models.
Transverse dispersion, or tracer spreading orthogonal to the mean flow direction, which is relevant e.g, for quantifying bio-degradation of contaminant plumes or mixing of reactive solutes, has been studied in the literature less than the longitudinal one. Inferring transverse dispersion coefficients from field experiments is a difficult and error-prone task, requiring a spatial resolution of solute plumes which is not easily achievable in applications. In absence of field data, it is a questionable common practice to set transverse dispersivities as a fraction of the longitudinal one, with the ratio 1/10 being the most prevalent. We collected estimates of field-scale transverse dispersivities from existing publications and explored possible scale relationships as guidance criteria for applications. Our investigation showed that a large number of estimates available in the literature are of low reliability and should be discarded from further analysis. The remaining reliable estimates are formation-specific, span three orders of magnitude and do not show any clear scale-dependence on the plume traveled distance. The ratios with the longitudinal dispersivity are also site specific and vary widely. The reliability of transverse dispersivities depends significantly on the type of field experiment and method of data analysis. In applications where transverse dispersion plays a significant role, inference of transverse dispersivities should be part of site characterization with the transverse dispersivity estimated as an independent parameter rather than related heuristically to longitudinal dispersivity.
Successfully designed and implemented plant-specific synthetic metabolic pathways hold promise to increase crop yield and nutritional value. Advances in synthetic biology have already demonstrated the capacity to design artificial biological pathways whose behavior can be predicted and controlled in microbial systems. However, the transfer of these advances to model plants and crops faces the lack of characterization of plant cellular pathways and increased complexity due to compartmentalization and multicellularity. Modern computational developments provide the means to test the feasibility of plant synthetic metabolic pathways despite gaps in the accumulated knowledge of plant metabolism. Here, we provide a succinct systematic review of optimization-based and retrobiosynthesis approaches that can be used to design and in silico test synthetic metabolic pathways in large-scale plant context-specific metabolic models. In addition, by surveying the existing case studies, we highlight the challenges that these approaches face when applied to plants. Emphasis is placed on understanding the effect that metabolic designs can have on native metabolism, particularly with respect to metabolite concentrations and thermodynamics of biochemical reactions. In addition, we discuss the computational developments that may help to transform the identified challenges into opportunities for plant synthetic biology.
Coherent network partitions
(2019)
Graph clustering is widely applied in the analysis of cellular networks reconstructed from large-scale data or obtained from experimental evidence. Here we introduce a new type of graph clustering based on the concept of coherent partition. A coherent partition of a graph G is a partition of the vertices of G that yields only disconnected subgraphs in the complement of G. The coherence number of G is then the size of the smallest edge cut inducing a coherent partition. A coherent partition of G is optimal if the size of the inducing edge cut is the coherence number of G. Given a graph G, we study coherent partitions and the coherence number in connection to (bi)clique partitions and the (bi)clique cover number. We show that the problem of finding the coherence number is NP-hard, but is of polynomial time complexity for trees. We also discuss the relation between coherent partitions and prominent graph clustering quality measures.
Understanding the strategies employed by plant species that live in extreme environments offers the possibility to discover stress tolerance mechanisms. We studied the physiological, antioxidant and metabolic responses to three temperature conditions (4, 15, and 23 degrees C) of Colobanthus quitensis (CQ), one of the only two native vascular species in Antarctica. We also employed Dianthus chinensis (DC), to assess the effects of the treatments in a non-Antarctic species from the same family. Using fused LASSO modelling, we associated physiological and biochemical antioxidant responses with primary metabolism. This approach allowed us to highlight the metabolic pathways driving the response specific to CQ. Low temperature imposed dramatic reductions in photosynthesis (up to 88%) but not in respiration (sustaining rates of 3.0-4.2 mu mol CO2 m(-2) s(-1)) in CQ, and no change in the physiological stress parameters was found. Its notable antioxidant capacity and mitochondrial cytochrome respiratory activity (20 and two times higher than DC, respectively), which ensure ATP production even at low temperature, was significantly associated with sulphur-containing metabolites and polyamines. Our findings potentially open new biotechnological opportunities regarding the role of antioxidant compounds and respiratory mechanisms associated with sulphur metabolism in stress tolerance strategies to low temperature.
In canoe sprint, the trunk muscles play an important role in stabilizing the body in an unstable environment (boat) and in generating forces that are transmitted through the shoulders and arms to the paddle for propulsion of the boat. Isokinetic training is well suited for sports in which propulsion is generated through water resistance due to similarities in the resistive mode. Thus, the purpose of this study was to determine the effects of isokinetic training in addition to regular sport-specific training on trunk muscular fitness and body composition in world-class canoeists and to evaluate associations between trunk muscular fitness and canoe-specific performance. Nine world-class canoeists (age: 25.6 ± 3.3 years; three females; four world champions; three Olympic gold medalists) participated in an 8-week progressive isokinetic training with a 6-week block “muscle hypertrophy” and a 2-week block “muscle power.” Pre- and post-tests included the assessment of peak isokinetic torque at different velocities in concentric (30 and 140∘s-1) and eccentric (30 and 90∘s-1) mode, trunk muscle endurance, and body composition (e.g., body fat, segmental lean mass). Additionally, peak paddle force was assessed in the flume at a water current of 3.4 m/s. Significant pre-to-post increases were found for peak torque of the trunk rotators at 30∘s-1 (p = 0.047; d = 0.4) and 140∘s-1 (p = 0.014; d = 0.7) in concentric mode. No significant pre-to-post changes were detected for eccentric trunk rotator torque, trunk muscle endurance, and body composition (p > 0.148). Significant medium-to-large correlations were observed between concentric trunk rotator torque but not trunk muscle endurance and peak paddle force, irrespective of the isokinetic movement velocity (all r ≥ 0.886; p ≤ 0.008). Isokinetic trunk rotator training is effective in improving concentric trunk rotator strength in world-class canoe sprinters. It is recommended to progressively increase angular velocity from 30∘s-1 to 140∘s-1 over the course of the training period.
Background: There is evidence that frontal plane lower limb malalignment (e.g., genu varus) is a risk factor for knee osteoarthritis development. However, only scarce information is available on gait biomechanics and muscle activity in boys with genu varus. Research question: To examine the effects of knee varus alignment on lower limb kinematics, kinetics and muscular activity during walking at self-selected speed in boys with genu varus versus healthy age-matched controls. Methods: Thirty-six boys were enrolled in this study and divided into a group of boys with genu varus (n = 18; age: 11.66 +/- 1.64 years) and healthy controls (n = 18; age: 11.44 +/- 1.78 years). Three-dimensional kinematics, ground reaction forces, loading rates, impulses and free moments of both limbs were recorded during five walking trials at self-selected speed. Surface electromyography was recorded for rectus femoris and vastus lateralis/medialis muscles. Results: No significant between-group differences were found for gait speed. Participants in the genu varus group versus controls showed larger peak knee flexion (p = 0.030; d = 0.77), peak knee adduction (p < 0.001; d = 1.63), and peak ankle eversion angles (p < 0.001; d = 2.06). Significantly higher peak ground reaction forces were found at heel contact (vertical [p = 0.002; d = 1.16] and posterior [p < 0.001; d = 1.63] components) and at push off (vertical [p = 0.010; d = 0.93] and anterior [p < 0.001; d = 1.34] components) for genu varus versus controls. Peak medial ground reaction force (p = 0.032; d = 0.76), vertical loading rate (p < 0.001; d = 1.52), anterior-posterior impulse (p = 0.011; d = 0.92), and peak negative free moment (p = 0.030; d = 0.77) were significantly higher in genu varus. Finally, time to reach peak forces was significantly shorter in genu varus boys compared with healthy controls (p < 0.01; d = 0.73-1.60). The genu varus group showed higher activities in vastus lateralis (p < 0.001; d = 1.82) and vastus medialis (p = 0.013; d = 0.90) during the loading phase of walking. Significance: Our study revealed genu varus specific gait characteristics and muscle activities. Greater knee adduction angle in genu varus boys may increase the load on the medial compartment of the knee joint. The observed characteristics in lower limb biomechanics and muscle activity could play a role in the early development of knee osteoarthritis in genu varus boys.
Physical fatigue and pronated feet constitute two risk factors for running-related lower limb injuries. Accordingly, different running shoe companies designed anti-pronation shoes with medial support to limit over pronation in runners. However, there is little evidence on the effectiveness and clinical relevance of anti-pronation shoes. This study examined lower limb kinematics and kinetics in young female runners with pronated feet during running with antipronation versus regular (neutral) running shoes in unfatigued and fatigued condition. Twenty-six female runners aged 24.1±5.6 years with pronated feet volunteered to participate in this study. Kinetic (3D Kistler force plate) and kinematic analyses (Vicon motion analysis system) were conducted to record participants’ ground reaction forces and joint kinematics when running with anti-pronation compared with neutral running shoes. Physical fatigue was induced through an individualized submaximal running protocol on a motorized treadmill using rate of perceived exertion and heart rate monitoring. The statistical analyses indicated significant main effects of “footwear” for peak ankle inversion, peak ankle eversion, and peak hip internal rotation angles (p<0.03; d = 0.46–0.95). Pair-wise comparisons revealed a significantly greater peak ankle inversion angle (p<0.03; d = 0.95; 2.70°) and smaller peak eversion angle (p<0.03; d = 0.46; 2.53°) when running with anti-pronation shoes compared with neutral shoes. For kinetic data, significant main effects of “footwear” were found for peak ankle dorsiflexor moment, peak knee extensor moment, peak hip flexor moment, peak hip extensor moment, peak hip abductor moment, and peak hip internal rotator moment (p<0.02; d = 1.00–1.79). For peak positive hip power in sagittal and frontal planes and peak negative hip power in horizontal plane, we observed significant main effects of “footwear” (p<0.03; d = 0.92–1.06). Pairwise comparisons revealed that peak positive hip power in sagittal plane (p<0.03; d = 0.98; 2.39 w/kg), peak positive hip power in frontal plane (p = 0.014; d = 1.06; 0.54 w/kg), and peak negative hip power in horizontal plane (p<0.03; d = 0.92; 0.43 w/kg) were greater with anti-pronation shoes. Furthermore, the statistical analyses indicated significant main effects of “Fatigue” for peak ankle inversion, peak ankle eversion, and peak knee external rotation angles. Pair-wise comparisons revealed a fatigue-induced decrease in peak ankle inversion angle (p<0.01; d = 1.23; 2.69°) and a fatigue-induced increase in peak knee external rotation angle (p<0.05; d = 0.83; 5.40°). In addition, a fatigue-related increase was found for peak ankle eversion (p<0.01; d = 1.24; 2.67°). For kinetic data, we observed a significant main effect of “Fatigue” for knee flexor moment, knee internal rotator moment, and hip extensor moment (p<0.05; d = 0.83–1.01). The statistical analyses indicated significant a main effect of “Fatigue” for peak negative ankle power in sagittal plane (p<0.01; d = 1.25). Finally, we could not detect any significant footwear by fatigue interaction effects for all measures of joint kinetics and kinematics. Running in anti-pronation compared with neutral running shoes produced lower peak moments and powers in lower limb joints and better control in rear foot eversion. Physical fatigue increased peak moments and powers in lower limb joints irrespective of the type of footwear.
Electron injection at high Mach number nonrelativistic perpendicular shocks is studied here for parameters that are applicable to young SNR shocks. Using high-resolution large-scale two-dimensional fully kinetic particle-in-cell simulations and tracing individual particles, we in detail analyze the shock-surfing acceleration (SSA) of electrons at the leading edge of the shock foot. The central question is to what degree the process can be captured in 2D3V simulations. We find that the energy gain in SSA always arises from the electrostatic field of a Buneman wave. Electron energization is more efficient in the out-of-plane orientation of the large-scale magnetic field because both the phase speed and the amplitude of the waves are higher than for the in-plane scenario. Also, a larger number of electrons is trapped by the waves compared to the in-plane configuration. We conclude that significant modifications of the simulation parameters are needed to reach the same level of SSA efficiency as in simulations with out-of-plane magnetic field or 3D simulations.
We study elements of the calculus of boundary value problems in a variant of Boutet de Monvel’s algebra (Acta Math 126:11–51, 1971) on a manifold N with edge and boundary. If the boundary is empty then the approach corresponds to Schulze (Symposium on partial differential equations (Holzhau, 1988), BSB Teubner, Leipzig, 1989) and other papers from the subsequent development. For non-trivial boundary we study Mellin-edge quantizations and compositions within the structure in terms a new Mellin-edge quantization, compared with a more traditional technique. Similar structures in the closed case have been studied in Gil et al.
We show that elliptic complexes of (pseudo) differential operators on smooth compact manifolds with boundary can always be complemented to a Fredholm problem by boundary conditions involving global pseudodifferential projections on the boundary (similarly as the spectral boundary conditions of Atiyah, Patodi, and Singer for a single operator). We prove that boundary conditions without projections can be chosen if, and only if, the topological Atiyah-Bott obstruction vanishes. These results make use of a Fredholm theory for complexes of operators in algebras of generalized pseudodifferential operators of Toeplitz type which we also develop in the present paper.
Swimming performance can be improved not only by in-water sport-specific training but also by means of dry land-training (e.g., plyometric jump training [PJT]). This study examined the effects of an 8-week PJT on proxies of muscle power and swimming performance in prepubertal male swimmers. Participants were randomly allocated to a PJT group (PJT; n = 14; age: 10.3 +/- 0.4 years, maturity-offset = -3 +/- 0.3) or a control group (CG; n = 12; age: 10.5 +/- 0.4 years, maturity-offset = -2.8 +/- 0.3). Swimmers in PJT and CG performed 6 training sessions per week. Each training session lasted between 80 and 90 minutes. Over the 8 weeks in-season training period, PJT performed two PJT sessions per week, each lasting between 25 to 30 minutes (similar to 1 hour per week) in replacement of sport-specific swimming drills. During that time, CG followed their regular sport-specific swimming training (e.g., coordination, breathing, improving swimming strokes). Overall training volume was similar between groups. Pre- and post-training, tests were conducted to assess proxies of muscle power (countermovement-jump [CMJ]), standing-long-jump [SLJ]) and sport-specific swimming performances (15-, 25-, and 50-m front-crawl, 25-m kick without push [25-m kick WP], and 25-m front-crawl WP). No training or test-related injuries were detected over the course of the study. Between-group analyses derived from magnitude-based inferences showed trivial-to-large effects in favour of PJT for all tests (ES = 0.28 to 1.43). Within-group analyses for the PJT showed small performance improvements for CMJ (effect-size [ES] = 0.53), 25-m kick WP (ES = 0.25), and 50-m front crawl (ES = 0.56) tests. Moderate performance improvements were observed for the SLJ, 25-m front-crawl WP, 15-m and 25-m front-crawl tests (ES = 0.95, 0.60, 0.99, and 0.85, respectively). For CG, the within-group results showed trivial performance declines for the CMJ (ES=-0.13) and the 50-m front-crawl test (ES = -0.04). In addition, trivial-to-small performance improvements were observed for the SLJ (ES = 0.09), 25-m kick WP (ES = 0.02), 25-m front-crawl WP (ES = 0.19), 25-m front-crawl (ES = 0.2), (SLJ [ES = 0.09, and 15-m front crawl (ES = 0.36). Short-term in-season PJT, integrated into the regular swimming training, was more effective than regular swimming training alone in improving jump and sport-specific swimming performances in prepubertal male swimmers.
We revisit the effect of nonlinear Landau (NL) damping on the electrostatic instability of blazar-induced pair beams, using a realistic pair-beam distribution. We employ a simplified 2D model in k-space to study the evolution of the electric-field spectrum and to calculate the relaxation time of the beam. We demonstrate that the 2D model is an adequate representation of the 3D physics. We find that nonlinear Landau damping, once it operates efficiently, transports essentially the entire wave energy to small wave numbers where wave driving is weak or absent. The relaxation time also strongly depends on the intergalactic medium temperature, T-IGM, and for T-IGM << 10 eV, and in the absence of any other damping mechanism, the relaxation time of the pair beam is longer than the inverse Compton (IC) scattering time. The weak late-time beam energy losses arise from the accumulation of wave energy at small k, that nonlinearly drains the wave energy at the resonant k of the pair-beam instability. Any other dissipation process operating at small k would reduce that wave-energy drain and hence lead to stronger pair-beam energy losses. As an example, collisions reduce the relaxation time by an order of magnitude, although their rate is very small. Other nonlinear processes, such as the modulation instability, could provide additional damping of the nonresonant waves and dramatically reduce the relaxation time of the pair beam. An accurate description of the spectral evolution of the electrostatic waves is crucial for calculating the relaxation time of the pair beam.
Small-aperture array as a tool to monitor fluid injection- and extraction-induced microseismicity
(2019)
The monitoring of microseismicity during temporary human activities such as fluid injections for hydrofracturing, hydrothermal stimulations or wastewater disposal is a difficult task. The seismic stations often cannot be installed on hard rock, and at quiet places, noise is strongly increased during the operation itself and the installation of sensors in deep wells is costly and often not feasible. The combination of small-aperture seismic arrays with shallow borehole sensors offers a solution. We tested this monitoring approach at two different sites: (1) accompanying a fracking experiment in sedimentary shale at 4km depth and (2) above a gas field under depletion. The small-aperture arrays were planned according to theoretical wavenumber studies combined with simulations considering the local noise conditions. We compared array recordings with recordings available from shallow borehole sensors and give examples of detection and location performance. Although the high-frequency noise on the 50-m-deep borehole sensors was smaller compared to the surface noise before the injection experiment, the signals were highly contaminated during injection by the pumping activities. Therefore, a set of three small-aperture arrays at different azimuths was more suited to detect small events, since noise recorded on these arrays is uncorrelated with each other. Further, we developed recommendations for the adaptation of the monitoring concept to other sites experiencing induced seismicity.
The advances in modern geodetic techniques such as the global navigation satellite system (GNSS) and synthetic aperture radar (SAR) provide surface deformation measurements with an unprecedented accuracy and temporal and spatial resolutions even at most remote volcanoes on Earth. Modelling of the high-quality geodetic data is crucial for understanding the underlying physics of volcano deformation processes. Among various approaches, mathematical models are the most effective for establishing a quantitative link between the surface displacements and the shape and strength of deformation sources. Advancing the geodetic data analyses and hence, the knowledge on the Earth’s interior processes, demands sophisticated and efficient deformation modelling approaches. Yet the majority of these models rely on simplistic assumptions for deformation source geometries and ignore complexities such as the Earth’s surface topography and interactions between multiple sources.
This thesis addresses this problem in the context of analytical and numerical volcano deformation modelling. In the first part, new analytical solutions for triangular dislocations (TDs) in uniform infinite and semi-infinite elastic media have been developed. Through a comprehensive investigation, the locations and causes of artefact singularities and numerical instabilities associated with TDs have been determined and these long-standing drawbacks have been addressed thoroughly. This approach has then been extended to rectangular dislocations (RDs) with full rotational degrees of freedom. Using this solution in a configuration of three orthogonal RDs a compound dislocation model (CDM) has been developed. The CDM can represent generalized volumetric and planar deformation sources efficiently. Thus, the CDM is relevant for rapid inversions in early warning systems and can also be used for detailed deformation analyses. In order to account for complex source geometries and realistic topography in the deformation models, in this thesis the boundary element method (BEM) has been applied to the new solutions for TDs. In this scheme, complex surfaces are simulated as a continuous mesh of TDs that may possess any displacement or stress boundary conditions in the BEM calculations. In the second part of this thesis, the developed modelling techniques have been applied to five different real-world deformation scenarios. As the first and second case studies the deformation sources associated with the 2015 Calbuco eruption and 2013–2016 Copahue inflation period have been constrained by using the CDM. The highly anisotropic source geometries in these two cases highlight the importance of using generalized deformation models such as the CDM, for geodetic data inversions. The other three case studies in this thesis involve high-resolution dislocation models and BEM calculations. As the third case, the 2013 pre-explosive inflation of Volcán de Colima has been simulated by using two ellipsoidal cavities, which locate zones of pressurization in the volcano’s lava dome. The fourth case study, which serves as an example for volcanotectonics interactions, the 3-D kinematics of an active ring-fault at Tendürek volcano has been investigated through modelling displacement time series over the 2003–2010 time period. As the fifth example, the deformation sources associated with North Korea’s underground nuclear test in September 2017 have been constrained. These examples demonstrate the advancement and increasing level of complexity and the general applicability of the developed dislocation modelling techniques.
This thesis establishes a unified framework for rapid and high-resolution dislocation modelling, which in addition to volcano deformations can also be applied to tectonic and humanmade deformations.
The occurrence of deep low-frequency (DLF) microearthquakes beneath volcanoes is commonly attributed to mass transport in the volcanic plumbing system and used to infer feeding channels from and into magma reservoirs. The key question is how magmas migrate from depth to the shallow crust and whether magma reservoirs are currently being recharged. For the first time since the improvement of the local seismic networks in the East Eifel region (Rhineland-Palatinate, Germany), we detect and locate recurrent DLF earthquakes in the lower crust and upper mantle beneath the Laacher See Volcano (LSV), using a joint data set of permanent sensors and a temporary deployment. So far, eight DLF earthquake sequences were observed in four distinct clusters between 10 and 40 km depth. These clusters of weak events (M-L< 2) align along an approximately 80. southeast dipping line south of the LSV. Moment tensor solutions of these events have large shear components, and the irregular dispersion and long coda of body waves indicate interaction processes between shear cracks and fluids. We find a rotation of P-axes orientation for shallow tectonic earthquakes compared to DLF events, indicating that the stress field in the depth interval of DLF events might favour a vertical migration of magma or magmatic fluids. The caldera of the LSV was formed by the last major eruption of the East Eifel Volcanic Field only 12.9 kyr ago, fed by a shallow magma chamber at 5-8 km depth and erupting a total magma volume of 6.7 km(3). The observed DLF earthquake activity and continuous volcanic gas emissions around the LSV indicate an active magmatic system, possibly connected with an upper mantle melt zone.
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.
Perovskite solar cells (PSCs) are one of the main research topics of the photovoltaic community; with efficiencies now reaching up to 24%, PSCs are on the way to catching up with classical inorganic solar cells. However, PSCs have not yet reached their full potential. In fact, their efficiency is still limited by nonradiative recombination, mainly via trap-states and by losses due to the poor transport properties of the commonly used transport layers (TLs). Indeed, state-of-the-art TLs (especially if organic) suffer from rather low mobilities, typically within 10(-5) and 10(-2) cm(-2) V-1 s(-1), when compared to the high mobilities, 1-10 cm(-2) V-1 s(-1), measured for perovskites. This work presents a comprehensive analysis of the effect of the mobility, thickness, and doping density of the transport layers based on combined experimental and modeling results of two sets of devices made of a solution-processed high-performing triple-cation (PCE approximate to 20%). The results are also cross-checked on vacuum-processed MAPbI(3) devices. From this analysis, general guidelines on how to optimize a TL are introduced and especially a new and simple formula to easily calculate the amount of doping necessary to counterbalance the low mobility of the TLs.
We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder.
The Seismic Hazard Inferred from Tectonics based on the Global Strain Rate Map (SHIFT_GSRM) earthquake forecast was designed to provide high-resolution estimates of global shallow seismicity to be used in seismic hazard assessment. This model combines geodetic strain rates with global earthquake parameters to characterize long-term rates of seismic moment and earthquake activity. Although SHIFT_GSRM properly computes seismicity rates in seismically active continental regions, it underestimates earthquake rates in subduction zones by an average factor of approximately 3. We present a complementary method to SHIFT_GSRM to more accurately forecast earthquake rates in 37 subduction segments, based on the conservation of moment principle and the use of regional interface seismicity parameters, such as subduction dip angles, corner magnitudes, and coupled seismogenic thicknesses. In seven progressive steps, we find that SHIFT_GSRM earthquake-rate underpredictions are mainly due to the utilization of a global probability function of seismic moment release that poorly captures the great variability among subduction megathrust interfaces. Retrospective test results show that the forecast is consistent with the observations during the 1 January 1977 to 31 December 2014 period. Moreover, successful pseudoprospective evaluations for the 1 January 2015 to 31 December 2018 period demonstrate the power of the regionalized earthquake model to properly estimate subduction-zone seismicity.
Strong light-matter coupling can re-arrange the exciton energies in organic semiconductors. Here, we exploit strong coupling by embedding a fullerene-free organic solar cell (OSC) photo-active layer into an optical microcavity, leading to the formation of polariton peaks and a red-shift of the optical gap. At the same time, the open-circuit voltage of the device remains unaffected. This leads to reduced photon energy losses for the low-energy polaritons and a steepening of the absorption edge. While strong coupling reduces the optical gap, the energy of the charge-transfer state is not affected for large driving force donor-acceptor systems. Interestingly, this implies that strong coupling can be exploited in OSCs to reduce the driving force for electron transfer, without chemical or microstructural modifications of the photoactive layer. Our work demonstrates that the processes determining voltage losses in OSCs can now be tuned, and reduced to unprecedented values, simply by manipulating the device architecture.
Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their VOC to values well below the Shockley–Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi‐Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the VOC of operational devices. These measurements prove that in state‐of‐the‐art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump‐probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome—paving the way to the thermodynamic efficiency limit.
2D Ruddlesden-Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite-based cells. Herein, 2D (CH3(CH2)(3)NH3)(2)(CH3NH3)(n-1)PbnI3n+1 perovskite cells with different numbers of [PbI6](4-) sheets (n = 2-4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open-circuit voltage (V-OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C-60 interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi-Fermi level splitting matches the device V-OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.
A proper assessment of seismic reference site conditions has important applications as they represent the basis on which ground motions and amplifications are generally computed. Besides accounting for the average S-wave velocity over the uppermost 30 m (V-S30), the parameterization of high-frequency ground motions beyond source-corner frequency received significant attention. kappa, an empirical parameter introduced by Anderson and Hough (1984), is often used to represent the spectral decay of the acceleration spectrum at high frequencies. The lack of hard-rock records and the poor understanding of the physics of kappa introduced significant epistemic uncertainty in the final seismic hazard of recent projects. Thus, determining precise and accurate regional hard-rock kappa(0) values is critical. We propose an alternative procedure for capturing the reference kappa(0) on regional scales by linking thewell-known high-frequency attenuation parameter kappa and the properties of multiple-scattered coda waves. Using geological and geophysical data around more than 1300 stations for separating reference and soft soil sites and based on more than 10,000 crustal earthquake recordings, we observe that kappa(0) from multiple-scattered coda waves seems to be independent of the soil type but correlated with the hard-rock kappa(0), showing significant regional variations across Europe. The values range between 0.004 s for northern Europe and 0.020 s for the southern and southeastern parts. On the other hand, measuring kappa (and correspondingly kappa(0)) on the S-wave window (as classically proposed), the results are strongly affected by transmitted (reflected, refracted, and scattered) waves included in the analyzed window biasing the proper assessment of kappa(0). This effect is more pronounced for soft soil sites. In this way, kappa(coda)(0) can serve as a proxy for the regional hard-rock kappa(0) at the reference sites.
If not oriented perfectly isotropically, the strong dipole moment of polar organic semiconductor materials such as tris-(8-hydroxyquinolate)aluminum (Alq3) will lead to the buildup of a giant surface potential (GSP) and thus to a macroscopic dielectric polarization of the organic film. Despite this having been a known fact for years, the implications of such high potentials within an organic layer stack have only been studied recently. In this work, the influence of the GSP on hole injection into organic layers is investigated. Therefore, we apply a concept called dipolar doping to devices consisting of the prototypical organic materials N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) as nonpolar host and Alq3 as dipolar dopant with different mixing ratios to tune the GSP. The mixtures are investigated in single-layer monopolar devices as well as bilayer metal/insulator/semiconductor structures. Characterization is done electrically using current-voltage (I-V) characteristics, impedance spectroscopy, and charge extraction by linearly increasing voltage and time of flight, as well as with ultraviolet photoelectron spectroscopy. We find a maximum in device performance for moderate to low doping concentrations of the polar species in the host. The observed behavior can be described on the basis of the Schottky effect for image-force barrier lowering, if the changes in the interface dipole, the carrier mobility, and the GSP induced by dipolar doping are taken into account.
This study aims to identify the best-performing site characterization proxy alternative and complementary to the conventional 30 m average shear-wave velocity V-S30, as well as the optimal combination of proxies in characterizing linear site response. Investigated proxies include T-0 (site fundamental period obtained from earthquake horizontal-to-vertical spectral ratios), V-Sz (measured average shear-wave velocities to depth z, z = 5, 10, 20 and 30 m), Z(0.8) and Z(1.0) (measured site depths to layers having shear-wave velocity 0.8 and 1.0 km/s, respectively), as well as Z(x-infer) (inferred site depths from a regional velocity model, x = 0.8 and 1.0, 1.5 and 2.5 km/s). To evaluate the performance of a site proxy or a combination, a total of 1840 surface-borehole recordings is selected from KiK-net database. Site amplifications are derived using surface-to-borehole response-, Fourier- and cross-spectral ratio techniques and then are compared across approaches. Next, the efficacies of 7 single-proxies and 11 proxy-pairs are quantified based on the site-to-site standard deviation of amplification residuals of observation about prediction using the proxy or the pair. Our results show that T-0 is the best-performing single-proxy among T-0, Z(0.8), Z(1.0) and V-Sz. Meanwhile, T-0 is also the best-performing proxy among T-0, Z(0.8), Z(1.0) and Z(x-infer) complementary to V-S30 in accounting for the residual amplification after V-S30-correction. Besides, T-0 alone can capture most of the site effects and should be utilized as the primary site indicator. Though (T-0, V-S30) is the best-performing proxy pair among (V-S30, T-0), (V-S30, Z(0.8)), (V-S30, Z(1.0)), (V-S30, Z(x-infer)) and (T-0, V-Sz), it is only slightly better than (T-0, V-S20). Considering both efficacy and engineering utility, the combination of T-0 (primary) and V-S20 (secondary) is recommended. Further study is needed to test the performances of various proxies on sites in deep sedimentary basins.
The in‐depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter‐related via the kinetics of charge transfer states—being singlet or triplet states. Although high‐charge‐photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low‐mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta‐analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field‐dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a “spin‐related factor” that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge‐generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin‐related factor.
Today's perovskite solar cells (PSCs) are limited mainly by their open‐circuit voltage (VOC) due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity‐dependent measurements of the quasi‐Fermi level splitting (QFLS) and of the VOC on the very same devices, including pin‐type PSCs with efficiencies above 20%, are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley‐Queisser theory. This has far‐reaching implications for the applicability of some well‐established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift‐diffusion simulations, the intensity dependence of the QFLS, the QFLS‐VOC offset and the ideality factor are consistently explained by trap‐assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS‐VOC relation is of great importance.
The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer.
Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11).
We derive a set of regional ground-motion prediction equations (GMPEs) in the Fourier amplitude spectra (FAS-GMPE) and in the spectral acceleration (SA-GMPE) domains for the purpose of interpreting the between-event residuals in terms of source parameter variability. We analyze a dataset of about 65,000 recordings generated by 1400 earthquakes (moment magnitude 2: 5 <= M-w <= 6: 5, hypocentral distance R-hypo <= 150 km) that occurred in central Italy between January 2008 and October 2017. In a companion article (Bindi, Spallarossa, et al., 2018), the nonparametric acceleration source spectra were interpreted in terms of omega-square models modified to account for deviations from a high-frequency flat plateau through a parameter named k(source). Here, the GMPEs are derived considering the moment (M-w), the local (M-L), and the energy (M-e) magnitude scales, and the between-event residuals are computed as random effects. We show that the between-event residuals for the FAS-GMPE implementing M-w are correlated with stress drop, with correlation coefficients increasing with increasing frequency up to about 10 Hz. Contrariwise, the correlation is weak for the FAS-GMPEs implementing M-L and M-e, in particular between 2 and 5 Hz, where most of the corner frequencies lie. At higher frequencies, all models show a strong correlation with k(source). The correlation with the source parameters reflects in a different behavior of the standard deviation tau of the between-event residuals with frequency. Although tau is smaller for the FAS-GMPE using M-w below 1.5 Hz, at higher frequencies, the model implementing either M-L or M-e shows smaller values, with a reduction of about 30% at 3 Hz (i.e., from 0.3 for M-w to 0.1 for M-L). We conclude that considering magnitude scales informative for the stress-drop variability allows to reduce the between-event variability with a significant impact on the hazard assessment, in particular for studies in which the ergodic assumption on site is removed.
Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.
The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C-60 and small amounts of organic donor molecules. We find a pronounced decline of all photovoltaic parameters with decreasing CT state energy. Using a combination of steady-state photocurrent measurements and time-delayed collection field experiments, we demonstrate that the power conversion efficiency, and more specifically, the fill factor of these devices, is mainly determined by the bias dependence of photocurrent generation. By combining these findings with the results from ultrafast transient absorption spectroscopy, we show that blends with small CT energies perform poorly because of an increased nonradiative CT state decay rate and that this decay obeys an energy-gap law. Our work challenges the common view that a large energy offset at the heterojunction and/or the presence of fullerene clusters guarantee efficient CT dissociation and rather indicates that charge generation benefits from high CT state energies through a slower decay to the ground state.
Shear-waves are the most energetic body-waves radiated from an earthquake, and are responsible for the destruction of engineered structures. In both short-term emergency response and long-term risk forecasting of disaster-resilient built environment, it is critical to predict spatially accurate distribution of shear-wave amplitudes. Although decades’ old theory proposes a deterministic, highly anisotropic, four-lobed shear-wave radiation pattern, from lack of convincing evidence, most empirical ground-shaking prediction models settled for an oversimplified stochastic radiation pattern that is isotropic on average. Today, using the large datasets of uniformly processed seismograms from several strike, normal, reverse, and oblique-slip earthquakes across the globe, compiled specifically for engineering applications, we could reveal, quantify, and calibrate the frequency-, distance-, and style-of-faulting dependent transition of shear-wave radiation between a stochastic-isotropic and a deterministic-anisotropic phenomenon. Consequent recalibration of empirical ground-shaking models dramatically improved their predictions: with isodistant anisotropic variations of ±40%, and 8% reduction in uncertainty. The outcomes presented here can potentially trigger a reappraisal of several practical issues in engineering seismology, particularly in seismic ground-shaking studies and seismic hazard and risk assessment.
Adjustment of median ground motion prediction equations (GMPEs) from one region to another region is one of the major challenges within the current practice of seismic hazard analysis. In our approach of generating response spectra, we derive two separate empirical models for a) Fourier amplitude spectrum (FAS) and b) duration of ground motion. To calculate response spectra, the two models are combined within the random vibration theory (RVT) framework. The models are calibrated on recordings obtained from shallow crustal earthquakes in active tectonic regions. We use a subset of NGA-West2 database with M3.2-7.9 earthquakes at distances 0-300 km. The NGA-West2 database expanded over a wide magnitude and distance range facilitates a better constraint over derived models. A frequency-dependent duration model is derived to obtain adjustable response spectral ordinates. Excellent comparison of our approach with other NGA-West2 models implies that it can also be used as a stand-alone model.
Organic semiconductors are a promising class of materials. Their special properties are the particularly good absorption, low weight and easy processing into thin films. Therefore, intense research has been devoted to the realization of thin film organic solar cells (OPVs). Because of the low dielectric constant of organic semiconductors, primary excitations (excitons) are strongly bound and a type II heterojunction needs to be introduced to split these excitations into free charges. Therefore, most organic solar cells consist of at least an electron donor and electron acceptor material. For such donor acceptor systems mainly three states are relevant; the photoexcited exciton on the donor or acceptor material, the charge transfer state at the donor-acceptor interface and the charge separated state of a free electron and hole. The interplay between these states significantly determines the efficiency of organic solar cells. Due to the high absorption and the low charge carrier mobilities, the active layers are usually thin but also, exciton dissociation and free charge formation proceeds rapidely, which makes the study of carrier dynamics highly challenging.
Therefore, the focus of this work was first to install new experimental setups for the investigation of the charge carrier dynamics in complete devices with superior sensitivity and time resolution and, second, to apply these methods to prototypical photovoltaic materials to address specific questions in the field of organic and hybrid photovoltaics.
Regarding the first goal, a new setup combining transient absorption spectroscopy (TAS) and time delayed collection field (TDCF) was designed and installed in Potsdam. An important part of this work concerned the improvement of the electronic components with respect to time resolution and sensitivity. To this end, a highly sensitive amplifier for driving and detecting the device response in TDCF was developed. This system was then applied to selected organic and hybrid model systems with a particular focus on the understanding of the loss mechanisms that limit the fill factor and short circuit current of organic solar cells.
The first model system was a hybrid photovoltaic material comprising inorganic quantum dots decorated with organic ligands. Measurements with TDCF revealed fast free carrier recombination, in part assisted by traps, while bias-assisted charge extraction measurements showed high mobility. The measured parameters then served as input for a successful description of the device performance with an analytical model.
With a further improvement of the instrumentation, a second topic was the detailed analysis of non-geminate recombination in a disordered polymer:fullerene blend where an important question was the effect of disorder on the carrier dynamics. The measurements revealed that early time highly mobile charges undergo fast non-geminate recombination at the contacts, causing an apparent field dependence of free charge generation in TDCF experiments if not conducted properly. On the other hand, recombination the later time scale was determined by dispersive recombination in the bulk of the active layer, showing the characteristics of carrier dynamics in an exponential density of state distribution. Importantly, the comparison with steady state recombination data suggested a very weak impact of non-thermalized carriers on the recombination properties of the solar cells under application relevant illumination conditions.
Finally, temperature and field dependent studies of free charge generation were performed on three donor-acceptor combinations, with two donor polymers of the same material family blended with two different fullerene acceptor molecules. These particular material combinations were chosen to analyze the influence of the energetic and morphology of the blend on the efficiency of charge generation. To this end, activation energies for photocurrent generation were accurately determined for a wide range of excitation energies. The results prove that the formation of free charge is via thermalized charge transfer states and does not involve hot exciton splitting. Surprisingly, activation energies were of the order of thermal energy at room temperature. This led to the important conclusion that organic solar cells perform well not because of predominate high energy pathways but because the thermalized CT states are weakly bound. In addition, a model is introduced to interconnect the dissociation efficiency of the charge transfer state with its recombination observable with photoluminescence, which rules out a previously proposed two-pool model for free charge formation and recombination. Finally, based on the results, proposals for the further development of organic solar cells are formulated.
Two new hole selective materials (HSMs) based on dangling methylsulfanyl groups connected to the C-9 position of the fluorene core are synthesized and applied in perovskite solar cells. Being structurally similar to a half of Spiro-OMeTAD molecule, these HSMs (referred as FS and DFS) share similar redox potentials but are endowed with slightly higher hole mobility, due to the planarity and large extension of their structure. Competitive power conversion efficiency (up to 18.6%) is achieved by using the new HSMs in suitable perovskite solar cells. Time-resolved photoluminescence decay measurements and electrochemical impedance spectroscopy show more efficient charge extraction at the HSM/perovskite interface with respect to Spiro-OMeTAD, which is reflected in higher photocurrents exhibited by DFS/FS-integrated perovskite solar cells. Density functional theory simulations reveal that the interactions of methylammonium with methylsulfanyl groups in DFS/FS strengthen their electrostatic attraction with the perovskite surface, providing an additional path for hole extraction compared to the sole presence of methoxy groups in Spiro-OMeTAD. Importantly, the low-cost synthesis of FS makes it significantly attractive for the future commercialization of perovskite solar cells.
The 2-D distinct element method (DEM) code (PFC2D_V5) is used here to simulate the evolution of subsidence-related karst landforms, such as single and clustered sinkholes, and associated larger-scale depressions. Subsurface material in the DEM model is removed progressively to produce an array of cavities; this simulates a network of subsurface groundwater conduits growing by chemical/mechanical erosion. The growth of the cavity array is coupled mechanically to the gravitationally loaded surroundings, such that cavities can grow also in part by material failure at their margins, which in the limit can produce individual collapse sinkholes. Two end-member growth scenarios of the cavity array and their impact on surface subsidence were examined in the models: (1) cavity growth at the same depth level and growth rate; (2) cavity growth at progressively deepening levels with varying growth rates. These growth scenarios are characterised by differing stress patterns across the cavity array and its overburden, which are in turn an important factor for the formation of sinkholes and uvalalike depressions. For growth scenario (1), a stable compression arch is established around the entire cavity array, hindering sinkhole collapse into individual cavities and favouring block-wise, relatively even subsidence across the whole cavity array. In contrast, for growth scenario (2), the stress system is more heterogeneous, such that local stress concentrations exist around individual cavities, leading to stress interactions and local wall/overburden fractures. Consequently, sinkhole collapses occur in individual cavities, which results in uneven, differential subsidence within a larger-scale depression. Depending on material properties of the cavity-hosting material and the overburden, the larger-scale depression forms either by sinkhole coalescence or by widespread subsidence linked geometrically to the entire cavity array. The results from models with growth scenario (2) are in close agreement with surface morphological and subsurface geophysical observations from an evaporite karst area on the eastern shore of the Dead Sea.
An understanding of the factors limiting the open-circuit voltage (V-oc) and related photon energy loss mechanisms is critical to increase the power conversion efficiency (PCE) of small-molecule organic solar cells (OSCs), especially those with near-infrared (NIR) absorbers. In this work, two NIR boron dipyrromethene (BODIPY) molecules are characterized for application in planar (PHJ) and bulk (BHJ) heterojunction OSCs. When two H atoms are substituted by F atoms on the peripheral phenyl rings of the molecules, the molecular aggregation type in the thin film changes from the H-type to J-type. For PHJ devices, the nonradiative voltage loss of 0.35 V in the J-aggregated BODIPY is lower than that of 0.49 V in the H-aggregated device. In BHJ devices with a nonradiative voltage loss of 0.35 V, a PCE of 5.5% is achieved with an external quantum efficiency (EQE) maximum of 68% at 700 nm.
Charge extraction in organic solar cells (OSCs) is commonly believed to be limited by bimolecular recombination of photogenerated charges. However, the fill factor of OSCs is usually almost entirely governed by recombination processes that scale with the first order of the light intensity. This linear loss was often interpreted to be a consequence of geminate or trap-assisted recombination. Numerical simulations show that this linear dependence is a direct consequence of the large amount of excess dark charge near the contact. The first-order losses increase with decreasing mobility of minority carriers, and we discuss the impact of several material and device parameters on this loss mechanism. This work highlights that OSCs are especially vulnerable to injected charges as a result of their poor charge transport properties. This implies that dark charges need to be better accounted for when interpreting electro-optical measurements and charge collection based on simple figures of merit.
Hippotheologie
(2019)
Electroluminescence (EL) spectra of hybrid charge transfer states at metal oxide/organic type-II heterojunctions exhibit bias-induced spectral shifts. The reasons for this phenomenon have been discussed controversially and arguments for either electric field-induced effects or the filling of trap states at the oxide surface have been put forward. Here, we combine the results of EL and photovoltaic measurements to eliminate the unavoidable effect of the series resistance of inorganic and organic components on the total voltage drop across the hybrid device. For SnOx combined with the conjugated polymer [ladder type poly-(para-phenylene)], we find a one-to-one correspondence between the blue-shift of the EL peak and the increase of the quasi-Fermi level splitting at the hybrid heterojunction, which we unambiguously assign to state filling. Our data are resembled best by a model considering the combination of an exponential density of states with a doped semiconductor. Published under license by AIP Publishing.
The one-dimensional (1-D) approach is still the dominant method to incorporate site effects in engineering applications. To bridge the 1-D to multidimensional site response analysis, we develop quantitative criteria and a reproducible method to identify KiK-net sites with significant deviations from 1-D behavior. We found that 158 out of 354 show two-dimensional (2-D) and three-dimensional (3-D) effects, extending the resonance toward shorter periods at which 2-D or 3-D site effects exceed those of the classic 1-D configurations and imposing an additional amplification to that caused by the impedance contrast alone. Such 2-D and 3-D effects go along with a large within-station ground motion variability. Remarkably, these effects are found to be more pronounced for small impedance contrasts. While it is hardly possible to identify common features in ground motion behavior for stations with similar topography typologies, it is not over-conservative to apply a safety factor to account for 2-D and 3-D site effects in ground motion modeling.
Charge extraction methods are popular for measuring the charge carrier density in thin film organic solar cells and to draw conclusions about the order and coefficient of nongeminate charge recombination. However, results from such studies may be falsified by inhomogeneous steady state carrier profiles or surface recombination. Here, we present a detailed drift-diffusion study of two charge extraction methods, bias-assisted charge extraction (BACE) and time-delayed collection field (TDCF). Simulations are performed over a wide range of the relevant parameters. Our simulations reveal that both charge extraction methods provide reliable information about the recombination order and coefficient if the measurements are performed under appropriate conditions. However, results from BACE measurements may be easily affected by surface recombination, in particular for small active layer thicknesses and low illumination densities. TDCF, on the other hand, is more robust against surface recombination due to its transient nature but also because it allows for a homogeneous high carrier density to be inserted into the active layer. Therefore, TDCF is capable to provide meaningful information on the order and coefficient of recombination even if the model conditions are not exactly fulfilled. We demonstrate this for an only 100 nm thick layer of a highly efficient nonfullerene acceptor (NFA) blend, comprising the donor polymer PM6 and the NFA Y6. TDCF measurements were performed as a function of delay time for different laser fluences and bias conditions. The full set of data could be consistently fitted by a strict second order recombination process, with a bias- and fluence-independent bimolecular recombination coefficient k(2) = 1.7 x 10(-17)m(3) s(-1). BACE measurements performed on the very same layer yielded the identical result, despite the very different excitation conditions. This proves that recombination in this blend is mostly through processes in the bulk and that surface recombination is of minor importance despite the small active layer thickness. Published under license by AIP Publishing.
Optimizing the photoluminescence (PL) yield of a solar cell has long been recognized as a key principle to maximize the power conversion efficiency. While PL measurements are routinely applied to perovskite films and solar cells under open circuit conditions (V-OC), it remains unclear how the emission depends on the applied voltage. Here, we performed PL(V) measurements on perovskite cells with different hole transport layer thicknesses and doping concentrations, resulting in remarkably different fill factors (FFs). The results reveal that PL(V) mirrors the current-voltage (JV) characteristics in the power-generating regime, which highlights an interesting correlation between radiative and nonradiative recombination losses. In particular, high FF devices show a rapid quenching of PL(V) from open-circuit to the maximum power point. We conclude that, while the PL has to be maximized at V-OC at lower biases < V-OC the PL must be rapidly quenched as charges need to be extracted prior to recombination.
In the Next Generation Attenuation West2 (NGA-West2) project, a 3D subsurface structure model (Japan Seismic Hazard Information Station [J-SHIS]) was queried to establish depths to 1.0 and 2.5 km/s velocity isosurfaces for sites without depth measurement in Japan. In this article, we evaluate the depth parameters in the J-SHIS velocity model by comparing them with their corresponding site-specific depth measurements derived from selected KiK-net velocity profiles. The comparison indicates that the J-SHIS model underestimates site depths at shallow sites and overestimates depths at deep sites. Similar issues were also identified in the southern California basin model. Our results also show that these underestimations and over-estimations have a potentially significant impact on ground-motion prediction using NGA-West2 ground-motion models (GMMs). Site resonant period may be considered as an alternative to depth parameter in the site term of a GMM.
Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces.
The computation of such synthetic GFs is computationally and operationally demanding. As a consequence, the onthe-fly recalculation of synthetic GFs in each iteration of an optimisation is time-consuming and impractical. Therefore, the pre-calculation and efficient storage of synthetic GFs on a dense grid of source to receiver combinations enables the efficient lookup and utilisation of GFs in time-critical scenarios. We present a Python-based framework and toolkit - Pyrocko-GF - that enables the pre-calculation of synthetic GF stores, which are independent of their numerical calculation method and GF transfer function. The framework aids in the creation of such GF stores by interfacing a suite of established numerical forward modelling codes in seismology (computational back ends). So far, interfaces to back ends for layered Earth model cases have been provided; however, the architecture of Pyrocko-GF is designed to cover back ends for other geometries (e.g. full 3-D heterogeneous media) and other physical quantities (e.g. gravity, pressure, tilt). Therefore, Pyrocko-GF defines an extensible GF storage format suitable for a wide range of GF types, especially handling elasticity and wave propagation problems. The framework assists with visualisations, quality control, and the exchange of GF stores, which is supported through an online platform that provides many pre-calculated GF stores for local, regional, and global studies. The Pyrocko-GF toolkit comes with a well-documented application programming interface (API) for the Python programming language to efficiently facilitate forward modelling of geophysical processes, e.g. synthetic waveforms or static displacements for a wide range of source models.
The task of downloading comprehensive datasets of event-based seismic waveforms has been made easier through the development of standardized webservices but is still highly nontrivial because the likelihood of temporary network failures or subtle data errors naturally increases when the amount of requested data is in the order of millions of relatively short segments. This is even more challenging because the typical workflow is not restricted to a single massive download but consists of fetching all possible available input data (e.g., with several repeated download executions) for a processing stage producing any desired user-defined output. Here, we present stream2segment, a highly customizable Python 2+3 package helping the user in the entire workflow of downloading, inspecting, and processing event-based seismic data by means of a relational database management system as archiving storage, which has clear performance and usability advantages, and an integrated processing subroutine requiring a configuration file and a single Python function to produce user-defined output. Stream2segment can also produce diagnostic maps or user-defined plots, which, unlike existing tools, do not require external software dependencies and are not static images but instead are interactive browser-based applications ideally suited for data inspection or annotation tasks and subsequent training of classifiers in foreseen supervised machine-learning applications. Stream2segment has already been used as a data quality tool for datasets within the European Integrated Data Archive and to create a weak-motion database (in the form of a so-called flat file) for the stable continental region of Europe in the context of the European Ground Shaking Intensity Model service, in turn an important building block for seismic hazard studies.
The in-depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter-related via the kinetics of charge transfer states-being singlet or triplet states. Although high-charge-photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low-mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta-analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field-dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a "spin-related factor" that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge-generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin-related factor.
Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their V-OC to values well below the Shockley-Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi-Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the V-OC of operational devices. These measurements prove that in state-of-the-art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump-probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome-paving the way to the thermodynamic efficiency limit.
Today's perovskite solar cells (PSCs) are limited mainly by their open‐circuit voltage (VOC) due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity‐dependent measurements of the quasi‐Fermi level splitting (QFLS) and of the VOC on the very same devices, including pin‐type PSCs with efficiencies above 20%, are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley‐Queisser theory. This has far‐reaching implications for the applicability of some well‐established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift‐diffusion simulations, the intensity dependence of the QFLS, the QFLS‐VOC offset and the ideality factor are consistently explained by trap‐assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS‐VOC relation is of great importance.
Power conversion efficiencies of donor/acceptor organic solar cells utilizing nonfullerene acceptors have now increased beyond the record of their fullerene-based counterparts. There remain many fundamental questions regarding nanomorphology, interfacial states, charge generation and extraction, and losses in these systems. Herein, we present a comparative study of bulk heterojunction solar cells composed of a recently introduced naphthothiadiazole-based polymer (NT812) as the electron donor and two different acceptor molecules, namely, [6,6]-phenyl-C71-butyric acid methyl ester (PCBM)[70] and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITIC). A comparison between the photovoltaic performance of these two types of solar cells reveals that the open-circuit voltage (Voc) of the NT812:ITIC-based solar cell is larger, but the fill factor (FF) is lower than that of the NT812:PCBM[70] device. We find the key reason behind this reduced FF in the ITIC-based device to be faster nongeminate recombination relative to the NT812:PCBM[70] system.
The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C-60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from similar to 1.23 eV for the bare absorber, just similar to 90 meV below the radiative limit, to similar to 1.10 eV when C-60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of similar to 30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure. [GRAPHICS] .
The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C-60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from similar to 1.23 eV for the bare absorber, just similar to 90 meV below the radiative limit, to similar to 1.10 eV when C-60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of similar to 30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure. [GRAPHICS] .