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The fact that organic solar cells perform efficiently despite the low dielectric constant of most photoactive blends initiated a long-standing debate regarding the dominant pathways of free charge formation. Here, we address this issue through the accurate measurement of the activation energy for free charge photogeneration over a wide range of photon energy, using the method of time-delayed collection field. For our prototypical low bandgap polymer:fullerene blends, we find that neither the temperature nor the field dependence of free charge generation depend on the excitation energy, ruling out an appreciable contribution to free charge generation though hot carrier pathways. On the other hand, activation energies are on the order of the room temperature thermal energy for all studied blends. We conclude that charge generation in such devices proceeds through thermalized charge transfer states, and that thermal energy is sufficient to separate most of these states into free charges.
Fullerene-based acceptors have dominated organic solar cells for almost two decades. It is only within the last few years that alternative acceptors rival their dominance, introducing much more flexibility in the optoelectronic properties of these material blends. However, a fundamental physical understanding of the processes that drive charge separation at organic heterojunctions is still missing, but urgently needed to direct further material improvements. Here a combined experimental and theoretical approach is used to understand the intimate mechanisms by which molecular structure contributes to exciton dissociation, charge separation, and charge recombination at the donor-acceptor (D-A) interface. Model systems comprised of polythiophene-based donor and rylene diimide-based acceptor polymers are used and a detailed density functional theory (DFT) investigation is performed. The results point to the roles that geometric deformations and direct-contact intermolecular polarization play in establishing a driving force ( energy gradient) for the optoelectronic processes taking place at the interface. A substantial impact for this driving force is found to stem from polymer deformations at the interface, a finding that can clearly lead to new design approaches in the development of the next generation of conjugated polymers and small molecules.
Ground‐motion prediction equations (GMPEs) are calibrated to predict the intensity of ground shaking at any given location, based on earthquake magnitude, source‐to‐site distance, local soil amplifications, and other parameters. GMPEs are generally assumed to be independent of time; however, evidence is increasing that large earthquakes modify the shallow soil conditions and those of the fault zone for months or years. These changes may affect the intensity of shaking and result in time‐dependent effects that can potentially be resolved by analyzing between‐event residuals (residuals between observed and predicted ground motion for individual earthquakes averaged over all stations). Here, we analyze a data set of about 65,000 recordings for about 1400 earthquakes in the moment magnitude range 2.5–6.5 that occurred in central Italy from 2008 to 2017 to capture the temporal variability of the ground shaking at high frequency. We first compute between‐event residuals for each earthquake in the Fourier domain with respect to a GMPE developed ad hoc for the analyzed data set. The between‐events show large changes after the occurrence of mainshocks such as the 2009 Mw 6.3 L'Aquila, the 2016 Mw 6.2 Amatrice, and Mw 6.5 Norcia earthquakes. Within the time span of a few months after the mainshocks, the between‐event contribution to the ground shaking varies by a factor 7. In particular, we find a large drop in the between‐events in the aftermath of the L'Aquila earthquake, followed by a slow positive trend that leads to a recovery interrupted by a new drop at the beginning of 2014. We also quantify the frequency‐dependent correlation between the Brune stress drop Δσ and the between‐events. We find that the temporal changes of Δσ resemble those of the between‐event residuals; in particular, during the period when the between‐events show the positive trend, the average logarithm of Δσ increases with an annual rate of 0.19 (i.e., the amplification factor for Δσ is 1.56 per year). Breakpoint analysis located a change in the linear trend coefficients of Δσ versus time in February 2014, although no large earthquakes occurred at that time. Finally, the temporal variability of Δσ mirrors the relative seismic‐velocity variations observed in previous studies for the same area and period, suggesting that both crack healing along the main fault system and healing of microcracks distributed at shallow depths throughout the surrounding region might be necessary to explain the wider observations of postearthquake recovery.
Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short-circuit currents (J(SC)) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open-circuit voltages (V-OC). Recently, reports have highlighted BHJ blends that are pushing at the accepted limits of energetic offsets necessary for high efficiency. Unfortunately, most of these BHJs have modest FF values. How the energetic offset impacts the solar cell characteristics thus remains poorly understood. Here, a comprehensive characterization of the losses in a polymer:fullerene BHJ blend, PIPCP:phenyl-C61-butyric acid methyl ester (PC61BM), that achieves a high V-OC (0.9 V) with very low energy losses (E-loss = 0.52 eV) from the energy of absorbed photons, a respectable J(SC) (13 mA cm(-2)), but a limited FF (54%) is reported. Despite the low energetic offset, the system does not suffer from field-dependent generation and instead it is characterized by very fast nongeminate recombination and the presence of shallow traps. The charge-carrier losses are attributed to suboptimal morphology due to high miscibility between PIPCP and PC61BM. These results hold promise that given the appropriate morphology, the J(SC), V-OC, and FF can all be improved, even with very low energetic offsets.
We propose an alternative procedure for the capture of the hard‐rock regional kappa (κ0ref). In our approach, we make use of a potential link between the well‐known κ parameter and the properties of coda waves. In our analysis, we consider near‐distance records of four crustal earthquakes of local magnitude 3.7–4.9 that occurred in four regions of France in different geological contexts: the crystalline axial chain of Pyrenees to the southwest, the large sedimentary basin to the southeast, the Alpine range to the east, and the extensional Rhine graben to the northeast. Each earthquake has been recorded at a pair of nearby soft‐ and hard‐rock station sites. The high‐frequency (16–32 Hz) spectral amplitudes of the coda window (carefully selected on the time series of the accelerograms) confirm an exponential decrease, which we quantify by κAHcoda and call “kappa of coda.” It is found that κAHcoda is independent of the soil type but shows significant regional variations. κ measurements (Anderson and Hough, 1984) over the coda window (κAHcoda) and full time series (κAH) show strong correlation at hard‐rock sites. This suggests that κAHcoda can provide a new proxy to estimate the regional hard rock κ0ref (Ktenidou et al., 2015). Theoretical analysis is also presented to relate the regional κAHcoda and coda quality factor Qc, which quantifies the average attenuation properties of the crust (both scattering and absorption). It allows interpreting κAHcoda as the time spent by the waves in the medium, weighted by its attenuation properties. This theoretical analysis also shows that the classical κ measurement should be frequency dependent; this was confirmed by the spectra of the observed records.
To evaluate the spatiotemporal variations of ground motions in northern Chile, we built a high-quality rock seismic acceleration database and an interface earthquakes catalog. Two ground-motion prediction equation (GMPE) models for subduction zones have been tested and validated for the area. They were then used as backbone models to describe the time-space variations of earthquake frequency content (Fourier and response spectra). Consistent with previous studies of large subduction earthquakes, moderate interface earthquakes in northern Chile show an increase of the high-frequency energy released with depth. A regional variability of earthquake frequency content is also observed, which may be related to a lateral segmentation of the mechanical properties of the subduction interface. Finally, interface earthquakes show a temporal evolution of their frequency content in the earthquake sequence associated with the 2014 Iquique M-w 8.1 megathrust earthquake. Surprisingly, the change does not occur with the mainshock but is associated with an 8 month slow slip preceding the megathrust. Electronic Supplement: Strong-motion database.
In catastrophe risk modeling, a defensible estimation of impact severity and its likelihood of occurrence to a portfolio of assets can only be made through a rigorous treatment of uncertainty and the consideration of multiple alternative models. This approach, however, requires repeating lengthy calculations multiple times. To limit the demand on computational time and resources, a frequent practice in the industry is to estimate the distribution of earthquake-induced portfolio losses using a simulated catalog of events from a single representative mean ground motion hazard model for the region. This simplified approach is faster but may provide biased estimates of the likelihood of occurrence of the large and infrequent losses that drive many risk mitigation decisions. Investigation through case studies of different portfolios of assets located in the San Francisco Bay Region shows the potential for both a bias in the mean loss estimates and an underestimation of their central 70% interpercentile. We propose a simplified and computationally practical approach that reduces the bias in the mean portfolio loss estimates. This approach does not improve the estimate of the interpercentile range, however, a quantity of no direct practical use.
The interplay between nanomorphology and efficiency of polymer-fullerene bulk-heterojunction (BHJ) solar cells has been the subject of intense research, but the generality of these concepts for small-molecule (SM) BHJs remains unclear. Here, the relation between performance; charge generation, recombination, and extraction dynamics; and nanomorphology achievable with two SM donors benzo[1,2-b:4,5-b]dithiophene-pyrido[3,4-b]-pyrazine BDT(PPTh2)(2), namely SM1 and SM2, differing by their side-chains, are examined as a function of solution additive composition. The results show that the additive 1,8-diiodooctane acts as a plasticizer in the blends, increases domain size, and promotes ordering/crystallinity. Surprisingly, the system with high domain purity (SM1) exhibits both poor exciton harvesting and severe charge trapping, alleviated only slightly with increased crystallinity. In contrast, the system consisting of mixed domains and lower crystallinity (SM2) shows both excellent exciton harvesting and low charge recombination losses. Importantly, the onset of large, pure crystallites in the latter (SM2) system reduces efficiency, pointing to possible differences in the ideal morphologies for SM-based BHJ solar cells compared with polymer-fullerene devices. In polymer-based systems, tie chains between pure polymer crystals establish a continuous charge transport network, whereas SM-based active layers may in some cases require mixed domains that enable both aggregation and charge percolation to the electrodes.
Mechanical and/or chemical removal of material from the subsurface may generate large subsurface cavities, the destabilisation of which can lead to ground collapse and the formation of sinkholes. Numerical simulation of the interaction of cavity growth, host material deformation and overburden collapse is desirable to better understand the sinkhole hazard but is a challenging task due to the involved high strains and material discontinuities. Here, we present 2-D distinct element method numerical simulations of cavity growth and sinkhole development. Firstly, we simulate cavity formation by quasi-static, stepwise removal of material in a single growing zone of an arbitrary geometry and depth. We benchmark this approach against analytical and boundary element method models of a deep void space in a linear elastic material. Secondly, we explore the effects of properties of different uniform materials on cavity stability and sinkhole development. We perform simulated biaxial tests to calibrate macroscopic geotechnical parameters of three model materials representative of those in which sinkholes develop at the Dead Sea shoreline: mud, alluvium and salt. We show that weak materials do not support large cavities, leading to gradual sagging or suffusion-style subsidence. Strong materials support quasi-stable to stable cavities, the overburdens of which may fail suddenly in a caprock or bedrock collapse style. Thirdly, we examine the consequences of layered arrangements of weak and strong materials. We find that these are more susceptible to sinkhole collapse than uniform materials not only due to a lower integrated strength of the overburden but also due to an inhibition of stabilising stress arching. Finally, we compare our model sinkhole geometries to observations at the Ghor Al-Haditha sinkhole site in Jordan. Sinkhole depth / diameter ratios of 0.15 in mud, 0.37 in alluvium and 0.33 in salt are reproduced successfully in the calibrated model materials. The model results suggest that the observed distribution of sinkhole depth / diameter values in each material type may partly reflect sinkhole growth trends.
The Engineering Strong-Motion (ESM) flatfile is a parametric table which contains verified and reliable metadata and intensity measures of manually processed waveforms included in the ESM database. The flatfile has been developed within the Seismology Thematic Core Service of EPOS-IP (European Plate Observing System Implementation Phase) and it is disseminated throughout a web portal for research and technical purposes. The adopted criteria for flatfile compilation aim to collect strong motion data and related metadata in a uniform, updated, traceable and quality-checked way to develop Ground Motion Models (GMMs) for Probabilistic Seismic Hazard Assessment (PSHA) and engineering applications. In this paper, we present the characteristics of ESM flatfile in terms of recording, event and station distributions, and we discuss the most relevant features of the Intensity Measures (IMs) of engineering interest included in the table. The dataset for flatfile compilation includes 23,014 recordings from 2179 earthquakes and 2080 stations from Europe and Middle-East. The events are characterized by magnitudes in the range 3.5-8.0 and refer to different tectonics regimes, such as shallow active crustal and subduction zones. Intensity measures include peak and integral parameters and duration of each waveform. The spectral amplitudes of the (5% damping) acceleration and displacement response are provided for 36 periods, in the interval 0.01-10 s, as well as the 103 amplitudes of the Fourier spectrum for the frequency range 0.04-50 Hz. Several statistics are shown with reference to the most significant metadata for GMMs calibrations, such as moment magnitude, focal depth, several distance metrics, style of faulting and parameters for site characterization. Furthermore, we also compare and explain the most relevant differences between the metadata of ESM flatfile with those provided by the previous flatfile derived in RESORCE (Reference Database for Seismic Ground Motion in Europe) project.