Insights into the Enhanced Cycle and Rate Performances of the F-Substituted P2-Type Oxide Cathodes f
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In recent years, substantial efforts have been made for the study of multinucleon transfer reactions at energies around the Coulomb barrier both experimentally and theoretically, aiming at the production of unknown neutron-rich heavy nuclei. It is crucial to provide reliable theoretical predictions based on microscopic theories with sufficient predictive power. Purpose: This article aims to clarify the applicability of the quantal diffusion approach based on the stochastic mean-field (SMF) theory for multinucleon transfer processes. Isotope production cross sections are evaluated for the reactions of 64 Ni + 208 Pb at E c.m. = 268 MeV and 58 Ni + 208 Pb at E c.m. = 270 MeV and are compared with available experimental data. Methods: Three-dimensional time-dependent Hartree-Fock (TDHF) calculations are carried out for a range of initial orbital angular momenta with Skyrme SLy4d functional. Quantal diffusion equations, derived based on the SMF theory, for variances and covariance of neutron and proton numbers of reaction products are solved, with microscopic drift and diffusion coefficients obtained from time evolution of occupied single-particle orbitals in TDHF. Secondary de-excitation processes, both particle evaporation and fission, are simulated by a statistical compound-nucleus de-excitation model, gemini++. Dynamics of a fast isospin equilibration process followed by a slow drift toward the mass symmetry are commonly observed, as expected. Various reaction outcomes are evaluated, including average mass and charge numbers of reaction products, total kinetic energy loss (TKEL), scattering angle, contact time, and production cross sections for primary and secondary products. By comparing with the experimental data, we find that SMF and TDHF quantitatively reproduce experimental data for few-nucleon-transfer channels around the average values. In contrast, for many-nucleon-transfer channels, we find that the SMF approach provides much better description of the experimentally measured isotopic distributions. The results underline the importance of beyond-mean-field effects, especially one-body (mean-field) fluctuations and correlations, in describing multinucleon transfer processes. Moreover, through a combined analysis of SMF with a statistical model, gemini++, we find a significant contribution of transfer-induced fission, which is consistent with the experimental observation. In some cases, the SMF approach overestimates the isotopic width, requiring further improvements of the theoretical description. Possible ways to improve the description are discussed. The SMF approach is designed to describe the quantum many-body problem according to an ensemble of mean-field trajectories, taking into account part of many-body correlations in the description. As it requires feasible computational costs comparable to the ordinary TDHF approach, together with further model improvements, it will be a promising tool in the search for optimal reaction conditions to produce yet-unknown neutron-rich heavy nuclei through the multinucleon transfer reaction.
Demand-Side Management (DSM) is an essential tool to ensure power system reliability and stability. In future smart grids, certain portions of a customer’s load usage could be under the automatic control of a cyber-enabled DSM program, which selectively schedules loads as a function of electricity prices to improve power balance and grid stability. In this scenario, the security of DSM cyberinfrastructure will be critical as advanced metering infrastructure and communication systems are susceptible to cyber-attacks. Such attacks, in the form of false data injections, can manipulate customer load profiles and cause metering chaos and energy losses in the grid. The feedback mechanism between load management on the consumer side and dynamic price schemes employed by independent system operators can further exacerbate attacks. To study how this feedback mechanism may worsen attacks in future cyber-enabled DSM programs, we propose a novel mathematical framework for (i) modeling the nonlinear relationship between load management and real-time pricing, (ii) simulating residential load data and prices, (iii) creating cyber-attacks, and (iv) detecting said attacks. In this framework, we first develop time-series forecasts to model load demand and use them as inputs to an elasticity model for the price-demand relationship in the DSM loop. This work then investigates the behavior of such a feedback loop under intentional cyber-attacks. We simulate and examine load-price data under different DSM-participation levels with three types of random additive attacks: ramp, sudden, and point attacks. We conduct two investigations for the detection of DSM attacks. The first studies a supervised learning approach, with various classification models, and the second studies the performance of parametric and nonparametric change point detectors. Results conclude that higher amounts of DSM participation can exacerbate ramp and sudden attacks leading to better detection of such attacks, especially with supervised learning classifiers. We also find that nonparametric detection outperforms parametric for smaller user pools, and random point attacks are the hardest to detect with any method.
High-performance indoor organic photovoltaics (IOPV) require large-bandgap material systems to absorb visible light efficiently and reduce energy loss. However, state-of-the-art non-fullerene acceptors (NFAs) have absorptions in the near-infrared region and are thus not suitable for IOPV applications. Herein, we report a series of large-bandgap (>1.70 eV) NFAs named FCC-Cl-C8, FCC-Cl-4Ph and FCC-Cl-6Ph by modifying the alkyl side chains with alkylphenyl chains partially or completely. Results show that the bulky alkylphenyl side chains can finely tune the absorption properties of the NFAs and also affect their morphological properties. Interestingly, the best-performing NFA is the one (named FCC-Cl-4Ph) with partial alkyl and alkylphenyl substitutions, which blue-shift the absorption of the NFAs while minimizing the negative morphological effect of the bulky alkylphenyl chains. As a result, FCC-Cl-4Ph can achieve excellent indoor efficiencies over 29% under a 3000 K LED lamp at 1000 lux and show better solution processability over FCC-Cl-C8. More importantly, FCC-Cl-4Ph can maintain high indoor performance (29.7–26.8% at 1000 lux) under a wide range of indoor lighting spectra (2600, 3000, 4000, and 6500 K LED lamps), which should be due to the blue-shifted spectra of FCC-Cl-4Ph and better matching with various indoor conditions. Finally, this work reveals an interesting structure-property relationship and offers useful strategies for the further design of NFAs toward efficient IOPV devices.
The Muon g-2 Experiment at Fermilab uses a gaseous straw tracking detector to make detailed measurements of the stored muon beam profile, which are essential for the experiment to achieve its uncertainty goals. Positrons from muon decays spiral inward and pass through the tracking detector before striking an electromagnetic calorimeter. The tracking detector is therefore located inside the vacuum chamber in a region where the magnetic field is large and non-uniform. As such, the tracking detector must have a low leak rate to maintain a high-quality vacuum, must be non-magnetic so as not to perturb the magnetic field and, to minimize energy loss, must have a low radiation length. The performance of the tracking detector has met or surpassed the design requirements, with adequate electronic noise levels, an average straw hit resolution of (110 ± 20) μm, a detection efficiency of 97% or higher, and no performance degradation or signs of aging. The tracking detector's measurements result in an otherwise unachievable understanding of the muon's beam motion, particularly at early times in the experiment's measurement period when there are a significantly greater number of muons decaying. This is vital to the statistical power of the experiment, as well as facilitating the precise extraction of several systematic corrections and uncertainties. This paper describes the design, construction, testing, commissioning, and performance of the tracking detector.
We report on the first search for nuclear ultraheavy dark matter (UHDM) in a dual-phase liquid argon time projection chamber using the DarkSide-50 experiment. Unlike conventional weakly interacting massive particles, a nuclear UHDM model may be composed of many dark nucleons and scatter numerous times while passing through the detector. Accounting for energy loss through the Earth’s overburden, we apply selection criteria optimized for multiscatter event topologies using the 532-day low-radiation campaign of the DarkSide-50 detector. Excluded limits on the UHDM-nucleon scattering cross section for dark nucleon masses of m χ = 10 , 50 , 100 , 500 GeV / c 2 are presented.
Despite significant advancements in fenestration technology in the last two decades, the thermal transmittance of fenestration products is still significantly higher than that of walls. This corresponds to 60% of the total energy loss of a modern building envelope through the windows. Hence, further development and improvements of fenestration products are necessary. Increasingly stringent codes and standards for fenestration stimulate industry to work on improved solutions. Thus, it is crucial that assessment techniques are able to account for innovations accurately. The thermal effects of non-continuous hardware in window frames are currently ignored by international rating procedures. A preliminary investigation conducted by our team showed significant performance degradation in two of the three out-opening casement profiles caused by the presence of operating hardware. Frames with the structure made of vinyl and fiberglass consist of many air cavities that are penetrated by operating hardware made of highly conductive materials. In these frames, in order to have an accurate assessment, it may be required to employ three-dimensional modeling due to the convective nature of heat transfer within the cavities. However, in this study, we demonstrate that the three-dimensional (3D) effects of non-continuous hardware can be approximated accurately with simpler two-dimensional (2D) simulations. We then develop a simplified model based on weighted average capable of replacing the time- and computation-intensive 3D simulations with 2D simulations and validate it against market available frames and their corresponding hardware. Validation results show that our approximation technique results in discrepancies lower than 0.05 W/(m2K), or 3% of the total thermal transmittance. Thus, we conclude that simplified 2D simulation models may be used for predicting hardware impact in window frames with reasonable accuracy. As windows and glazing structures are becoming ever better thermally insulated, it is becoming even more important to be able to model the impact of the operating hardware on the total thermal performance in order to design the best windows possible and not let the operating hardware ruin an otherwise well-proven design, which is hence addressed in this study.
In this article, elevated temperature molten Na batteries are seeing a resurgence of interest for low-cost electrochemical energy storage for the grid. Of the many recent innovations in this battery concept, new methods focused on intermediate temperature operation (e.g. 110–190 °C) have gained prominence as a way to enable comparable performance with less thermal energy loss and lower-cost materials of construction. However, the poor wettability of molten Na on suitable solid-electrolyte separators such as sodium Beta Alumina Solid-Electrolyte (Na-β”-Al 2 O 3 , ‘BASE’) requires continued innovation in interface engineering to promote full utilization of the solid-electrolyte surface area and minimize cell resistance. There have been many successful approaches to improve Na-wettability to-date including heat treatment in an inert atmosphere to remove adsorbed surface species, deposition of alloying metals such as Pb, Sn, or Bi, and use of carbon-based interfacial layers. However, these approaches either lack the ability to provide good wetting at very low temperatures (near the melting point of Na) or rely on non-scalable processes and/or toxic/expensive metals. To solve these issues, a new carbon-based sodiophilic treatment is demonstrated, which utilizes inexpensive components to form a meso/macroporous sodiophilic layer, is easily applied via drop-casting or spray-coating, provides excellent wetting as low as 110 °C, and is completely metal-free. It is found that the good sodium wetting can be attributed to the wider range of pore sizes in the carbon layers demonstrated in this study. Na wetting may occur as surface tension is initially broken by larger pores, followed by the intrusion of molten Na into smaller pores due to the apparent intrinsic affinity of Na-metal for carbon surfaces, in conjunction with the capillarity effect. Low cell-level area specific resistances of 20–30 and 13–15 Ω·cm 2 are demonstrated at 110 and 140 °C respectively. Finally, the utility of this metal-free wetting layer for solid-Na anodes is explored, showing that the metal-free wetting layer can reach a critical current density of 1.88 mA·cm -2 at 30 °C.
Significant demand for lithium-ion batteries necessitates alternatives to Co- and Ni-based cathode materials. Cation-disordered materials using earth-abundant elements are being explored as promising candidates. Here, in this paper, we demonstrate a coprecipitation synthetic approach that allows direct preparation of disordered rocksalt Li 2.4 Fe 1.0 Ti 1.0 O 4.7 (r-LFTO·C) and spinel structured hybrid Li 0.5 Fe 1.0 Ti 0.9 O 3.2 ·C (s-LFTO·C) nanoparticles with a conformal conductive carbon coating. High-angle annular dark-field imaging coupled with electron energy loss spectroscopy mapping shows uniform Fe/Ti distribution with minor compositional variation among particles. Cation disorder was confirmed for both of the materials at an atomic level, with a short-range order more pronounced in r-LFTO·C. Operando X-ray absorption spectroscopy, ex situ hard X-ray photoelectron spectroscopy, ex situ soft X-ray absorption spectroscopy, and ex situ synchrotron X-ray diffraction were used to investigate (de)lithiation in the bulk and at the surface. Structurally, the r-LFTO·C demonstrated reversible partial Fe center migration between octahedral and tetrahedral sites during (de)lithiation. The r-LFTO·C evidenced that the redox of O was coincident with iron redox during initial electrochemical cycling, while iron redox dominated later cycling. In contrast, s-LFTO·C electrochemistry involved iron redox throughout the cycling process. The findings rationalize the differences in the electrochemistry where r-LFTO·C shows higher initial capacity yet poorer capacity retention over a voltage window where O redox can be accessed, while the s-LFTO·C shows lower initial capacity yet improved capacity retention.
We present a study directly measuring the electron-beam-induced plasticity of amorphous Al 2 O 3 coatings. Core–shell nanostructures are employed as small-scale model systems for two-dimensional coatings made by atomic layer deposition (ALD). Copper nanowires (NWs) are used as substrates for ALD deposition, representing a model system for interconnects commonly found in integrated circuits. Experiments are performed in situ in a transmission electron microscope (TEM) and further analyzed with electron energy loss spectroscopy (EELS). Our in situ TEM tensile experiments reveal the highly plastic behavior of the ALD shell, which withstands a maximum strain of 188%. Comparable samples under beam-off conditions show a brittle fracture, which underlines the effect of electron irradiation. The electron-beam-activated bond switching within the amorphous network enables compensation of the applied tensile strain, leading to viscous flow. By incorporating an intermediate nanocrystalline layer within the Al 2 O 3 shell, the plasticity is suppressed and brittle fracture occurs. This work directly demonstrates the tuning of mechanical properties in amorphous ALD structures through electron irradiation.
Novel confinement techniques facilitate the formation of non-layered 2D materials. Here it is demonstrated that the formation and properties of 2D oxides (GaO x , InO x , SnO x ) at the epitaxial graphene (EG)/silicon carbide (SiC) interface is dependent on the EG buffer layer properties prior to element intercalation. Using 2D Ga, it is demonstrated that defects in the EG buffer layer lead to Ga transforming to GaO x with non-periodic oxygen in a crystalline Ga matrix via air oxidation at room temperature. However, crystalline monolayer GaO 2 and bilayer Ga 2 O 3 with ferroelectric wurtzite structure(FE-WZ') can then be formed via subsequent high-temperature O 2 annealing. Furthermore, the graphene/X/SiC (X = 2D Ga or Ga 2 O 3 ) junction is tunable from Ohmic to a Schottky or tunnel barrier depending on the interface species. Finally, using vertical transport measurements and electron energy loss spectroscopy analysis, the bandgap of 2D gallium oxide is identified as 6.6 ± 0.6 eV, significantly larger than that of bulk β-Ga 2 O 3 (≈4.8 eV), suggesting strong quantum confinement effects at the 2D limit. Furthermore, the study presented here is foundational for development of atomic-scale, vertical 2D/3D heterostructure for applications requiring short transit times, such as GHz and THz devices.
The molecular conformation of giant molecule acceptors (GMAs) plays a significant role in regulating the intermolecular interactions and their photovoltaic performances in organic solar cells (OSCs). For the linear GMA GT‐l, the stronger homo‐molecular interaction causes its aggregation being weakly affected by the donor, thus forming an ordered molecular stacking and proper phase separation in its blend film. The star‐shaped GMA GT‐s‐based blend film shows a dominant hetero‐molecular interaction that suppresses the aggregation of the donor and acceptor, resulting in smaller phase separation and more uniform vertical phase distribution. While for another star‐shaped GMA GTs, the weakest hetero‐molecular interaction causes its blend film to form larger phase separation. Therefore, the GT‐l based OSC with PM6 as donor shows the highest charge mobilities, the fastest charge transfer (CT) process, reduced energy loss and less charge recombination, contributing to a higher power conversion efficiency (PCE) of 19.03%. Comparatively, the PCEs of the OSCs based on GTs and GT‐s are 18.05% and 17.58% respectively. Notably, all the three GMAs based OSCs show excellent thermal stability and long‐term storage stability. This study provides a facile strategy by tuning the linking unit and its connecting mode for designing highly efficient and stable organic photovoltaic materials.
Breaking time-reversal symmetry by introducing magnetic order, thereby opening a gap in the topological surface state bands, is essential for realizing useful topological properties such as the quantum anomalous Hall and axion insulator states. In this work, a novel topological antiferromagnetic (AFM) phase is created at the interface of a sputtered, c-axis-oriented, topological insulator/ferromagnet heterostructure—Bi 2 Te 3 /Ni 80 Fe 20 because of diffusion of Ni in Bi 2 Te 3 (Ni-Bi 2 Te 3 ). The AFM property of the Ni-Bi2Te3 interfacial layer is established by observation of spontaneous exchange bias in the magnetic hysteresis loop and compensated moments in the depth profile of the magnetization using polarized neutron reflectometry. Analysis of the structural and chemical properties of the Ni-Bi2Te3 layer is carried out using selected-area electron diffraction, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. These studies, in parallel with first-principles calculations, indicate a solid-state chemical reaction that leads to the formation of Ni=Te bonds and the presence of topological antiferromagnetic (AFM) compound NiBi 2 Te 4 in the Ni-Bi 2 Te 3 interface layer. The Neél temperature of the Ni-Bi 2 Te 3 layer is ≈ 63 K, which is higher than that of typical magnetic topological insulators (MTIs). The presented results provide a pathway toward industrial complementary metal-oxide-semiconductor (CMOS)-process-compatible sputtered-MTI heterostructures, leading to novel materials for topological quantum devices.
Abstract Grain boundaries (GBs) are a prolific microstructural feature that dominates the functionality of a wide class of materials. The functionality at a GB results from the unique atomic arrangements, different from those in the grain, that have driven extensive experimental and theoretical studies correlating atomic‐scale GB structures to macroscopic electronic, infrared optical, and thermal properties. In this work, a SrTiO 3 GB is examined using atomic‐resolution aberration‐corrected scanning transmission electron microscopy and ultrahigh‐energy‐resolution monochromated electron energy‐loss spectroscopy, in conjunction with density functional theory. This combination enables the correlation of the GB structure, nonstoichiometry, and chemical bonding with a redistribution of vibrational states within the GB dislocation cores. The new experimental access to localized GB vibrations provides a direct route to quantifying the impact of individual boundaries on macroscopic properties.
Constructing tandem and multi-blend organic solar cells (OSCs) is an effective way to overcome the absorption limitations of conventional single-junction devices. However, these methods inevitably require tedious multilayer deposition or complicated morphology-optimization procedures. Herein, sequential deposition is utilized as an effective and simple method to fabricate multicomponent OSCs with a double-bulk heterojunction (BHJ) structure of the active layer to further improve photovoltaic performance. Two efficient donor-acceptor pairs, D18-Cl:BTP-eC9 and PM6:L8-BO, are sequentially deposited to form the D18-Cl:BTP-eC9/PM6:L8-BO double-BHJ active layer. In these double-BHJ OSCs, light absorption is significantly improved, and optimal morphology is also retained without requiring a more complicated morphology optimization involved in quaternary blends. Compared to the quaternary blend devices, energy loss (E loss ) is also reduced by rationally matching each donor with an appropriate acceptor. Consequently, the power conversion efficiency (PCE) is improved from 18.25% for D18-Cl:BTP-eC9 and 18.69% for PM6:L8-BO based binary blend OSCs to 19.61% for the double-BHJ OSCs. In contrast, a D18-Cl:PM6:L8-BO:BTP-eC9 quaternary blend of OSCs exhibited a dramatically reduced PCE of 15.83%. Finally, these results demonstrate that a double-BHJ strategy, with a relatively simple processing procedure, can potentially enhance the device performance of OSCs and lead to more widespread use.
Organic photovoltaics (OPVs) based on non-fullerene acceptors (NFAs) have achieved a power conversion efficiency close to 20%. These NFA OPVs can generate free carriers efficiently despite a very small energy level offset at the donor/acceptor interface. Why these NFAs can enable efficient charge separation (CS) with low energy losses remains an open question. Here, the CS process in the PM6:Y6 bulk heterojunction is probed by time-resolved two-photon photoemission spectroscopy. It is found that the CS, the conversion from bound charge transfer (CT) excitons to free carriers, is an endothermic process with an enthalpy barrier of 0.15 eV. The CS can occur spontaneously despite being an endothermic process, which implies that it is driven by entropy. It is further argued that the morphology of the PM6:Y6 film and the anisotropic electron delocalization restrict the electron and hole wavefunctions within the CT exciton such that they can primarily contact each other through point-like junctions. Furthermore, this configuration can maximize the entropic driving force.
Abstract Inorganic–organic hybrid MXenes (h‐MXenes) are a family of 2D transition metal carbides and nitrides functionalized with alkylimido and alkylamido surface groups. Using cryogenic and room temperature scanning transmission electron microscopy (STEM) and electron energy‐loss spectroscopy (EELS), it is shown that ripplocations, a form of a fundamental defect in 2D and layered structures, are abundant in this family of materials. Furthermore, detailed studies of electron probe sample interactions, focusing on structural deformations caused by the electron beam are presented. The findings indicate that at cryogenic temperatures (≈100 K) and below a specific dose threshold, the structure of h‐MXenes remains largely intact. However, exceeding this threshold leads to electron beam‐induced deformation through ripplocations. Interestingly, the deformation behavior, required dose, and resultant structure are highly dependent on temperature. At 100 K, it is demonstrated that the electron beam can induce ripplocations in situ with a high degree of precision.
Understanding the atomic structure of quantum emitters, often originating from point defects or impuritie, is essential for designing and optimizing materials for quantum technologies such as quantum computing, communication, and sensing. Despite the availability of atomic-resolution scanning transmission electron microscopy and nanoscale cathodoluminescence microscopy, experimentally determining the atomic structure of individual emitters is challenging due to the conflicting needs for thick samples to generate strong cathodoluminescence signals and thin samples for structural analysis. To overcome this challenge, significantly enhanced cathodoluminescence at twisted interfaces is leveraged to achieve sub-nanometer localization precision for the first time in mapping individual quantum emitters in carbon-implanted hexagonal boron nitride. This unprecedent spatial sensitivity, together with correlative electron energy loss spectroscopy quantitative scanning transmission electron microscopy imaging, and first principles density functional theory calculations, enables the identification of the atomic structure of the 440 nm blue emitter in hexagonal boron nitride as a substituted vertical carbon dimer. Building on the atomic structure insights, nanoscale spatially precise creation of blue emitters is demonstrated by electron beam irradiation of carbon-coated hexagonal boron nitride. This advancement in correlating atomic structures with optical properties lays the foundation for a deeper understanding and precise engineering of quantum emitters, significantly advancing the development of cutting-edge quantum information technologies.