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At least 343 records · Page 19

Ion-driven instabilities in the solar wind: Wind observations of 19 March 2005

Intervals of enhanced magnetic fluctuations have been frequently observed in the solar wind. However, it remains an open question as to whether these waves are generated at the Sun and then transported outward by the solar wind or generated locally in the interplanetary medium. Magnetic field and plasma measurements from the Wind spacecraft under slow solar wind conditions on 19 March 2005 demonstrate seven events of enhanced magnetic fluctuations at spacecraft-frame frequencies somewhat above the proton cyclotron frequency and propagation approximately parallel or antiparallel to the background magnetic field B o . The proton velocity distributions during these events are characterized by two components: a more dense, slower core and a less dense, faster beam. In conclusion, observed plasma parameters are used in a kinetic linear dispersion equation analysis for electromagnetic fluctuations at k x B o = 0; for two events the most unstable mode is the Alfvén-cyclotron instability driven by a proton component temperature anisotropy T ⊥ /T || > 1 (where the subscripts denote directions relative to B o ), and for three events the most unstable mode is the right-hand polarized magnetosonic instability driven primarily by ion component relative flows. Thus, both types of ion anisotropies and both types of instabilities are likely to be local sources of these enhanced fluctuation events in the solar wind.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Morphology of a Ternary Blend Solar Cell Based on Small Molecule:Conjugated Polymer:Fullerene Fabricated by Blade Coating

Abstract Here, conjugated polymer is added as third component to tune the solution viscosity, morphology, and function of small molecule (SM) based bulk‐heterojunction (BHJ) solar cells, which are fabricated using blade coating. Novel information about the effect of blade coating speed on the nanoscale morphology and function of ternary blend solar cells is provided. The crystal sizes increase with an increase of coating speed for both binary and ternary blends, while the addition of the third component tends to favor smaller SM crystal grains and improves the connectivity of SM crystals. Small angle neutron scattering experiments provide the first clear experimental evidence that the addition of the third component would significantly impact the fullerene phase separation, which is crucial for bimolecular recombination and charge transport. It shows that for both binary and ternary blends, the concentration and sizes of [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) aggregates increase with an increase of coating speed, while addition of third component does not affect the volume fraction of PCBM aggregates but impacts the size of PCBM aggregates. It is demonstrated that the judicious selection of blade coating speed and addition of conjugated polymer optimize the morphology of SM‐BHJ, providing guidelines for high performance SM‐BHJs from roll‐to‐roll production.

Wu, Xiaomin↗

Unravelling the Role of Electron Acceptors for the Universal Enhancement of Charge Transport in Quinoid-Donor-Acceptor Polymers for High-Performance Transistors

The quinoid-donor-acceptor (Q-D-A) strategy has recently emerged as a promising approach for constructing high mobility semiconducting polymers. In order to fully explore the potential of this strategy in improving the charge transport and elucidating the structure-property-performance relationships in Q-D-A polymers, a series of new polymers with different electron acceptor units and backbone coplanarity have been synthesized and characterized. In this work, all of the resulting Q-D-A polymers exhibit much more planar backbone conformations in comparison to their donor-acceptor (D-A) counterparts. Moreover, organic field-effect transistors based on Q-D-A polymers exhibit excellent effective hole mobilities in a range of 0.44 to 3.35 cm 2 V –1 s –1 , most of which are orders of magnitude higher than those of their corresponding D-A polymers. Notably, the hole mobility of 3.35 cm 2 V –1 s –1 is among the highest for the quinoidal-aromatic polymers characterized by conventional spin-coating methods. Furthermore, the role of electron acceptors in Q-D-A polymers has been comprehensively investigated. Polymers with stronger acceptor units are more inclined to deliver edge-on lamellas, high film crystallinity, small effective hole masses, and decent operational stability. The detailed structure-property-device performance relationship will pave the way toward high performance semiconducting polymers using the potent Q-D-A strategy.

36 MATERIALS SCIENCE↗

Superhydrophobic Phosphonium Modified Robust 3D Covalent Organic Framework for Preferential Trapping of Charge Dispersed Oxoanionic Pollutants

Abstract Charge dispersed and less hydrophilic anionic pollutants are often difficult to be preferentially captured by common cationic framework materials. A gamma radiation modification approach is employed to anchor a superhydrophobic phosphonium‐containing coating on a robust crystalline 3D covalent organic framework (COF). By regulating the surface hydrophobicity, the prepared 3DCOF‐ g ‐VBPPh 3 Cl is endowed with a strong affinity for charge dispersed and less hydrophilic oxoanions, such as MnO 4 − , TcO 4 − and ReO 4 − , to surmount the Hofmeister bias, which much favors remediation of oxoanionic pollutants in complex aqueous systems. Batch and column experiments with 3DCOF‐g‐VBPPh 3 Cl in both tap water and simulated groundwater are performed, and rapid sequestration is achieved with removal efficacy up to 99.995%, record‐high distribution coefficient of 1.0 × 10 8 mL g −1 , and desirable priority over competing anions such as Cl − , SO 4 2− , HCO 3 − , and NO 3 − , confirming promise for remediation of charge dispersed anionic pollutants. Theoretical calculations reveal a mechanism of preferential capture based on electrostatic and dispersion interaction between charge dispersed anions and 3DCOF‐g‐VBPPh 3 Cl that effectively competes with solvation of the aqueous anions.

Wang, Yue↗

Zinc‐Imidazolate Films as an All‐Dry Resist Technology

Here, motivated by the drawbacks of solution phase processing, an all‐dry resist formation process is presented that utilizes amorphous zinc‐imidazolate (aZnMIm) films deposited by atomic/molecular layer deposition (ALD/MLD), patterned with electron beam lithography (EBL), and developed by novel low temperature (120 °C) gas phase etching using 1,1,1,5,5,5‐hexafluoroacetylacetone (hfacH) to achieve well‐resolved 22 nm lines with a pitch of 30 nm. The effects of electron beam irradiation on the chemical structure and hfacH etch resistance of aZnMIm films are investigated, and it is found that electron irradiation degrades the 2‐methylimidazolate ligands and transforms aZnMIm into a more dense material that is resistant to etching by hfacH and has a C:N:Zn ratio effectively identical to that of unmodified aZnMIm. These findings showcase the potential for aZnMIm films to function in a dry resist technology. Sensitivity, contrast, and critical dimensions of the patterns are determined to be 37 mC cm −2 , 0.87, and 29 nm, respectively, for aZnMIm deposited on silicon substrates and patterned at 30 keV. This work introduces a new direction for solvent‐free resist processing, offering the prospect of scalable, high‐resolution patterning techniques for advanced semiconductor fabrication processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High‐Pressure Synthesis of Ultra‐Incompressible, Hard and Superconducting Tungsten Nitrides

Abstract Transition metal nitrides, particularly those of 5 d metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high‐pressure investigation of the W–N system, two novel ultra‐incompressible tungsten nitride superconductors, namely W 2 N 3 and W 3 N 5 , are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N 2 and W in laser‐heated diamond anvil cells. Their crystal structure is determined using synchrotron single‐crystal X‐ray diffraction. While the W 2 N 3 solid's sole constituting nitrogen species are N 3‐ units, W 3 N 5 features both discrete N 3‐ as well as N 2 4‐ pernitride anions. The bulk modulus of W 2 N 3 and W 3 N 5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra‐incompressible behavior is rationalized by their constituting WN 7 polyhedra and their linkages. Importantly, both W 2 N 3 and W 3 N 5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W 2 N 3 and W 3 N 5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W 2 N 3 corroborate with the calculations.

Chemistry↗

Impact of Linker Engineering in Core‐Linked Dimeric Acceptors for High‐Performance Organic Solar Cells

Abstract The dimerization of small molecule acceptors (SMAs) is a promising strategy for enhancing the long‐term stability and power conversion efficiency (PCE) of organic solar cells (OSCs). However, the reported DSMAs are primarily limited to end‐linked molecular configurations, highlighting the need for further exploration of various dimer architectures. Herein, the development of two distinct core‐linked dimerized SMAs (DYF‐V and DYF‐E) are reported with tailored linker structures (vinylene and ethynyl, respectively), achieving high‐performance OSCs (PCE = 18.53%). Interestingly, a subtle change in the linker structures results in markedly different molecular properties and photovoltaic performances of the dimer acceptors. DYF‐E with an ethynyl linker exhibits more twisted backbone conformation and mitigated aggregation property compared to DYF‐V, inducing desirable blend morphologies with a polymer donor including high crystallinity, face‐on oriented packing structures, and well‐intermixed domains. Thus, the DYF‐E‐based OSCs exhibit a high PCE (17.02%), which significantly outperforms the DYF‐V‐based OSCs (PCE = 9.98%). Furthermore, the ternary OSCs based on DYF‐E achieve a higher PCE of 18.53%. Thus, this study highlights the significance of selecting an appropriate linker in core‐linked dimerized SMAs for producing high‐performance OSCs.

Oh, Shinbee↗

Designing a Zn–Ag Catalyst Matrix and Electrolyzer System for CO 2 Conversion to CO and Beyond

CO 2 emissions can be transformed into high-added-value commodities through CO 2 electrocatalysis; however, efficient low-cost electrocatalysts are needed for global scale-up. Inspired by other emerging technologies, the authors report the development of a gas diffusion electrode containing highly dispersed Ag sites in a low-cost Zn matrix. Here, this catalyst shows unprecedented Ag mass activity for CO production: –614 mA cm –2 at 0.17 mg of Ag. Subsequent electrolyte engineering demonstrates that halide anions can further improve stability and activity of the Zn–Ag catalyst, outperforming pure Ag and Au. Membrane electrode assemblies are constructed and coupled to a microbial process that converts the CO to acetate and ethanol. Combined, these concepts present pathways to design catalysts and systems for CO 2 conversion toward sought-after products.

36 MATERIALS SCIENCE↗

Topological Crystalline Insulator Candidate ErAsS with Hourglass Fermion and Magnetic-Tuned Topological Phase Transition

Topological crystalline insulators (TCIs) with hourglass fermion surface state have attracted a lot of attention and are further enriched by crystalline symmetries and magnetic order. Here, the emergence of hourglass fermion surface state and exotic phases in the newly discovered, air-stable ErAsS single crystals are shown. In the paramagnetic phase, ErAsS is expected to be a TCI with hourglass fermion surface state protected by the nonsymmorphic symmetry. Dirac-cone-like bands and nearly linear dispersions in large energy range are experimentally observed, consistent well with theoretical calculations. Below T N ≈ 3.27 K, ErAsS enters a collinear antiferromagnetic state, which is a trivial insulator breaking the time-reversal symmetry. An intermediate incommensurate magnetic state appears in a narrow temperature range (3.27–3.65 K), exhibiting an abrupt change in magnetic coupling. Overall, the results reveal that ErAsS is an experimentally available TCI candidate and provide a unique platform to understand the formation of hourglass fermion surface state and explore magnetic-tuned topological phase transitions.

36 MATERIALS SCIENCE↗

High‐Efficiency Magnon‐Mediated Magnetization Switching in All‐Oxide Heterostructures with Perpendicular Magnetic Anisotropy

Abstract The search for efficient approaches to realize local switching of magnetic moments in spintronic devices has attracted extensive attention. One of the most promising approaches is the electrical manipulation of magnetization through electron‐mediated spin torque. However, the Joule heat generated via electron motion unavoidably causes substantial energy dissipation and potential damage to spintronic devices. Here, all‐oxide heterostructures of SrRuO 3 /NiO/SrIrO 3 are epitaxially grown on SrTiO 3 single‐crystal substrates following the order of the ferromagnetic transition metal oxide SrRuO 3 with perpendicular magnetic anisotropy, insulating and antiferromagnetic NiO, and metallic transition metal oxide SrIrO 3 with strong spin–orbit coupling. It is demonstrated that instead of the electron spin torques, the magnon torques present in the antiferromagnetic NiO layer can directly manipulate the perpendicular magnetization of the ferromagnetic layer. This magnon mechanism may significantly reduce the electron motion‐related energy dissipation from electron‐mediated spin currents. Interestingly, the threshold current density to generate a sufficient magnon current to manipulate the magnetization is one order of magnitude smaller than that in conventional metallic systems. These findings suggest a route for developing highly efficient all‐oxide spintronic devices operated by magnon current.

Zheng, Dongxing↗

Stabilizing the Deep Sodiation Process in Layered Sodium Manganese Cathodes by Anchoring Boron Ions

Advanced high-energy-density sodium-ion batteries (SIBs) are inseparable from cathode materials with high specific capacities. Layered manganese-rich oxides (Na x MnO 2 , 0.6 ≤ x ≤1) are promising cathode materials owing to their ease of intercalation and extraction of a considerable amount of sodium ions. However, lattice interactions, especially electrostatic repulsive forces and anisotropic stresses, are usually caused by deep desodiatin/sodiation process, resulting in intragranular cracks and capacity degradation in SIBs. Here, boron ions are introduced into the layered structure to build up B-O-Mn bonds. Further, the regulated electronic structure in Na 0.637 B 0.038 MnO 2 (B-NMO) materials inhibits the deformation of MnO 6 octahedra, which finally achieves a gentle structural transition during the deep sodiation process. B-NMO electrode exhibits a high capacity (141 mAh g –1 ) at 1 C with a capacity retention of 81% after 100 cycles. Therefore, anchoring boron to manganese-rich materials inhibits the detrimental structural evolution of deep sodiation and can be used to obtain excellent cathode materials for SIBs.

25 ENERGY STORAGE↗

Broadband Metamaterial Absorbers

The recent rise of metamaterials opens new opportunities for absorbers due to their designed electrodynamic properties and effects, allowing the creation of materials with effective values of permittivity and permeability that are not available in naturally occurring materials. Since their first experimental demonstration in 2008, recent literature has offered great advances in metamaterial perfect absorbers (MMPAs) operating at frequencies from radio to optical. Broadband absorbers are indispensable in thermophotovoltaics, photodetection, bolometry, and manipulation of mechanical resonances. Although it is easy to obtain MMPAs with single band or multiband, achieving broadband MMPA (BMMPA) remains a challenge due to the intrinsically narrow bandwidth of surface plasmon polaritons, localized surface plasmon resonances generated on metallic surfaces at nanoscale or high Q-factor in GHz region. To guide future development of BMMPA, recent progress is reviewed here: the methods to create broadband absorption and their potential applications. The four mainstream methods to achieve BMMPAs are introduced, including planar and vertical element arrangements, their welding with lumped elements and the use of plasmonic nanocomposites, accompanied by the description of other, less common approaches. Following this, applications of BMMPA in solar photovoltaics, photodetection, bolometry, and manipulation of mechanical resonances are reviewed. Finally, challenges and prospects are discussed.

36 MATERIALS SCIENCE↗

Boron Substituted Na 3 V 2 (P 1 -x B x O 4 ) 3 Cathode Materials with Enhanced Performance for Sodium-Ion Batteries

The development of excellent performance of Na-ion batteries remains great challenge owing to the poor stability and sluggish kinetics of cathode materials. Herein, B substituted Na 3 V 2 P 3–x B x O 12 (0 ≤ x ≤ 1) as stable cathode materials for Na-ion battery is presented. A combined experimental and theoretical investigations on Na 3 V 2 P 3–x B x O 12 (0 ≤ x ≤ 1) are undertaken to reveal the evolution of crystal and electronic structures and Na storage properties associated with various concentration of B. X-ray diffraction results indicate that the crystal structure of Na 3 V 2 P 3–x B x O 12 (0 ≤ x ≤ 1/3) consisted of rhombohedral Na 3 V 2 (PO 4 ) 3 with tiny shrinkage of crystal lattice. X-ray absorption spectra and the calculated crystal structures all suggest that the detailed local structural distortion of substituted materials originates from the slight reduction of V–O distances. Na 3 V 2 P 3-1/6 B 1/6 O 12 significantly enhances the structural stability and electrochemical performance, giving remarkable enhanced capacity of 100 and 70 mAh g -1 when the C-rate increases to 5 C and 10 C. Spin-polarized density functional theory (DFT) calculation reveals that, as compared with the pristine Na 3 V 2 (PO 4 ) 3 , the superior electrochemical performance of the substituted materials can be attributed to the emergence of new boundary states near the band gap, lower Na + diffusion energy barriers, and higher structure stability.

36 MATERIALS SCIENCE↗

Unblocking Oxygen Charge Compensation for Stabilized High‐Voltage Structure in P2‐Type Sodium‐Ion Cathode

Abstract Layered transition‐metal (TM) oxides are ideal hosts for Li + charge carriers largely due to the occurrence of oxygen charge compensation that stabilizes the layered structure at high voltage. Hence, enabling charge compensation in sodium layered oxides is a fascinating task for extending the cycle life of sodium‐ion batteries. Herein a Ti/Mg co‐doping strategy for a model P2‐Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode material is put forward to activate charge compensation through highly hybridized O 2 p TM 3 d covalent bonds. In this way, the interlayer OO electrostatic repulsion is weakened upon deeply charging, which strongly affects the systematic total energy that transforms the striking P2–O2 interlayer contraction into a moderate solid‐solution‐type evolution. Accordingly, the cycling stability of the codoped cathode material is improved superiorly over the pristine sample. This study starts a perspective way of optimizing the sodium layered cathodes by rational structural design coupling electrochemical reactions, which can be extended to widespread battery researches.

25 ENERGY STORAGE↗

Pathway Evolution Through a Bottlenecking-Debottlenecking Strategy and Machine Learning-Aided Flux Balancing

The evolution of pathway enzymes enhances the biosynthesis of high-value chemicals, crucial for pharmaceutical, and agrochemical applications. However, unpredictable evolutionary landscapes of pathway genes often hinder successful evolution. Here, the presence of complex epistasis is identifued within the representative naringenin biosynthetic pathway enzymes, hampering straightforward directed evolution. Subsequently, a biofoundry-assisted strategy is developed for pathway bottlenecking and debottlenecking, enabling the parallel evolution of all pathway enzymes along a predictable evolutionary trajectory in six weeks. This study then utilizes a machine learning model, ProEnsemble, to further balance the pathway by optimizing the transcription of individual genes. The broad applicability of this strategy is demonstrated by constructing an Escherichia coli chassis with evolved and balanced pathway genes, resulting in 3.65 g L -1 naringenin. The optimized naringenin chassis also demonstrates enhanced production of other flavonoids. This approach can be readily adapted for any given number of enzymes in the specific metabolic pathway, paving the way for automated chassis construction in contemporary biofoundries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Large-Area 2D/3D MoS 2 -MoO 2 Heterostructures with Thermally Stable Exciton and Intriguing Electrical Transport Behaviors

To date, scale-up fabrication of transition metal dichalcogenide (TMD-) based 2D/2D or 2D/3D heterostructures with specific functionalities is still a great challenge. This study, for the first time, reports on the controllable synthesis of large-area and continuous 2D/3D semiconductor/metal heterostructures consisting of monolayer MoS 2 and bulk MoO 2 with unique electrical and optical properties via one-step, vapor-transport-assisted rapid thermal processing. The temperature-dependent electrical transport measurements reveal that the 2D/3D MoS 2 –MoO 2 heterostructure grown on SiO 2 /Si substrates exhibits metallic phase, while this heterostructure becomes a low-resistance semiconductor when it is grown on fused silica, which is attributed to the different degrees of sulfurization on different substrates, as being confirmed by surface potential analyses. Photoluminescence measurements taken on the MoS 2 –MoO 2 heterostructures reveal the simultaneous presence of both negative trions and neutral excitons, while only neutral excitons are observed in the monolayer MoS 2 . The trion-binding energy is determined to be ≈27 meV, and the trion signal persists up to 330 K, indicating significant stability at room temperature. This work not only provides a new platform for understanding the intriguing physics in TMD-based heterostructures but also enables the design of more complicated devices with potential applications in nanoelectronics and nanophotonics.

36 MATERIALS SCIENCE↗

High Throughput Discovery of Solar Fuels Photoanodes in the CuO-V 2 O 5 System

Solar photoelectrochemical generation of fuel is a promising energy technology yet the lack of an efficient, robust photoanode remains a primary materials challenge in the development and deployment of solar fuels generators. Metal oxides comprise the most promising class of photoanode materials, but no known material meets the demanding requirements of low band gap energy, photoelectrocatalysis of the oxygen evolution reaction, and stability under highly oxidizing conditions. Here, we report the identification of new photoelectroactive materials through a strategic combination of combinatorial materials synthesis, high-throughput photoelectrochemistry, optical spectroscopy, and detailed electronic structure calculations. We identify 4 photoelectrocatalyst phases - α-Cu 2 V 2 O 7 , β-Cu 2 V 2 O 7 , γ-Cu 3 V 2 O 8 , and Cu 11 V 6 O 26 - with band gap energy at or below 2 eV. The photoelectrochemical properties and 30-minute stability of these copper vanadate phases are demonstrated in 3 different aqueous electrolytes (pH 7, pH 9, and pH 13), with select combinations of phase and electrolyte exhibiting unprecedented photoelectrocatalytic stability for metal oxides with sub-2 eV band gap. Through integration of experimental and theoretical techniques, we determine new structure-property relationships and establish CuO-V 2 O 5 as the most prominent composition system for OER photoelectrocatalysts, providing crucial information for materials genomes initiatives and paving the way for continued development of solar fuels photoanodes.

14 SOLAR ENERGY↗