Synthesis of Novel Phases in Si Nanowires Using Diamond Anvil Cells at High Pressures and Temperatures
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Complementary to bulk synthesis, here we propose a designer lattice with extremely high magnetic frustration and demonstrate the possible realization of a quantum spin liquid state from both experiments and theoretical calculations. In an ultrathin (111) CoCr 2 O 4 slice composed of three triangular and one kagome cation planes, the absence of a spin ordering or freezing transition is demonstrated down to 0.03 K, in the presence of strong antiferromagnetic correlations in the energy scale of 30 K between Co and Cr sublattices, leading to the frustration factor of similar to 1000. Persisting spin fluctuations are observed at low temperatures via low-energy muon spin relaxation. Our calculations further demonstrate the emergence of highly degenerate magnetic ground states at the 0 K limit, due to the competition among multiply altered exchange interactions. Furthermore, these results collectively indicate the realization of a proximate quantum spin liquid state on the synthetic lattice.
Understanding the behavior of high-entropy alloy (HEA) materials under hydrogen (H 2 ) environment is of utmost importance for their promising applications in structural materials, catalysis, and energy-related reactions. Herein, the reduction behavior of oxidized FeCoNiCuPt HEA nanoparticles (NPs) in atmospheric pressure H-2 environment was investigated by in situ gas-cell transmission electron microscopy (TEM). The reduction reaction front was maintained at the external surface of the oxide. During reduction, the oxide layer expanded and transformed into porous structures where oxidized Cu was fully reduced to Cu NPs while Fe, Co, and Ni remained in the oxidized form. In situ chemical analysis showed that the expansion of the oxide layer resulted from the outward diffusion flux of all transition metals (Fe, Co, Ni, Cu). Revealing the H-2 reduction behavior of HEA NPs facilitates the development of advanced multicomponent alloys for applications targeting H 2 formation and storage, catalytic hydrogenation, and corrosion removal.
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Active sites and catalytic activity of heterogeneous catalysts is determined by their surface atomic structures. However, probing the surface structure at an atomic resolution is difficult, especially for solution ensembles of catalytic nanocrystals, which consist of heterogeneous particles with irregular shapes and surfaces. In this study, we constructed 3D maps of the coordination number (CN) and generalized CN ($\bar{C}\bar{N}$) for individual surface atoms of sub-3 nm Pt nanocrystals. Our results reveal that the synthesized Pt nanocrystals are enclosed by islands of atoms with nonuniform shapes that lead to complex surface structures, including a high ratio of low-coordination surface atoms, reduced domain size of low-index facets, and various types of exposed high-index facets. 3D maps of $\bar{C}\bar{N}$ are directly correlated to catalytic activities assigned to individual surface atoms with distinct local coordination structures, which explains the origin of high catalytic performance of small Pt nanocrystals in important reactions such as oxygen reduction reactions and CO electro-oxidation.
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An antiferromagnet offers many important functionalities such as opportunities for electrical control of magnetic domains, immunity from magnetic perturbations, and fast spin dynamics. Introducing some of these intriguing features of an antiferromagnet into a low dimensional semiconductor core–shell nanowire offers an exciting pathway for its usage in antiferromagnetic semiconductor spintronics. Here, using a quantum mechanical approach, we predict that the Cr-doped Ge-core/Si-shell nanowire behaves as an antiferromagnetic semiconductor. In this work, the origin of antiferromagnetic spin alignments between Cr is attributed to the superexchange interaction mediated by the p z orbitals of the Ge atoms that are bonded to Cr. A weak spin–orbit interaction was found in this material, suggesting a longer spin coherence length. The spin-dependent quantum transport calculations in the Cr-doped nanowire junction reveals a switching feature with a high ON/OFF current ratio (~41 times higher for the ON state at a relatively small bias of 0.83 V).
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The ability to create nanoengineered silicon carbide (SiC) architectures is important for the diversity of optical, electronic, and mechanical applications. Here, we report a fabrication of periodic three-dimensional (3D) SiC nanoscale architectures using a self-assembled and designed 3D DNA-based framework. The assembly is followed by the templating into silica and subsequent conversion into SiC using a lower temperature pathway (<700 °C) via magnesium reduction. The formed SiC framework lattice has a unit size of about 50 nm and domains over 5 μm, and it preserves the integrity of the original 3D DNA lattice. The spectroscopic and electron microscopy characterizations reveal SiC crystalline morphology of 3D nanoarchitectured lattices, whereas electrical probing shows 2 orders of magnitude enhancements of electrical conductivity over the precursor silica framework. The reported approach offers a versatile methodology toward creating highly structured and spatially prescribed SiC nanoarchitectures through the DNA-programmable assembly and the combination of templating processes.
The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. Here, we investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ~110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.
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Self-assembly of small amphiphilic molecules in water can lead to nanostructures of varying geometries with pristine internal molecular organization. Here we introduce a photoswitchable aramid amphiphile (AA), designed to exhibit extensive hydrogen bonding and robust mechanical properties upon self-assembly, while containing a vinylnitrile group for photoinduced cis-trans isomerization. We demonstrate spontaneous self-assembly of the vinylnitrile-containing AA in water to form nanoribbons. Upon UV irradiation, trans-to-cis isomerizations occur concomitantly with a morphological transition from nanoribbons to nanotubes. The nanotube structure persists in water for over six months, stabilized by strong and collective intermolecular interactions. We demonstrate that the nanoribbon-to-nanotube transition is reversible upon heating and that switching between states can be achieved repeatedly. Finally, we use electron microscopy to capture the transition and propose mechanisms for nanoribbon-to-nanotube rearrangement and vice versa. This stability and switchability of photoresponsive AA nanostructures make them viable for a range of future applications.
All-solid-state lithium batteries promise significant improvements in energy density and safety over traditional liquid electrolyte batteries. The Al-doped Li 7 La 3 Zr 2 O 12 (LLZO) solid-state electrolyte shows excellent potential given its high ionic conductivity and good thermal, chemical, and electrochemical stability. Nevertheless, further improvements on electrochemical and mechanical properties of LLZO call for an in-depth understanding of its local microstructure. Here, we employ Bragg coherent diffractive imaging to investigate the atomic displacements inside single grains of LLZO with various Al-doping concentrations, resulting in cubic, tetragonal, and cubic-tetragonal mixed structures. We observe coexisting domains of different crystallographic orientations in the tetragonal structure. We further show that Al doping leads to crystal defects such as dislocations and phase boundaries in the mixed- and cubic-phase grain. This study addresses the effect of Al doping on the nanoscale structure within individual grains of LLZO, which is informative for the future development of solid-state batteries.
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Low-power trapping of nanoscale objects can be achieved by using the enhanced fields near plasmonic nanoantennas. Unfortunately, in this approach the trap site is limited to the position of the plasmonic hotspots and continuous dynamic manipulation is not feasible. In this work, we report a low-frequency electrothermoplasmonic tweezer (LFET) that provides low-power, high-stability and continuous dynamic manipulation of a single nanodiamond. LFET harnesses the combined action of the laser illumination of a plasmonic nanopillar antenna array and low-frequency alternating current (ac) electric field to establish an electrohydrodynamic potential capable of the stable trapping and dynamic manipulation of single nanodiamonds. We experimentally demonstrate the fast transport, trapping, and dynamic manipulation of a single nanodiamond using a low-frequency ac field below 5 kHz and low-laser power of 1 mW. This nanotweezer platform for nanodiamond manipulation holds promise for the scalable assembly of single photon sources for quantum information processing and low noise quantum sensors.
Imposing additional confinement in two-dimensional (2D) materials can yield further control over the associated electronic, optical, and topological properties. However, synthesis of ultra-narrow nanoribbons (NRs) remains a challenge, particularly for the transition metal dichalcogenides (TMDs), and synthesizing TMD NRs narrower than 50 nm has remained elusive. In this paper, we report the vapor-phase synthesis of ultra-narrow TaS 2 NRs. The NRs are grown within the hollow cavity of carbon nanotubes, thereby limiting their lateral dimensions and layer number, while simultaneously stabilizing them against the environment. The NRs reach the monolayer (ML) limit and exhibit widths as low as 2.5 nm. Atomic-resolution scanning transmission electron microscopy (STEM) reveals the detailed atomic structure of the ultra-narrow NRs and we observe a hitherto unseen atomic structure supermodulation phenomenon of ordered defect arrays within the NRs. First-principles calculations based on density functional theory (DFT) show the presence of flat bands, as well as edge- and boundary-localized states, and help identify the atomic configuration of the supermodulation. Nanotube-templated synthesis represents a unique, transferable, and broadly deployable route toward ultra-narrow TMD NR growth.
Topological Hall effect (THE) has been used as a powerful tool to unlock spin chirality in novel magnetic materials. Recent focus has been widely paid to THE and possible chiral spin textures in two-dimensional (2D) layered magnetic materials. However, the room-temperature THE has been barely reported in 2D materials, which hinders its practical applications in 2D spintronics. In this paper, we report a possible THE signal featuring antisymmetric peaks in a wide temperature window up to 320 K in Cr 1.2 Te 2 , a new quasi-2D ferromagnetic material. The temperature, thickness, and magnetic field dependences of the THE lead to potential spin chirality origin that is associated with the spin canting under external magnetic fields. Furthermore, our work holds promise for practical applications in future chiral spin-based vdW spintronic devices.
Excellent photovoltaic performance is predicted in a pentagonal covalent network of Si in a hollow structure exhibiting both thermal and dynamical stability. Consisting of a combination of sp 2 and sp 3 hybridized Si atomic orbitals, the GW0 computed band structure shows an indirect band gap near the zone edge and also a manifold of directly absorbing transitions at frequencies in the window of visible light, in distinction with conventional Si. Hydrogenation of a single sp 2 site is predicted to lead to a robust local magnetic moment. In this study, we find a low formation energy at low pressure that is compatible with other experimentally known phases, suggesting that a stable phase might be obtained.