Nanoscale Magnetic Arrays through Block Copolymer Templating of Polyoxometalates.

Magnetic nanoarrays promise to enable new energy-efficient computations based on spintronics or magnonics. In this work, we present a block copolymer-assisted strategy for fabricating ordered magnetic nanostructures on silicon and permalloy substrates. Block copolymer micelle-like structures were used as a template in which polyoxometalate (POM) clusters could assemble in an opal-like structure. A combination of microscopy and scattering techniques was used to confirm the structural and organizational features of the fabricated materials. The magnetic properties of these materials were investigated by polarized neutron reflectometry, nuclear magnetic resonance, and magnetometry measurements. The data show that a magnetic structural design was achieved and that a thin layer of patterned POMs strongly influenced an underlying permalloy layer. This work demonstrates that the bottom-up pathway is a potentially viable method for patterning magnetic substrates on a sub-100 nm scale, toward the magnetic nanostructures needed for spintronic or magnonic crystal devices.

Epitaxial Nickel Ferrocyanide Stabilizes Jahn-Teller Distortions of Manganese Ferrocyanide for Sodium-Ion Batteries.

Manganese-based Prussian Blue, Na2-δ Mn[Fe(CN)6 ] (MnPB), is a good candidate for sodium-ion battery cathode materials due to its high capacity. However, it suffers from severe capacity decay during battery cycling due to the destabilizing Jahn-Teller distortions it undergoes as Mn2+ is oxidized to Mn3+ . Herein, the structure is stabilized by a thin epitaxial surface layer of nickel-based Prussian Blue (Na2-δ Ni[Fe(CN)6 ]). The one-pot synthesis relies on a chelating agent with an unequal affinity for Mn2+ and Ni2+ ions, which prevents Ni2+ from reacting until the Mn2+ is consumed. This is a new and simpler synthesis of core-shell materials, which usually needs several steps. The material has an electrochemical capacity of 93 mA h g-1 , of which it retains 96 % after 500 charge-discharge cycles (vs. 37 % for MnPB). Its rate capability is also remarkable: at 4 A g-1 (ca. 55 C) it can reversibly store 70 mA h g-1 , which is also reflected in its diffusion coefficient of ca. 10-8  cm2 s-1 . The epitaxial outer layer appears to exert an anisotropic strain on the inner layer, preventing the Jahn-Teller distortions it normally undergoes during de-sodiation.

Possible Excitonic Insulating Phase in Quantum-Confined Sb Nanoflakes.

In the 1960s, it was proposed that in small indirect band-gap materials, excitons can spontaneously form because the density of carriers is too low to screen the attractive Coulomb interaction between electrons and holes. The result is a novel strongly interacting insulating phase known as an excitonic insulator. Here we employ scanning tunnelling microscopy (STM) and spectroscopy (STS) to show that the enhanced Coulomb interaction in quantum-confined elemental Sb nanoflakes drives the system to the excitonic insulator state. The unique feature of the excitonic insulator, a charge density wave (CDW) without periodic lattice distortion, is directly observed. Furthermore, STS shows a gap induced by the CDW near the Fermi surface. Our observations suggest that the Sb(110) nanoflake is an excitonic insulator.

Development and Investigation of a NASICON-Type High-Voltage Cathode Material for High-Power Sodium-Ion Batteries.

Herein, we introduce a 4.0 V class high-voltage cathode material with a newly recognized sodium superionic conductor (NASICON)-type structure with cubic symmetry (space group P21 3), Na3 V(PO3 )3 N. We synthesize an N-doped graphene oxide-wrapped Na3 V(PO3 )3 N composite with a uniform carbon coating layer, which shows excellent rate performance and outstanding cycling stability. Its air/water stability and all-climate performance were carefully investigated. A near-zero volume change (ca. 0.40 %) was observed for the first time based on in situ synchrotron X-ray diffraction, and the in situ X-ray absorption spectra revealed the V3.2+ /V4.2+ redox reaction with high reversibility. Its 3D sodium diffusion pathways were demonstrated with distinctive low energy barriers. Our results indicate that this high-voltage NASICON-type Na3 V(PO3 )3 N composite is a competitive cathode material for sodium-ion batteries and will receive more attention and studies in the future.

Discovery of a Voltage-Stimulated Heartbeat Effect in Droplets of Liquid Gallium.

Chemomechanical effects are known to initiate fluid oscillations in certain liquid metals; however, they typically produce an irregular motion that is difficult to deactivate or control. Here we show that stimulating liquid gallium with electrochemistry can cause a metal drop to exhibit a heart beating effect by shape shifting at a telltale frequency. Unlike the effects reported in the past for mercury, the symmetry-breaking forces generated by using gallium propel the drop several millimeters with velocities of the order of 1 cm per second. We demonstrate pulsating dynamics between 0 and 610 beats per minute for 50-150 µL droplets in a NaOH electrolyte at 34 °C. The underlying mechanism is a self-regulating cycle initiated by fast electrochemical oxidation that adjusts the drop's surface tension and causes a transformation from spherical to pancake form, followed by detachment from the circular electrode. As the beat frequency can be activated and controlled using a dc voltage, the electrochemical mechanism opens the way for fluid-based timers and actuators.

Direct measurements of the temperature, depth and processing dependence of phenyl ring dynamics in polystyrene thin films by ß-detected NMR.

There is indirect evidence that the dynamics of a polymer near a free surface are enhanced compared with the bulk but there are few studies of how dynamics varies with depth. ß-Detected nuclear spin relaxation of implanted 8Li+ has been used to directly probe the temperature and depth dependence of the γ-relaxation mode, which is due to phenyl rings undergoing restricted rotation, in thin films of atactic deuterated polystyrene (PS-d8) and determine how the depth dependence of dynamics is affected by sample processing, such as annealing, floating on water and the inclusion of a surfactant, and by the presence of a buried interface. The activation energy for the γ-relaxation process is lower near the free surface. Annealing the PS-d8 films and then immersing in water to mimic the floating procedure used to transfer films had negligible effects on the thickness of the region near the free surface with enhanced mobility. Measurements on a bilayer film indicate enhanced phenyl ring dynamics near the buried interface compared with a single film at the same depth. PS-d8 films annealed with the surfactant sodium dodecyl sulfate (SDS) deposited on the surface show enhanced dynamics in the bulk compared with a pure PS-d8 film and a PS-d8 film where the SDS was washed away. There is less contrast between the surface and bulk in the SDS-treated sample, which could account for the elimination of the Tg confinement effect observed in films containing SDS [Chen and Torkelson, Polymer, 2016, 87, 226].

Heat transfer from nanoparticles for targeted destruction of infectious organisms.

Whereas the application of optically or magnetically heated nanoparticles to destroy tumours is now well established, the extension of this concept to target pathogens has barely begun. Here we examine the challenge of targeting pathogens by this means and, in particular, explore the issues of power density and heat transfer. Depending on the rate of heating, either hyperthermia or thermoablation may occur. This division of the field is fundamental and implies very different sources of excitation and heat transfer for the two modes, and different strategies for their clinical application. Heating by isolated nanoparticles and by agglomerates of nanoparticles is compared: hyperthermia is much more readily achieved with agglomerates and for large target volumes, a factor which favours magnetic excitation and moderate power densities. In contrast, destruction of planktonic pathogens is best achieved by localised thermoablation and very high power density, a scenario that is best delivered by pulsed optical excitation.

ß-NMR measurements of molecular-scale lithium-ion dynamics in poly(ethylene oxide)-lithium-salt thin films.

ß-detected NMR (ß-NMR) has been used to study the molecular-scale dynamics of lithium ions in thin films of poly(ethylene oxide) (PEO) containing either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium trifluoroacetate (LiTFA) salts at monomer-to-salt ratios (EO/Li) of 8.3. The results are compared with previous ß-NMR measurements on pure PEO and PEO with lithium triflate (LiOTf) at the same loading [McKenzie et al., J. Am. Chem. Soc. 136, 7833 (2014)]. Activated hopping of 8Li+ was observed in all of the films above ∼250 K, with the hopping parameters strongly correlated with the ionicity of the lithium salt rather than the polymer glass transition temperature. The pre-exponential factor increases exponentially with ionicity, while the activation energy for hopping increases approximately linearly, going from 6.3±0.2 kJ mol-1 in PEO:LiTFA to 17.8±0.2 kJ mol-1 in PEO:LiTFSI. The more rapid increase in the pre-exponential factor outweighs the effect of the larger activation energy and results in 8Li+ hopping being fastest in PEO followed by PEO:LiTFSI, PEO:LiOTf, and PEO:LiTFA.

Epitaxial graphene growth on cubic silicon carbide on silicon with high temperature neutron reflectometry: an operando study.

The growth of graphene on silicon carbide on silicon offers a very attractive route towards novel wafer-scale photonic and electronic devices that are easy to fabricate and can be integrated in silicon manufacturing. Using a Ni/Cu catalyst for the epitaxial growth of graphene has been successful in the mitigation of the very defective nature of the underlying silicon carbide on silicon, leading to a consistent graphene coverage over large scales. A more detailed understanding of this growth mechanism is warranted in order to further optimise the catalyst composition, preferably via the use of operando characterization measurements. Here, we report in situ neutron reflectometry measurements of (Ni, Cu)/SiC films on silicon wafers, annealed from room temperature to 1100 °C, which initiates graphene formation at the buried (Ni, Cu)/SiC interface. Detailed modelling of the high temperature neutron reflectometry and corresponding scattering length density profiles yield insights into the distinct physical mechanisms within the different temperature regimes. The initially smooth solid metallic layers undergo intermixing and roughening transitions at relatively low temperatures below 500 °C, and then metal silicides begin to form above 600 °C from interfacial reactions with the SiC, releasing atomic carbon. At the highest temperature range of 600-1100 °C, the low neutron scattering length density at high temperature is consistent with a silicon-rich, liquid surface phase corresponding to molten nickel silicides and copper. This liquid catalyst layer promotes the liquid-phase epitaxial growth of a graphene layer by precipitating the excess carbon available at the SiC/metal interface.

Spin Reorientation Transition and Negative Magnetoresistance in Ferromagnetic NdCrSb3 Single Crystals.

High-quality NdCrSb3 single crystals are grown using a Sn-flux method, for electronic transport and magnetic structure study. Ferromagnetic ordering of the Nd3+ and Cr3+ magnetic sublattices are observed at different temperatures and along different crystallographic axes. Due to the Dzyaloshinskii-Moriya interaction between the two magnetic sublattices, the Cr moments rotate from the b axis to the a axis upon cooling, resulting in a spin reorientation (SR) transition. The SR transition is reflected by the temperature-dependent magnetization curves, e.g., the Cr moments rotate from the b axis to the a axis with cooling from 20 to 9 K, leading to a decrease in the b-axis magnetization f and an increase in the a-axis magnetization. Our elastic neutron scattering along the a axis shows decreasing intensity of magnetic (300) peak upon cooling from 20 K, supporting the SR transition. Although the magnetization of two magnetic sublattices favours different crystallographic axes and shows significant anisotropy in magnetic and transport behaviours, their moments are all aligned to the field direction at sufficiently large fields (30 T). Moreover, the magnetic structure within the SR transition region is relatively fragile, which results in negative magnetoresistance by applying magnetic fields along either a or b axis. The metallic NdCrSb3 single crystal with two ferromagnetic sublattices is an ideal system to study the magnetic interactions, as well as their influences on the electronic transport properties.

Top-down patterning of topological surface and edge states using a focused ion beam.

The conducting boundary states of topological insulators appear at an interface where the characteristic invariant ℤ2 switches from 1 to 0. These states offer prospects for quantum electronics; however, a method is needed to spatially-control ℤ2 to pattern conducting channels. It is shown that modifying Sb2Te3 single-crystal surfaces with an ion beam switches the topological insulator into an amorphous state exhibiting negligible bulk and surface conductivity. This is attributed to a transition from ℤ2 = 1 → ℤ2 = 0 at a threshold disorder strength. This observation is supported by density functional theory and model Hamiltonian calculations. Here we show that this ion-beam treatment allows for inverse lithography to pattern arrays of topological surfaces, edges and corners which are the building blocks of topological electronics.

Advice on describing Bayesian analysis of neutron and X-ray reflectometry.

As a result of the availability of modern software and hardware, Bayesian analysis is becoming more popular in neutron and X-ray reflectometry analysis. The understandability and replicability of these analyses may be harmed by inconsistencies in how the probability distributions central to Bayesian methods are represented in the literature. Herein advice is provided on how to report the results of Bayesian analysis as applied to neutron and X-ray reflectometry. This includes the clear reporting of initial starting conditions, the prior probabilities, the results of any analysis and the posterior probabilities that are the Bayesian equivalent of the error bar, to enable replicability and improve understanding. It is believed that this advice, grounded in the authors' experience working in the field, will enable greater analytical reproducibility in the work of the reflectometry community, and improve the quality and usability of results.

Experimental Confirmation of the Universal Law for the Vibrational Density of States of Liquids.

An analytical model describing the vibrational density of states (VDOS) of liquids has long been elusive, owing to the complexities of liquid dynamics. Nevertheless, Zaccone and Baggioli have recently developed such a model which was proposed to be the universal law for the vibrational density of states of liquids. Distinct from the Debye law, g(ω) ∝ ω2, for solids, the universal law for liquids reveals a linear relationship, g(ω) ∝ ω, in the low-energy region. We have confirmed this universal law with experimental VDOS measured by inelastic neutron scattering on real liquid systems including water, liquid metal, and polymer liquids, and have applied this model to extract the effective relaxation rate for the short time dynamics for each liquid. The model has also been further evaluated in the prediction of the specific heat with comparison to existing experimental data as well as with values obtained by different approaches.

Large Magnetic Gap in a Designer Ferromagnet-Topological Insulator-Ferromagnet Heterostructure.

Combining magnetism and nontrivial band topology gives rise to quantum anomalous Hall (QAH) insulators and exotic quantum phases such as the QAH effect where current flows without dissipation along quantized edge states. Inducing magnetic order in topological insulators via proximity to a magnetic material offers a promising pathway toward achieving the QAH effect at a high temperature for lossless transport applications. One promising architecture involves a sandwich structure comprising two single-septuple layers (1SL) of MnBi2 Te4 (a 2D ferromagnetic insulator) with ultrathin few quintuple layer (QL) Bi2 Te3 in the middle, and it is predicted to yield a robust QAH insulator phase with a large bandgap greater than 50 meV. Here, the growth of a 1SL MnBi2 Te4 /4QL Bi2 Te3 /1SL MnBi2 Te4 heterostructure via molecular beam epitaxy is demonstrated and the electronic structure probed using angle-resolved photoelectron spectroscopy. Strong hexagonally warped massive Dirac fermions and a bandgap of 75 ± 15 meV are observed. The magnetic origin of the gap is confirmed by the observation of the exchange-Rashba effect, as well as the vanishing bandgap above the Curie temperature, in agreement with density functional theory calculations. These findings provide insights into magnetic proximity effects in topological insulators and reveal a promising platform for realizing the QAH effect at elevated temperatures.

Ultra-small cobalt particles embedded in titania by ion beam synthesis: Additional datasets including electron microscopy, neutron reflectometry, modelling outputs and particle size analysis.

This Data-in-brief article includes datasets of electron microscopy, polarised neutron reflectometry and magnetometry for ultra-small cobalt particles formed in titania thin films via ion beam synthesis. Raw data for polarised neutron reflectometry, magnetometry and the particle size distribution are included and made available on a public repository. Additional elemental maps from scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) are also presented. Data were obtained using the following types of equipment: the NREX and PLATYPUS polarised neutron reflectometers; a Quantum Design Physical Property Measurement System (14 T); a JEOL JSM-6490LV SEM, and a JEOL ARM-200F scanning transmission electron microscope (STEM). The data is provided as supporting evidence for the article in Applied Surface Science (A. Bake et al., Appl. Surf. Sci., vol. 570, p. 151068, 2021, DOI 10.1016/j.apsusc.2021.151068), where a full discussion is given. The additional supplementary reflectometry and modelling datasets are intended to assist future scientific software development of advanced fitting algorithms for magnetization gradients in thin films.

Liquid-Metal-Assisted Deposition and Patterning of Molybdenum Dioxide at Low Temperature.

Molybdenum dioxide (MoO2), considering its near-metallic conductivity and surface plasmonic properties, is a great material for electronics, energy storage devices and biosensing. Yet to this day, room-temperature synthesis of large area MoO2, which allows deposition on arbitrary substrates, has remained a challenge. Due to their reactive interfaces and specific solubility conditions, gallium-based liquid metal alloys offer unique opportunities for synthesizing materials that can meet these challenges. Herein, a substrate-independent liquid metal-based method for the room temperature deposition and patterning of MoO2 is presented. By introducing a molybdate precursor to the surrounding of a eutectic gallium-indium alloy droplet, a uniform layer of hydrated molybdenum oxide (H2MoO3) is formed at the interface. This layer is then exfoliated and transferred onto a desired substrate. Utilizing the transferred H2MoO3 layer, a laser-writing technique is developed which selectively transforms this H2MoO3 into crystalline MoO2 and produces electrically conductive MoO2 patterns at room temperature. The electrical conductivity and plasmonic properties of the MoO2 are analyzed and demonstrated. The presented metal oxide room-temperature deposition and patterning method can find many applications in optoelectronics, sensing, and energy industries.

Spin-wave propagation in α-Fe2O3 nanorods: the effect of confinement and disorder.

Spin-wave excitations in α-Fe2O3 nanorods were directly detected using time-of-flight inelastic neutron spectroscopy. The dispersive magnon features are compared with those in bulk α-Fe2O3 particles at various temperatures to highlight differences in mode intensity and width. The interchanged spectral intensities in the nanorod are a consequence of a suppressed spin orientation, and this is also evident in the neutron diffraction which demonstates that the weak ferromagnetic phase survives to 1.5 K. Transmission electron microscopy shows that the ellipsoidal particles are single-crystalline with a typical length of 300 ± 100 nm and diameter of 60 ± 10 nm. The main magnon features are similar in bulk and nanoforms and can be explained using a model Hamiltonian based on Samuelson and Shirane's classical theory with exchange constants of J 1 = -1.03 meV, J 2 = -0.28 meV, J 3 = 5.12 meV and J 4 = 4.00 meV. Numerical simulations show that two distinct mechanisms may contribute to the magnon line broadening in the nanorods: a distribution of exchange interactions caused by disorder, and a shortened quasiparticle lifetime caused by the scattering of spin waves at surfaces.

In Operando Study of the Hydrogen-Induced Switching of Magnetic Anisotropy at the Co/Pd Interface for Magnetic Hydrogen Gas Sensing.

Heterostructures exhibiting perpendicular magnetic anisotropy (PMA) have traditionally served the magnetic recording industry. However, an opportunity exists to expand the applications of PMA heterostructures into the realm of hydrogen sensing using ferromagnetic resonance (FMR) by exploiting the hydrogen-induced modifications to PMA that occur at the interface between Pd and a ferromagnet. Here, we present the first in operando depth-resolved study of the in-plane interfacial magnetization of a Co/Pd film which features tailorable PMA in the presence of hydrogen gas. We combine polarized neutron reflectometry with in situ FMR to explore how the absorption of hydrogen at the Co/Pd interface affects the heterostructures spin-resonance condition during hydrogen cycling. Experimental data and modeling reveal that the Pd layer expands when exposed to hydrogen gas, while the in-plane magnetic moment of the Co/Pd film increases as the interfacial PMA is reduced to affect the FMR frequency. This work highlights a potential route for magnetic hydrogen gas sensing.

NASICON-type air-stable and all-climate cathode for sodium-ion batteries with low cost and high-power density.

The development of low-cost and long-lasting all-climate cathode materials for the sodium ion battery has been one of the key issues for the success of large-scale energy storage. One option is the utilization of earth-abundant elements such as iron. Here, we synthesize a NASICON-type tuneable Na4Fe3(PO4)2(P2O7)/C nanocomposite which shows both excellent rate performance and outstanding cycling stability over more than 4400 cycles. Its air stability and all-climate properties are investigated, and its potential as the sodium host in full cells has been studied. A remarkably low volume change of 4.0% is observed. Its high sodium diffusion coefficient has been measured and analysed via first-principles calculations, and its three-dimensional sodium ion diffusion pathways are identified. Our results indicate that this low-cost and environmentally friendly Na4Fe3(PO4)2(P2O7)/C nanocomposite could be a competitive candidate material for sodium ion batteries.

Direct Measurement of the Intrinsic Sharpness of Magnetic Interfaces Formed by Chemical Disorder Using a He+ Beam.

Using ion beams to locally modify material properties and subsequently drive magnetic phase transitions is rapidly gaining momentum as the technique of choice for the fabrication of magnetic nanoelements. This is because the method provides the capability to engineer in three dimensions on the nanometer length scale. This will be an important consideration for several emerging magnetic technologies (e.g., spintronic devices and racetrack and random-access memories) where device functionality will hinge on the spatial definition of the incorporated magnetic nanoelements. In this work, the fundamental sharpness of a magnetic interface formed by nanomachining FePt3 films using He+ irradiation is investigated. Through careful selection of the irradiating ion energy and fluence, room-temperature ferromagnetism is locally induced into a fractional volume of a paramagnetic (PM) FePt3 film by modifying the chemical order parameter. A combination of transmission electron microscopy, magnetometry, and polarized neutron reflectometry measurements demonstrates that the interface over which the PM-to-ferromagnetic modulation occurs in this model system is confined to a few atomic monolayers only, while the structural boundary transition is less well-defined. Using complementary density functional theory, the mechanism for the ion-beam-induced magnetic transition is elucidated and shown to be caused by an intermixing of Fe and Pt atoms in antisite defects above a threshold density.