Evidence of Surface-Mediated Carrier-Phonon Scattering in MXene.

In a two-dimensional (2D) metallic nanostructure, when a sample's thickness is shorter than a carrier mean free path, the ultrathin thickness may influence carrier and energy transport, owing to surface scattering. However, to date, for metallic 2D transition-metal carbides (MXenes), experiments and calculations related to surface scattering have not been performed. The contribution of ultrathin structures to carrier surface scattering in MXene is yet to be explored. Herein, to reveal this effect, we design various models, including metal/MXene, dielectric/MXene, and bulk structure, and analyze their carrier dynamics via ultrafast spectroscopy. The results related to carrier dynamics indicate that the influence of the dielectric/MXene interface and the temperature is negligible. In contrast, the carrier dynamic lifetimes are prolonged owing to weakened surface scattering in metal/MXene, which is supported by ab initio calculations. These results suggest that the carrier-phonon scattering is dominated by surface scattering. These findings can help guide effective energy transport and enhance energy conversion and catalysis.

Rugged Forest Morphology of Magnetoplasmonic Nanorods that Collect Maximum Light for Photoelectrochemical Water Splitting.

A feasible nanoscale framework of heterogeneous plasmonic materials and proper surface engineering can enhance photoelectrochemical (PEC) water-splitting performance owing to increased light absorbance, efficient bulk carrier transport, and interfacial charge transfer. This article introduces a new magnetoplasmonic (MagPlas) Ni-doped Au@Fex Oy nanorods (NRs) based material as a novel photoanode for PEC water-splitting. A two stage procedure produces core-shell Ni/Au@Fex Oy MagPlas NRs. The first-step is a one-pot solvothermal synthesis of Au@Fex Oy . The hollow Fex Oy nanotubes (NTs) are a hybrid of Fe2 O3 and Fe3 O4 , and the second-step is a sequential hydrothermal treatment for Ni doping. Then, a transverse magnetic field-induced assembly is adopted to decorate Ni/Au@Fex Oy on FTO glass to be an artificially roughened morphologic surface called a rugged forest, allowing more light absorption and active electrochemical sites. Then, to characterize its optical and surface properties, COMSOL Multiphysics simulations are carried out. The core-shell Ni/Au@Fex Oy MagPlas NRs increase photoanode interface charge transfer to 2.73 mAcm-2 at 1.23 V RHE. This improvement is made possible by the rugged morphology of the NRs, which provide more active sites and oxygen vacancies as the hole transfer medium. The recent finding may provide light on plasmonic photocatalytic hybrids and surface morphology for effective PEC photoanodes.

The role of self-occluding contours in material perception.

The human visual system extracts both the three-dimensional (3D) shape and the material properties of surfaces from single images.1,2,3,4,5,6,7,8,9,10,11,12,13,14 Understanding this remarkable ability is difficult because the problem of extracting both shape and material is formally ill posed: information about one appears to be needed to recover the other.14,15,16,17 Recent work has suggested that a particular class of image contours formed by a surface curving smoothly out of sight (self-occluding contours) contains information that co-specifies both surface shape and material for opaque surfaces.18 However, many natural materials are light permeable (translucent); it is unknown whether there is information along self-occluding contours that can be used to distinguish opaque and translucent materials. Here, we present physical simulations, which demonstrate that variations in intensity generated by opaque and translucent materials are linked to different shape attributes of self-occluding contours. Psychophysical experiments demonstrate that the human visual system exploits the different forms of intensity-shape covariation along self-occluding contours to distinguish opaque and translucent materials. These results provide insight into how the visual system manages to solve the putatively ill-posed problem of extracting both the shape and material properties of 3D surfaces from images.

Anisotropic Resistivity Size Effect in Epitaxial Mo(001) and Mo(011) Layers.

Mo(001) and Mo(011) layers with thickness d = 4-400 nm are sputter-deposited onto MgO(001) and α-Al2O3(112¯0) substrates and their resistivity is measured in situ and ex situ at room temperature and 77 K in order to quantify the resistivity size effect. Both Mo(001) and Mo(011) layers are epitaxial single crystals and exhibit a resistivity increase with decreasing d due to electron surface scattering that is well described by the classical Fuchs and Sondheimer model. Data fitting yields room temperature effective electron mean free paths λ*= 14.4 ± 0.3 and 11.7 ± 0.3 nm, respectively, indicating an anisotropy with a smaller resistivity size effect for the Mo(011) orientation. This is attributed to a smaller average Fermi velocity component perpendicular to (011) surfaces, causing less surface scattering and a suppressed resistivity size effect. First-principles electronic structure calculations in combination with Boltzmann transport simulations predict an orientation dependent transport with a more pronounced resistivity increase for Mo(001) than Mo(011). This is in agreement with the measurements, confirming the effect of the Fermi surface shape on the thin-film resistivity. The predicted anisotropy λ001*/λ011* = 1.57 is in reasonable agreement with 1.66 and 1.23 measured at 77 and 295 K. The overall results indicate that the resistivity size effect in Mo is relatively small, with a measured product of the bulk resistivity times the effective electron mean free path ρoλ* = (7.7 ± 0.3) and (6.2 ± 0.2) × 10-16 Ωm2 for Mo(001) and Mo(011) layers. The latter value is in excellent agreement with the first-principles-predicted ρoλ = 5.99 × 10-16 Ωm2 and is 10% and 40% smaller than the reported measured ρoλ for Cu and W, respectively, indicating the promise of Mo as an alternate conductor for narrow interconnects.

Machine learning for scattering data: strategies, perspectives and applications to surface scattering.

Machine learning (ML) has received enormous attention in science and beyond. Discussed here are the status, opportunities, challenges and limitations of ML as applied to X-ray and neutron scattering techniques, with an emphasis on surface scattering. Typical strategies are outlined, as well as possible pitfalls. Applications to reflectometry and grazing-incidence scattering are critically discussed. Comment is also given on the availability of training and test data for ML applications, such as neural networks, and a large reflectivity data set is provided as reference data for the community.

Observation of Dirac Charge-Density Waves in Bi2Te2Se.

While parallel segments in the Fermi level contours, often found at the surfaces of topological insulators (TIs), would imply "strong" nesting conditions, the existence of charge-density waves (CDWs)-periodic modulations of the electron density-has not been verified up to now. Here, we report the observation of a CDW at the surface of the TI Bi2Te2Se(111), below ≈350K, by helium-atom scattering and, thus, experimental evidence for a CDW involving Dirac topological electrons. Deviations of the order parameter observed below 180K, and a low-temperature break of time reversal symmetry, suggest the onset of a spin-density wave with the same period as the CDW in the presence of a prominent electron-phonon interaction, originating from Rashba spin-orbit coupling.

Chiral surface spin textures in Cu2OSeO3 unveiled by soft X-ray scattering in specular reflection geometry.

Resonant elastic soft X-ray magnetic scattering (XRMS) is a powerful tool to explore long-periodic spin textures in single crystals. However, due to the limited momentum transfer range imposed by long wavelengths of photons in the soft x-ray region, Bragg diffraction is restricted to crystals with the large lattice parameters. Alternatively, small-angle X-ray scattering has been involved in the soft energy X-ray range which, however, brings in difficulties with the sample preparation that involves focused ion beam milling to thin down the crystal to below a few hundred nm thickness. We show how to circumvent these restrictions using XRMS in specular reflection from a sub-nanometer smooth crystal surface. The method allows observing diffraction peaks from the helical and conical spin modulations at the surface of a Cu   2 OSeO   3 single crystal and probing their corresponding chirality as contributions to the dichroic scattered intensity. The results suggest a promising way to carry out XRMS studies on a plethora of noncentrosymmetric systems hitherto unexplored with soft X-rays due to the absence of the commensurate Bragg peaks in the available momentum transfer range.

Scaled Sea Surface Design and RCS Measurement Based on Rough Film Medium.

The electromagnetic (EM) scattering characteristics of the rough sea surface is very important for target surveying and detection in a sea environment. This work proposes a scaled sea surface designing method based on a rough thin-film medium. For the prototype sea surface, the permittivity is calculated with the seawater temperature, salinity, and EM wave frequency according to the Debye model. The scale film material is mixed with carbon black and epoxy, whose volume ratio is optimized with the genetic algorithm through the existing electromagnetic parameter library. This method can overcome the previous difficulties of adjusting the same permittivity of the prototype sea water. According to the EM scaled theory, the scaled geometric sample is numerically generated with the D-V spectrum for the given wind speed, and is fabricated using 3D printing to keep the similar seawater shape. Then, the sample is sprayed with a layer of film material for EM scattering measurement. The simulated and measured radar cross-section (RCS) results show good consistency for the prototype seawater and scaled materials, which indicates the proposed scaled method is a more efficient method to get the seawater scattering characteristics.

Molecular Dynamics Simulations of Nitric Oxide Scattering Off Graphene.

We performed classical molecular dynamics simulations to model the scattering process of nitric oxide, NO, off graphene supported on gold. This is motivated by our desire to probe the energy transfer in collisions with graphene. Since many of these collision systems comprising of graphene and small molecules have been shown to scatter non-reactively, classical molecular dynamics appear to describe such systems sufficiently. We directed thousands of trajectories of NO molecules onto graphene along the surface normal, while varying impact position, but also speed, orientation, and rotational excitation of the nitric oxide, and compare the results with experimental data. While experiment and theory do not match quantitatively, we observe agreement that the relative amount of kinetic energy lost during the collision increases with increasing initial kinetic energy of the NO. Furthermore, while at higher collision energies, all NO molecules lose some energy, and the vast majority of NO is scattered back, in contrast at low impact energies, the fraction of those nitric oxide molecules that are trapped at the surface increases, and some NO molecules even gain some kinetic energy during the collision process. The collision energy seems to preferentially go into the collective motion of the carbon atoms in the graphene sheet.

Multiple echoes in beam spin-echo spectroscopy and their effect on measurements of ultra-fast dynamics.

Helium (3He) spin-echo is a powerful experimental technique used to probe ultra-fast atomic scale surface dynamics. The analysis of these measurements is typically performed assuming there is only a single spin-echo condition, expected to produce a constant signal for pure elastic scattering, a monotonically decaying signal for quasi-elastic scattering and oscillations from inelastic scattering events. In the present work, we show that there are in fact four spin-echoes which must be correctly accounted for, and that even in the case of elastic scattering these additional echoes lead to oscillations which could mistakenly be interpreted as being due to inelastic scattering. We demonstrate that it is possible to accurately simulate the experimental data by propagating the3He through the measured magnetic field profile of the apparatus and considering the geometry of the machine, allowing the effect of these additional echoes to be disentangled from inelastic scattering events in future3He spin-echo measurements.

Physics-Based Forward Modeling of Ocean Surface Swell Effects on SMAP L1-C NRCS Observations.

This paper examines the impact of ocean surface swell waves on near-coastal L-band high-resolution synthetic aperture radar (SAR) data collected using the National Aeronautics and Space Administration's (NASA) Soil Moisture Active/Passive (SMAP) radar at 40° incidence angle. The two-scale model and a more efficient off-nadir approximation of the second-order small-slope-approximation are used for co- and cross-polarized backscatter normalized radar cross-section (NRCS) predictions of the ocean surface, respectively. Backscatter NRCS predictions are modeled using a combined wind and swell model where wind-driven surface roughness is characterized using the Durden-Vesecky directional spectrum, while swell effects are represented through their contribution to the long wave slope variance (mean-square slopes, or MSS). The swell-only MSS is numerically computed based on a model defined using the JONSWAP spectrum with parameters calculated using the National Data Buoy Center and Wave Watch III data. The backscatter NRCS model is further refined to include fetch-limited and low-wind corrections. The results show an improved agreement between modeled and observed HH-polarized backscatter NRCS when swell effects are included and indicate a relatively larger swell impact on L-band compared to higher radar frequencies. Preliminary investigations into the potential swell retrieval capabilities in the form of excess MSS are encouraging, however further refinements are required to make broadly applicable conclusions.

Water adsorption and dynamics on graphene and other 2D materials: Computational and experimental advances.

The interaction of water and surfaces, at molecular level, is of critical importance for understanding processes such as corrosion, friction, catalysis and mass transport. The significant literature on interactions with single crystal metal surfaces should not obscure unknowns in the unique behaviour of ice and the complex relationships between adsorption, diffusion and long-range inter-molecular interactions. Even less is known about the atomic-scale behaviour of water on novel, non-metallic interfaces, in particular on graphene and other 2D materials. In this manuscript, we review recent progress in the characterisation of water adsorption on 2D materials, with a focus on the nano-material graphene and graphitic nanostructures; materials which are of paramount importance for separation technologies, electrochemistry and catalysis, to name a few. The adsorption of water on graphene has also become one of the benchmark systems for modern computational methods, in particular dispersion-corrected density functional theory (DFT). We then review recent experimental and theoretical advances in studying the single-molecular motion of water at surfaces, with a special emphasis on scattering approaches as they allow an unparalleled window of observation to water surface motion, including diffusion, vibration and self-assembly.

Backscattering limit of nanoscale heat conduction.

Being able to achieve extremely low thermal conductivities is of fundamental importance as well as of practical interest for thermal energy conversion and storage materials. By incorporating backscattering effects on thermal phonon transport, here we introduce a new lower limit for the thermal conductivities of nanoscale engineered materials. Our formulation shows that surface backscattering allows to reach a minimum limit for thermal energy transport at the nanoscale, achieving thermal conductivities which are orders of magnitude smaller than those obtained with classical approaches.

Chemical Identification in the Specular and Off-Specular Rough-Surface Scattered Terahertz Spectra Using Wavelet Shrinkage.

We present the development and implementation of a novel wavelet shrinkage technique for the retrieval of obscured characteristic resonant signatures in the scattered terahertz (THz) reflectivity of molecular crystals. In this implementation, the wavelet basis functions associated with the absorption features were identified using the second-order total variation of the wavelet coefficients. Additionally, wavelet coefficients at certain scales were modified using the phase function corrections and wavelet hard thresholding. Reconstruction of the original spectra using these modified wavelet coefficients yielded the exact resonant frequencies of the chemicals, which were otherwise unrecognizable in the spectral artifacts of the rough surface scattering. We examined the robustness of this method over controlled levels of rough surface scattering, validated using the Kirchhoff approximation, in spectroscopic targets made from α-lactose monohydrate and 4-aminobenzoic acid (PABA), which have close spectral lines. We successfully retrieved the spectral absorption fingerprints in both specular and off-specular reflection geometries. This technique can be utilized for stand-off material characterization using the THz reflection spectroscopy in uncontrolled environments and potentially can be adopted for other broadband spectroscopic modalities.

Phase Function Effects on Identification of Terahertz Spectral Signatures Using the Discrete Wavelet Transform.

We describe the application of the Discrete Wavelet Transform (DWT) in extracting the characteristic absorption signatures of materials from terahertz reflection spectra. We compare the performance of different mother wavelets, including Daubechies, Least Asymmetric (LA), and Coiflet, based on their phase and gain functions and filter lengths. We show that the phase functions of the wavelet and scaling filters result in spectral shifts to the absorption lines in the wavelet domain. We provide a solution by calculating advancement coefficients necessary to achieve effective zero-phase-function DWT. We demonstrate the utility of this signal processing technique using α-lactose monohydrate/polyethylene samples with different levels of rough surface scattering. In all cases, the DWT-based algorithm successfully extracts resonant signatures at 0.53 and 1.38 THz, even when they are obscured by the rough surface scattering effects. The DWT analysis with accompanying phase corrections can be utilized as a robust technique for material identification in non-destructive evaluation (NDE) using terahertz spectroscopy.

Non-reciprocal acoustics in a viscous environment.

It is demonstrated that acoustic transmission through a phononic crystal with anisotropic solid scatterers becomes non-reciprocal if the background fluid is viscous. In an ideal (inviscid) fluid, the transmission along the direction of broken P symmetry is asymmetric. This asymmetry is compatible with reciprocity since time-reversal symmetry (T symmetry) holds. Viscous losses break T symmetry, adding a non-reciprocal contribution to the transmission coefficient. The non-reciprocal transmission spectra for a phononic crystal of metallic circular cylinders in water are experimentally obtained and analysed. The surfaces of the cylinders were specially processed in order to weakly break P symmetry and increase viscous losses through manipulation of surface features. Subsequently, the non-reciprocal part of transmission is separated from its asymmetric reciprocal part in numerically simulated transmission spectra. The level of non-reciprocity is in agreement with the measure of broken P symmetry. The reported study contradicts commonly accepted opinion that linear dissipation cannot be a reason leading to non-reciprocity. It also opens a way for engineering passive acoustic diodes exploring the natural viscosity of any fluid as a factor leading to non-reciprocity.

Stability of Ligands on Nanoparticles Regulating the Integrity of Biological Membranes at the Nano-Lipid Interface.

When nanoparticles interact with cellular or organelle membranes, the coating ligands are known to affect the integrity of the membranes, which regulate cell death and inflammation. However, the molecular mechanisms of this modulation remain unresolved. Here, we use synchrotron X-ray liquid surface scattering and molecular dynamics simulations to study interface structures between phospholipids and gold nanorods (AuNRs) coated by surfactant and polyelectrolyte. These ligands are two types of widely used surface modification with different self-assembled structures and stabilities on the surface of nanoparticles. We reveal distinct mechanisms of the ligand stability in disrupting membrane integrity. We find that the cationic surfactant ligand cetyltrimethylammonium bromide detaches from the AuNRs and inserts into phospholipids, resulting in reduced membrane thickness by compressing the phospholipids to align with the shorter ligand. Conversely, the cationic polyelectrolyte ligand poly(diallyldimethylammonium chloride) is more stable on AuNRs; although it adsorbs onto the membrane, it does not cause much impairment. The distinct coating ligand interactions with phospholipids are further verified by cellular responses including impaired lysosomal membranes and triggered inflammatory effects in macrophages. Together, the quantitative analysis of interface structures elucidates key bio-nano interactions and highlights the importance of surface ligand stability for safety and rational design of nanoparticles.

MoS2 for Enhanced Electrical Performance of Ultrathin Copper Films.

Copper nanowires are widely used as on-chip interconnects due to their superior conductivity. However, with aggressive Cu interconnect scaling, surface scattering of electrons drastically increases the electrical resistivity. In this work, we have studied the electrical performance of Cu thin films deposited on different materials. By comparing the thickness dependence of Cu films' resistivity on MoS2 and SiO2, we have demonstrated that MoS2 can be used to enhance the electrical performance of ultrathin Cu films due to improved specular surface scattering by up to 40%. By fitting the experimental data with the theoretical Fuchs-Sondheimer (FS) model, we have determined the specularity parameter at the Cu/MoS2 interface to be p ≈ 0.4 at room temperature. Furthermore, first principle calculations based on density functional theory (DFT) indicate that the localized density of states (LDOS) at the Cu/amorphous SiO2 interface is larger than the LDOS at the Cu/MoS2 interface, which is believed to be responsible for the higher resistivity in the Cu thin films that are deposited on SiO2 substrates. Our results suggest that MoS2 may serve as a performance enhancer for future generations of Cu interconnects.

Spatial frequency domain imaging using an analytical model for separation of surface and volume scattering.

A method to correct for surface scattering in spatial frequency domain imaging (SFDI) is presented. The use of a modified analytical solution of the radiative transfer equation allows calculation of the reflectance and the phase of a rough semi-infinite geometry so that both spatial frequency domain reflectance and phase can be applied for precise retrieval of the bulk optical properties and the surface scattering. For validation of the method, phantoms with different surface roughness were produced. Contrarily, with the modified theory, it was possible to dramatically reduce systematic errors due to surface scattering. The evaluation of these measurements with the state-of-the-art theory and measuring modality, i.e., using crossed linear polarizers, reveals large errors in the determined optical properties, depending on the surface roughness, of up to ≈100 % . These results were confirmed with SFDI measurements on a phantom that has a structured rough surface.

Effect of Surface Scattering of Electrons on Ratios of Optical Absorption and Scattering to Extinction of Gold Nanoshell.

Gold nanoshell's high light scattering and absorption at its resonance wavelength have found applications in biomedical imaging and photothermal therapy. However, at nanoscale, metallic material's dielectric function is affected by nanoparticle's size, mainly via a mechanism called surface scattering of conduction electrons. In this work, the effect of surface scattering of electrons on the ratios of optical absorption and scattering to extinction (which is the sum of the absorption and scattering) of gold nanoshell is investigated. Simulation results for several shell thicknesses are compared. It is found that the electrons' surface scattering increases the optical absorption ratio, and the thinner the shell thickness, the larger the increase in the difference of the absorption ratio between the situations with and without the surface scattering considered. The increase of absorption ratio is then verified by comparing simulation results to experimental measurements for three nanoshells. The parameters of the simulations to fit the experimental measurements show that the damping of conduction electrons in metallic shell geometry is larger than that predicted by the billiard scattering model.