Atomic Scale Research Articles

Terahertz spectroscopy of collective charge density wave dynamics at the atomic scale

AbstractCharge density waves are wave-like modulations of a material’s electron density that display collective amplitude and phase dynamics. The interaction with atomic impurities induces strong spatial heterogeneity of the charge-ordered phase. Direct real-space observation of phase excitation dynamics of such defect-induced charge modulation is absent. Here, by utilizing terahertz pump–probe spectroscopy in a scanning tunnelling microscope, we measure the ultrafast collective dynamics of the charge density wave in the transition metal dichalcogenide 2H-NbSe2 with atomic spatial resolution. The tip-enhanced electric field of the terahertz pulses excites oscillations of the charge density wave that vary in magnitude and frequency on the scale of individual atomic impurities. Overlapping phase excitations originating from the randomly distributed atomic defects in the surface create this spatially structured response of the charge density wave. This ability to observe collective charge order dynamics with local probes makes it possible to study the dynamics of correlated materials at the intrinsic length scale of their underlying interactions.

Frictional resistance and delamination mechanisms in 2D tungsten diselenide revealed by multi-scale scratch and in-situ observations

Friction phenomena in two-dimensional (2D) materials are conventionally studied at atomic length scales in a few layers using low-load techniques. However, the advancement of 2D materials for semiconductor and electronic applications requires an understanding of friction and delamination at a few micrometers length scale and hundreds of layers. To bridge this gap, the present study investigates frictional resistance and delamination mechanisms in 2D tungsten diselenide (WSe2) at 10 µm length and 100–500 nm depths using an integrated atomic force microscopy (AFM), high-load nanoscratch, and in-situ scanning electron microscopic (SEM) observations. AFM revealed a heterogenous distribution of frictional resistance in a single WSe2 layer originating from surface ripples, with the mean increasing from 8.7 to 79.1 nN as the imposed force increased from 20 to 80 nN. High-load in-situ nano-scratch tests delineated the role of the individual layers in the mechanism of multi-layer delamination under an SEM. Delamination during scratch consists of stick-slip motion with friction force increasing in each successive slip, manifested as increasing slope of lateral force curves with scratch depth from 10.9 to 13.0 (× 103) Nm−1. Delamination is followed by cyclic fracture of WSe2 layers where the puckering effect results in adherence of layers to the nanoscratch probe, increasing the local maximum of lateral force from 89.3 to 205.6 µN. This establishment of the interconnectedness between friction in single-layer and delamination at hundreds of layers harbors the potential for utilizing these materials in semiconductor devices with reduced energy losses and enhanced performance.

Study on the influence of rolling process parameters on the microscopic plastic deformation of nickel-based superalloy single crystal at atomic scale

Nickel-based superalloy workpieces strengthened by rolling process are widely used in the aviation field. However, there remains a need for further investigation into the influence of rolling parameters on the micro-plastic deformation of nickel-based superalloys. In this study, we establish micro-rolling and analysis models to investigate the impact of rolling parameters on nickel-based superalloy single crystals. We delve into the micro-effects of rolling depth, rolling speed, roller rotation speed, and roller radius. The micro-analysis model elucidates the influence mechanism of rolling parameters on nickel-based superalloy single crystals. The research methods and findings offer a novel microscopic perspective and approach for studying the strengthening of nickel-based superalloys through rolling. Additionally, they provide a microscopic theoretical foundation for optimizing rolling parameters.

Novel Class of Crystal/Glass Ultrafine Nanolaminates with Large and Tunable Mechanical Properties.

The control of local heterogeneities in metallic glasses (MGs) represents an emerging field to improve their plasticity, preventing the propagation of catastrophic shear bands (SBs) responsible for the macroscopically brittle failure. To date, a nanoengineered approach aimed at finely tuning local heterogeneities controlling SB nucleation and propagation is still missing, hindering the potential to develop MGs with large and tunable strength/ductility balance and controlled deformation behavior. In this work, we exploited the potential of pulsed laser deposition (PLD) to synthesize a novel class of crystal/glass ultrafine nanolaminates (U-NLs) in which a ∼4 nm thick crystalline Al separates 6 and 9 nm thick Zr50Cu50 glass nanolayers, while reporting a high density of sharp interfaces and large chemical intermixing. In addition, we tune the morphology by synthesizing compact and nanogranular U-NLs, exploiting, respectively, atom-by-atom or cluster-assembled growth regimes. For compact U-NLs, we report high mass density (∼8.35 g/cm3) and enhanced and tunable mechanical behavior, reaching maximum values of hardness and yield strength of up to 9.3 and 3.6 GPa, respectively. In addition, we show up to 3.6% homogeneous elastoplastic deformation in compression as a result of SB blocking by the Al-rich sublayers. On the other hand, nanogranular U-NLs exhibit slightly lower yield strength (3.4 GPa) in combination with enhanced elastoplastic deformation (∼6%) followed by the formation of superficial SBs, which are not percolative even at deformations exceeding 15%, as a result of the larger free volume content within the cluster-assembled structure and the presence of crystal/glass nanointerfaces, enabling to accommodate SB events. Overall, we show how PLD enables the synthesis of crystal/glass U-NLs with ultimate control of local heterogeneities down to the atomic scale, providing new nanoengineered strategies capable of deep control of the deformation behavior, surpassing traditional trade-off between strength and ductility. Our approach can be extended to other combinations of metallic materials with clear interest for industrial applications such as structural coatings and microelectronics (MEMS and NEMS).

Screw dislocation dipoles in niobium: combination of STM observations and atomistic simulations

Abstract We recently developed an experimental device that allows us to observe the slip traces under stress at the atomic scale. Here, we report experimental results obtained at the latter scale on Nb single crystals making it possible to observe dislocation dipoles, which are evidenced by two slip traces formed by emerging moving dislocations of opposite Burgers vectors ending very close to each other. The geometry and stability of the dislocation dipoles were fully characterized in the framework of linear anisotropic elasticity theory and by atomistic simulations. This allows us to calculate a local opposite stress impeding dislocation motion of the dislocations of the dipole.

Screw dislocation dipoles in niobium: combination of STM observations and atomistic simulations

Abstract We recently developed an experimental device that allows us to observe the slip traces under stress at the atomic scale. Here, we report experimental results obtained at the latter scale on Nb single crystals making it possible to observe dislocation dipoles, which are evidenced by two slip traces formed by emerging moving dislocations of opposite Burgers vectors ending very close to each other. The geometry and stability of the dislocation dipoles were fully characterized in the framework of linear anisotropic elasticity theory and by atomistic simulations. This allows us to calculate a local opposite stress impeding dislocation motion of the dislocations of the dipole.

Multiscale Simulation of CVD Diamond Growth on (1 0 0)‐, (1 1 1)‐, and (1 1 0)‐Oriented Faces

The growth of chemical vapor deposition diamond in microwave plasma ignited in H2/CH4 gas mixture is investigated using a multiscale approach. The plasma composition and temperatures are determined as a function of the growth conditions using an axial one‐dimensional simulator. The growth process is then studied at the atomic scale using a kinetic Monte‐Carlo simulator developed for (1 0 0), (1 1 1), and (1 1 0) orientations. The calculated growth rates are then injected in a geometric model that predicts the final morphology of the crystal. The simulation of the growth on an etch pit shows that the time necessary to entirely fill the pit is around half an hour. The study of the growth on the three orientations reveals that the surface temperature and methane concentration influence the number, shape, and size of the islands when they appear. On the (1 0 0) surface, the formation of islands may be related to Stranski–Krastanov growth mode, whereas the (1 1 1) surface conducts to Frank–van der Merwe growth mode, and the (1 1 0) surface is governed by Volmer–Weber growth mode.

Innovations of metallic contacts on semiconducting 2D transition metal dichalcogenides toward advanced 3D-structured field-effect transistors.

2D semiconductors, represented by transition metal dichalcogenides (TMDs), have the potential to be alternative channel materials for advanced 3D field-effect transistors, such as gate-all-around field-effect-transistors (GAAFETs) and complementary field-effect-transistors (C-FETs), due to their inherent atomic thinness, moderate mobility, and short scaling lengths. However, 2D semiconductors encounter several technological challenges, especially the high contact resistance issue between 2D semiconductors and metals. This review provides a comprehensive overview of the high contact resistance issue in 2D semiconductors, including its physical background and the efforts to address it, with respect to their applicability to GAAFET structures.

Sliding Memristor in Parallel-Stacked Hexagonal Boron Nitride.

Sliding ferroelectricity in 2D materials, arising from interlayer sliding-induced interlayer hybridization and charge redistribution at the van der Waals interface, offers a means to manipulate spontaneous polarization at the atomic scale through various methods such as stacking order, interfacial contact, and electric field. However, the practical application of extending 2D sliding ferroelectricity remains challenging due to the contentious mechanisms and the complex device structures required for ferroelectric switching. Here, a sliding memristor based on a graphene/parallel-stacked hexagonal boron nitride/graphene tunneling device, featuring a stable memristive hysteresis induced by interfacial polarizations and barrier height modulations, is presented. As the tunneling current density increases, the memristive window broadens, achieving an on/off ratio of ≈103 and 2 order decrease of the trigger current density, attributed to the interlayer migration of positively charged boron ions and the formation of conductive filaments, as supported by the theoretical calculations. The findings open a path for exploring the sliding memristor via a tunneling device and bridge the gap between sliding ferroelectricity and memory applications.

Enhancing microwave dielectric properties of Li4NbO4F for LTCC applications through tantalum ion doping

The atomic scale variation of tantalum ion doped Li4NbO4F ceramics is initially predicted through first principle calculations. Subsequently, Li4Nb(1-x)TaxO4F (0.00 ≤ x ≤ 0.10) ceramics are prepared using the solid phase reaction method. After sintering at 875 °C for 4hours, the Li4Nb0.96Ta0.04O4F ceramics exhibit optimum dielectric properties: εr = 14.73 ± 0.19, Q × f = 83,439 ± 2810GHz (@9.31GHz, improved by 41%), τf = - 28.33 ± 1.36 ppm/°C. Both the increase in relative density from 95.9 ± 0.32% to 96.2 ± 0.34% and the increase in grain size from 14.9 μm to 15.6 μm are non-intrinsic factors that contribute to the optimization of the dielectric properties. Instead, the internal factors suggest that the primary cause of the gradual decrease in εr is the redshift of the Raman wave number. The reduction in dielectric loss is attributable to the weakening of damping behavior, as well as the increase in lattice energy and electron cloud density. Finally, promising potential of Li4Nb0.96Ta0.04O4F ceramics for low-temperature co-fired ceramic (LTCC) applications is indicated by their favourable chemical compatibility with Ag electrodes.

At the Limit of Interfacial Sharpness in Nanowire Axial Heterostructures.

As semiconductor devices approach dimensions at the atomic scale, controlling the compositional grading across heterointerfaces becomes paramount. Particularly in nanowire axial heterostructures, which are promising for a broad spectrum of nanotechnology applications, the achievement of sharp heterointerfaces has been challenging owing to peculiarities of the commonly used vapor-liquid-solid growth mode. Here, the grading of Al across GaAs/AlxGa1-xAs/GaAs heterostructures in self-catalyzed nanowires is studied, aiming at finding the limits of the interfacial sharpness for this technologically versatile material system. A pulsed growth mode ensures precise control of the growth mechanisms even at low temperatures, while a semiempirical thermodynamic model is derived to fit the experimental Al-content profiles and quantitatively describe the dependences of the interfacial sharpness on the growth temperature, the nanowire radius, and the Al content. Finally, symmetrical Al profiles with interfacial widths of 2-3 atomic planes, at the limit of the measurement accuracy, are obtained, outperforming even equivalent thin-film heterostructures. The proposed method enables the development of advanced heterostructure schemes for a more effective utilization of the nanowire platform; moreover, it is considered expandable to other material systems and nanostructure types.

RevGraphVAMP: A protein molecular simulation analysis model combining graph convolutional neural networks and physical constraints

Molecular simulation (MD) is a crucial research domain within the life sciences, focusing on comprehending the mechanisms of biomolecular interactions at atomic scales. Protein simulation, as a critical subfield, often utilizes MD for implementation, with trajectory data play a pivotal role in drug discovery. The advancement of high-performance computing and deep learning technology becomes popular and critical to predict protein properties from vast trajectory data, posing challenges regarding data features extraction from the complicated simulation data and dimensionality reduction. Simultaneously, it is essential to provide a meaningful explanation of the biological mechanism behind dimensionality. To tackle this challenge, we propose a new unsupervised model named RevGraphVAMP to intelligently analyze the simulation trajectory. This model is based on the variational approach for Markov processes (VAMP) and integrates graph convolutional neural networks and physical constraint optimization to enhance the learning performance. Additionally, we introduce attention mechanism to assess the importance of key interaction region, facilitating the interpretation of molecular mechanism. In comparison to other VAMPNets models, our model showcases competitive performance, improved accuracy in state transition prediction, as demonstrated through its application to two public datasets and the Shank3-Rap1 complex, which is associated with autism spectrum disorder. Moreover, it enhanced dimensionality reduction discrimination across different substates and provides interpretable results for protein structural characterization.

Tunable Multistate Ferroelectricity of Unit-Cell-Thick BaTiO3 Revived by a Ferroelectric SnS Monolayer via Interfacial Sliding.

Stabilization of multiple polarization states at the atomic scale is pivotal for realizing high-density memory devices beyond prevailing bistable ferroelectric architectures. Here, we show that two-dimensional ferroelectric SnS or GeSe is able to revive and stabilize the ferroelectric order of three-dimensional ferroelectric BaTiO3, even when the latter is thinned to one unit cell in thickness. The underlying mechanism for overcoming the conventional detrimental critical thickness effect is attributed to facile interfacial inversion symmetry breaking by robust in-plane polarization of SnS or GeSe. Furthermore, when invoking interlayer sliding, we can stabilize multiple polarization states and achieve efficient interstate switching in the heterostructures, accompanied by dynamical ferroelectric skyrmionic excitations. When invoking sliding and twisting, the moiré domains exhibit nontrivial polar vortexes, which can be laterally displaced via different sliding schemes. These findings provide an intuitive avenue for simultaneously overcoming the standing critical thickness issue in bulk ferroelectrics and weak polarization issue in sliding ferroelectricity.

Insights into in situ surface reconstruction in cobalt perovskite oxides for enhanced catalytic activity

An depth understanding of the fundamental interactions between surface termination and catalytic activity is crucial to prompt the properties of functional perovskite materials. The elastic energy due to size mismatch and electrostatic attraction of the charged Sr dopant by positively charged oxygen vacancies induced inert A-site surface enrichment rearrangement for perovskites. Lower temperatures could reduce A-site enrichment, but it is difficult to form perovskite crystals. La0.8Sr0.2CoO3-δ (LSCO) as a model perovskite oxide was modified with additive urea to reduce the crystallization temperature, and suppress Sr segregation. The LSCO catalysts with 600 °C annealing temperature (LSCO-600) exhibited a 19.4-fold reaction reactivity of toluene oxidation than that with 800 °C annealing temperature (LSCO-800). Combined surface-sensitive and depth-resolved techniques for surface and sub-surface analysis, surface Sr enrichment was effectively suppressed due to decreased oxygen vacancy concentration and smaller electrostatic driving force. DFT calculations and in-situ DRIFTs spectra well revealed that tuning the surface composition/termination affected the intrinsic reactivity. The catalyst surface with lower Sr enrichment could easily adsorb toluene, cleave, and decompose benzene rings, thus contributing to toluene degradation to CO2. This work demonstrates a green and efficient way to control surface composition and termination at the atomic scale for higher catalytic activity.

Anisotropy Dependence of Material Deformation Mechanisms in Nanoscratching Monocrystalline BaF2: Experiments and Atomic Simulations.

Monocrystalline barium fluoride (BaF2), known for its exceptional optical properties in the infrared spectrum, exhibits anisotropy that influences surface quality and material removal efficiency during ultraprecision machining. This research explores the impact of anisotropy on the deformation and removal mechanisms of monocrystalline BaF2 by integrating nanoscratch tests with molecular dynamics (MD) simulations. Nanoscratch tests conducted on variously oriented monocrystalline BaF2 surfaces using a ramp loading mode facilitated the identification of surface cracks and a systematic description of material removal behaviors. This study elucidates the effect of crystal orientation on the ductile-brittle transition (DBT) of monocrystalline BaF2, further developing a critical depth prediction model for DBT on the (111) crystal plane to reveal the underlying anisotropy mechanisms. Moreover, nanofriction and wear behaviors in monocrystalline BaF2 are found to be predominantly influenced by scratch direction, crystal surface, and applied load, with the (110) and (100) planes showing pronounced frictional and wear anisotropy. A coefficient of friction model, accounting for the material's elastic recovery, establishes the intrinsic relationship between anisotropic friction and wear behaviors, the size effect, and scratch direction. Lastly, MD modeling of nanoscratched monocrystalline BaF2 reveals the diversity of dislocations and strain distributions along the (111) [-110] and [-1-12] crystal directions, offering atomic scale insights into the origins of BaF2 anisotropy. Thus, this study provides a theoretical foundation for the efficient processing of fluorine-based infrared optic materials exhibiting anisotropy.

Atomic scale insights on mechanical behavior and crack propagation in Mg-Al based nanolaminates

In this paper, the mechanical properties and plastic deformation mechanisms of Mg25Al75 metallic glass (MG) and three Mg-Al based nanoscale crystal/glass nanolaminates (NCGNLs) during crack propagation under tension loading are investigated using Molecular Dynamics (MD) simulations. The results observed in NCGNLs are compared with those related to pure MG to determine the effect of the NCGNLs on material strength and fracture toughness. The results show that the NCGNLs have a higher Young's modulus (E) and ultimate tensile strength (UTS) compared to pure MG. Which mean that the heterogeneous interphase between the crystalline layers and the amorphous pure glass behaves as the barriers behind the plastic deformation. Nano-patterning involving Aluminum (Al) and Magnesium (Mg) positively affects the fracture toughness of the material, while Mg25Al75/glass NCGNLs was found to be the most brittle and most prone to failure under tensile strain. The Al/glass NCGNLs is found to be the most ductile and able to withstand higher levels of strain before cracking. The simulations also reveal the deformation mechanisms at the atomic level, showing the nucleation/emission of dislocations types, twin boundary (TB), and stacking faults (SF) from the amorphous layer and their propagation to the Mg and Al crystal phases, respectively. These findings provide valuable insights into the mechanical properties of Mg-Al based nanolaminates and can inform the design of stronger and more durable materials.

Versatile fitting approach for operando spectroscopic imaging ellipsometry of HfS2 oxidation

Facile mapping of 2D heterostructures and resolving anisotropic formation kinetics down to the monolayer level are critical to developing scalable interfacing solutions and unlocking their application potential in emerging nano-optoelectronics. We adapt a Kramers–Kronig constrained variational fitting algorithm for spectroscopic imaging ellipsometry (SIE) to facilitate multi-scale heterostructure analysis comprising films with unknown complex dielectric functions and demonstrate how this enables non-destructive, scalable mapping and operando capability for the model system of HfS2 oxidation. This methodology proves highly accurate for assessing the thickness of buried HfS2 layers, oxide quality, and lateral and vertical uniformity. We capture dynamic stack evolution during thermal oxidation up to 400 ∘C, providing insights into the temperature and time-dependent nature of self-limiting oxide growth and reaction kinetics that involve the localised trapping and release of sulphur reaction products. Our methodology is versatile in material and device horizons, and advantageously agnostic to the underlying substrate. Combined with the various modes of SIE operation, it unlocks fast, high-throughput, large-area capability to accelerate process development at the atomic scale.

On the formation trajectory of diverse corrosion morphologies associated with T phases in an Al-Cu-Li alloy

Four different types of localized corrosion morphologies associated with Al20Cu2Mn3 dispersoids (T phases) in an AA2195 alloy were traced using atom-resolved characterizations and quasi-in-situ experiments. At the atomic scale, we demonstrated that the rod-shaped T dispersoid is homogeneous within the grain but enriched with Cu on the side surfaces, leading to a depletion of T1 precipitates nearby and an abundance near the tips. This plays a significant role in the initiation of galvanic corrosion between T dispersoids and the matrix. Combined with heterogeneous nucleation, the subsequent redeposition of noble metal clusters results in four typical corrosion morphologies.

Design, preparation, and enhanced mechanical properties of novel plate-like grains toughened (Zr, Ti, W, Ta)C medium-entropy ceramics fabricated by in-situ reaction hot-pressing

Novel plate-like (Ti, Zr)B2 toughened (Zr, Ti, W, Ta)C medium-entropy ceramics were designed based on the atomic scale, nanoscale, and microscale, and prepared via the in-situ reaction hot-pressing adopting (Ti, W, Ta)C and ZrB2 powders. The multiphase ceramics were primarily composed of the (Zr, Ti, W, Ta)C matrix and plate-like (Ti, Zr)B2. When the addition of ZrB2 exceeds 50 mol%, the residual ZrB2 causes the secondary primary phase to change from (Ti, Zr)B2 to (Zr, Ti)B2. The improvement of fracture toughness is primarily influenced by the plate-like (Ti, Zr)B2 on crack propagation mechanisms such as bridging effect and crack deflection. (Ti, W, Ta)C- 50 mol% ZrB2 (raw powder composition) exhibits outstanding mechanical properties, boasting a Vickers hardness of 24.9 GPa, fracture toughness of 5.5 MPa·m1/2, and flexural strength of 552 MPa, which present a novel avenue for achieving a synergistic enhancement in Vickers hardness and fracture toughness within medium-entropy carbide ceramics.

Influence of water on the machinability of calcium fluoride crystal

Calcium fluoride (CaF2) optical components are produced by ultra-precision machining, but the often-neglected ambient water may potentially affect its processing. This work provides a systematic study on the role of water in the machinability of single-crystal CaF2. Micro-scratching experiments revealed poor machinability and reduced deformability under water adsorption. Atomic scratching simulations reproduced the mechanical deformation and identified the enhancement in dislocation nucleation with water, which led to the reduction in deformability due to dense cross-linking of dislocations. Atomic scale cutting simulations also identified easier formation of subsurface cracks under water adsorption. With the aid of mechanical schematic models based on the simplification of the scratching process, this work revealed that while water enhances the plastic flow of the material during machining, the accumulation of dislocations creates stress conditions sufficient to induce material fracture, which is a unique influence of water adsorption on the reduction in machinability of CaF2.