Surface Steps Research Articles

Dependence of Growth Parameters of Atomic Chains on Changes in the Substrate Temperature

The growth and evolution of one-dimensional nanostructures on metal stepped surfaces were studied using the kinetic Monte Carlo method. The distribution of nanochain lengths was shown to change differently when the substrate was heated and cooled. Regularities are described that connect the nature of changes in the length distribution and the relative values of diffusion barriers for adatoms on the surface, which will make it possible to predict the length distribution of the resulting one-dimensional nanostructures.

Interplay between Topological States and Rashba States as Manifested on Surface Steps at Room Temperature.

The unique spin texture of quantum states in topological materials underpins many proposed spintronic applications. However, realizations of such great potential are stymied by perturbations, such as temperature and local fields imposed by impurities and defects, that can render a promising quantum state uncontrollable. Here, we report room-temperature scanning tunneling microscopy/spectroscopy observation of interaction between Rashba states and topological surface states, which manifests local electronic structure along step edges controllable by the layer thickness of thin films. The first-principles theoretical calculation elucidates the robust Rashba states coexisting with topological surface states along the surface steps with characteristic spin textures in momentum space. Furthermore, the Rashba edge states can be switched off by reducing the thickness of a topological insulator Bi2Se3 to bolster their interaction with the hybridized topological surface states. The study unveils a manipulating mechanism of the spin textures at room temperature, reinforcing the necessity of thin film technology in controlling the quantum states.

Steric Effect and Intrinsic Electrophilicity and Nucleophilicity from Conceptual Density Functional Theory and Information-Theoretic Approach as Quantitative Probes of Chemical Reactions.

Appreciating reactivity in terms of physicochemical effects for chemical processes is one of the most important undertakings in chemistry. While transition state (TS) theory provides the framework enabling the reliable calculation of the barrier height for a given elementary step, analytical tools are necessary to gain insight into key factors governing the different processes during chemical reactions. In this contribution, we partition the potential energy surface of an elementary step along the intrinsic coordinate into three segments, the so-called Pre-TS, TS, and Post-TS regions, and then determine the most important factors dictating each segment. This analysis is based on the use of both reactivity descriptors from conceptual density functional theory and concepts from the information-theoretic approach in density functional theory. We found that in both Pre-TS and Post-TS regions, steric effects are the dominant factors, whereas in the TS region, it is the intrinsic electrophilic and nucleophilic propensity of the transition state structure that governs the reactivity. The wide applicability of our approach is shown by a validation for a total of 37 organic and inorganic reactions. Different partition approaches from density functional theory, energy decomposition analysis and wavefunction-based resonance theory are employed to support our main conclusions.

Printing of Random Patterns on Stepped Surfaces Using Speckle Lithography

Printing of Random Patterns on Stepped Surfaces Using Speckle Lithography

Probing water adsorption characteristics of Pt step-edge decorated Cu(211) surface

The surface structure and atomic composition can affect the adsorption characteristics of water on metal surfaces. In this study, we investigated the adsorption of water on Cu(211) stepped surfaces decorated with Pt by a combination of infrared reflection absorption spectroscopy (IRRAS) and temperature-programmed desorption (TPD) studies. We have observed that step sites of Cu can increase the strength of the binding of water molecules to the surface and facilitate water partial dissociation and the formation of OH groups on the surface. Step decoration by Pt can change the water adsorption characteristics and eliminate the water dissociation. Water adsorbs molecularly on the fully Pt-decorated steps of the Cu(211) surface. Molecular water and OH adsorbed on Cu(211), which can make a chain structure, are disrupted with Pt atoms.

영남지역 신라·가야 토성의 축조기술

Research on Silla and Gaya Earthen Fortification in Yeongnam Area has grown quantitatively and qualitatively enough to enable comprehensive analysis thanks to the recent accumulation of survey results. Accordingly, the characteristics of each construction process were analyzed for 6 sites of Silla and 7 sites of Gaya, and were compared by synthesizing them. Both Silla and Gaya Organic matter such as the Leaf mat method and the designated pile were used in the low wetland or soft ground, and the frictional force was maximized by using a stepped or uneven surface stopping method on the slope. In particular, in the case of the embankment technique, by setting the soil of the narrow-type embankment technique through the cases of Wolseong and Bonghwangtoseong, there was a result of subdividing it into a narrow-type (A1) and a flat-type (A2). Gaya is reinforced by adding a stone shaft part during the construction of the reinforcement of the wall or the finishing of the reinforcement wall of the construction of the wall. The longer the plate mass, which was created by repeated dismantling and re-installing the plate shaft structure, is another peculiarity of Gaya. This may be a primitive form of the phenomenon of increasing the length of the plate mass in the “Gidanseokryeol plate shaft fortress” stage that appears after the “pure plate shaft fortress”. Therefore, it is noteworthy that it is located as a technical and historical link in the transformation of the fortress construction technology.

Theoretical study of structure sensitivity on ceria-supported single platinum atoms and its influence on carbon monoxide adsorption.

Density functional theory (DFT) calculations explore the stability of a single platinum atom on various flat, stepped, and defective ceria surfaces, in the context of single-atom catalysts (SACs) for the water-gas shift (WGS) reaction. The adsorption properties and diffusion kinetics of the metal strongly depend on the support termination with large stability on metastable and stepped CeO2(100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO2(111) and (110) terminations weakly bind the platinum atom and can promote the growth of metallic clusters thanks to fast diffusion kinetics. The adsorption of carbon monoxide on the single platinum atom supported on the various ceria terminations is also sensitive to the surface structure. Carbon monoxide weakly binds to the single platinum atom supported on reduced CeO2(111) and (211) terminations. The desorption of the CO2 formed during the WGS reaction is thus facilitated on the latter terminations. A vibrational analysis underlines the significant changes in the calculated scaled anharmonic CO stretching frequency on these catalysts.

Effect of Dynamic and Preferential Decoration of Pt Catalyst Surfaces by WOx on Hydrodeoxygenation Reactions.

Catalysts containing Pt nanoparticles and reducible transition-metal oxides (WOx, NbOx, TiOx) exhibit remarkable selectivity to aromatic products in hydrodeoxygenation (HDO) reactions for biomass valorization, contrasting the undesired aromatic hydrogenation typically observed for metal catalysts. However, the active site(s) responsible for the high selectivity remains elusive. Here, theoretical and experimental analyses are combined to explain the observed HDO reactivity by interrogating the organization of reduced WOx domains on Pt surfaces at sub-monolayer coverage. The SurfGraph algorithm is used to develop model structures that capture the configurational space (∼1000 configurations) for density functional theory (DFT) calculations of a W3O7 trimer on stepped Pt surfaces. Machine-learning models trained on the DFT calculations identify the preferential occupation of well-coordinated Pt sites (≥8 Pt coordination number) by WOx and structural features governing WOx-Pt stability. WOx/Pt/SiO2 catalysts are synthesized with varying W loadings to test the theoretical predictions and relate them to HDO reactivity. Spectroscopy- and microscopy-based catalyst characterizations identify the dynamic and preferential decoration of well-coordinated sites on Pt nanoparticles by reduced WOx species, consistent with theoretical predictions. The catalytic consequences of this preferential decoration on the HDO of a lignin model compound, dihydroeugenol, are clarified. The effect of WOx decoration on Pt nanoparticles for HDO involves WOx inhibition of aromatic ring hydrogenation by preferentially blocking well-coordinated Pt sites. The identification of preferential decoration on specific sites of late-transition-metal surfaces by reducible metal oxides provides a new perspective for understanding and controlling metal-support interactions in heterogeneous catalysis.

Testing functional anchor groups for the efficient immobilization of molecular catalysts on silver surfaces

Modifications of complexes by attachment of anchor groups are widely used to control molecule-surface interactions. This is of importance for the fabrication of (catalytically active) hybrid systems, viz. of surface immobilized molecular catalysts. In this study, the complex fac-Re(S-Sbpy)(CO)3Cl (S-Sbpy = 3,3′-disulfide-2,2′-bipyridine), a sulfurated derivative of the prominent Re(bpy)(CO)3Cl class of CO2 reduction catalysts, was deposited onto the clean Ag(001) surface at room temperature. The complex is thermostable upon sublimation as supported by infrared absorption and nuclear magnetic resonance spectroscopy. Its anchoring process has been analyzed using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The growth behavior was directly contrasted to the one of the parent complex fac-Re(bpy)(CO)3Cl (bpy = 2,2′-bipyridine). The sulfurated complex nucleates as single molecule at different surface sites and at molecule clusters. In contrast, for the parent complex nucleation only occurs in clusters of several molecules at specifically oriented surface steps. While this shows that surface immobilization of the sulfurated complex is more efficient as compared to the parent, symmetry analysis of the STM topographic data supported by DFT calculations indicates that more than 90% of the complexes adsorb in a geometric configuration very similar to the one of the parent complex.

Effect of a Physisorbed Tetrabutylammonium Cation Film on Alkaline Hydrogen Evolution Reaction on Pt Single-Crystal Electrodes.

The addition of tetrabutylammonium (TBA+) to alkaline electrolytes enhances the hydrogen evolution reaction (HER) activity on Pt single-crystal electrodes. The concentration of TBA+ significantly influences the HER on Pt(111). Concentrations of ≤1 mM yield no significant effect on HER currents or the coverage of adsorbed hydrogen (H*) but exhibit an interaction with the OHads on the surface. Conversely, concentrations of >1 mM result in an apparent site-blocking effect for underpotential-deposited H* caused by the physisorption of the organic cation, which counterintuitively leads to an increase in the HER activity. The physisorption of TBA+ is linked to its accumulation in the diffuse layer, as it can be reversibly removed by the addition of nonadsorbing cations such as sodium. Following the previous literature on the TBA+ interaction with electrode surfaces, we ascribe this effect to the formation of a two-dimensional TBA+ film in the double layer. On stepped Pt single-crystal surfaces, TBA+ enhances HER activity at all concentrations, primarily at step sites. Our findings not only highlight the complexities of TBA+ accumulation on Pt electrodes but also offer important molecular-level insights for optimizing the HER by organic film formation on various atomic-level electrode structures.

Origin of the surface facet dependence in the thermal degradation of the diamond (111) and (100) surfaces in vacuum investigated by machine learning molecular dynamics simulations

We perform machine learning molecular dynamics simulations to gain an atomic-level understanding of the dependence of the graphitization and thermal degradation behavior of diamond to the (111) and (100) surface facets. The interatomic potential is constructed using graph neural network model, trained using energies and forces from spin-polarized van der Walls-corrected density functional theory calculations. Our results show that the C(111) surface is more susceptible to thermal degradation, which occurs from 2850 K through synchronized bilayer exfoliation mechanism. In comparison, the C(100) surface thermally degrade from a higher temperature of 3680 K through the formation of sp1 carbon chains and amorphous sp2-sp3 carbon network. Due to the dangling bonds at the step edges, the stepped surfaces are more susceptible to thermal degradation compared to the corresponding flat surfaces, with the stepped C(111) and C(100) surfaces thermally degrading from 1810 K and 3070 K, respectively. We propose potential applications of this study in diamond tool wear suppression, diamond polishing, and production of graphene directly from the diamond surface.

Molecular dynamics simulation of fatigue damage formation in single-crystal/polycrystalline aluminum

The fatigue plasticity mechanisms and local defect characteristics of engineering materials are critical for addressing fatigue damage. This study aims to identify the formation mechanisms of fatigue damage and delineate the microstructural characteristics that resisted or facilitated fatigue-induced plastic accumulation. The fatigue mechanical properties and microstructural evolution processes of single-crystal/polycrystalline aluminum were investigated through strain-controlled fatigue testing, considering three distinct strain amplitudes. The initiation and cumulative occurrence of local plasticity in single-crystal aluminum occur at the intersections of slip planes, which serve as sources of dislocations. The cumulative formation of irreversible surface steps results in local stress concentration, ultimately leading to fatigue damage at the free surface. Polycrystalline aluminum undergoes grain rotation and merging during cyclic loading, leading to a gradual increase in grain size during plastic deformation. The initiation and cumulative occurrence of local plasticity occur at grain boundaries, ultimately leading to fatigue damage at the grain boundaries.

Deep ensemble learning for material removal rate prediction in chemical mechanical planarization with pad surface topography

Chemical mechanical planarization (CMP) stands as a critical process in semiconductor manufacturing, necessitating precise prediction of material removal rate (MRR) to achieve optimal global planarization of material surface step heights. A notable hurdle in MRR prediction lies in the nonlinear pad-wafer interaction stemming from variations in the polishing pad surface. Despite numerous extant studies examining the asperity of the pad surface and the wafer-pad contact, aspects such as slurry lubrication and micro-topographical structure of the pad surface remain unaddressed. This study firstly proposes a deep ensemble learning-based approach for MRR prediction, leveraging the intricate interactions between the overall features of the pad surface and the polishing pressure. We experimentally generated diverse pad surfaces by controlling the process variables governing pad surface topography. The Multi-TabNet model, constructed by independently training multiple TabNet instances with distinct initialization and hyperparameters, furnishes a framework for MRR prediction across a broad spectrum of pad surface features, encompassing pores and cores. The results demonstrate a root mean square error of 80 Å/min, with the error margin reduced by up to 70 % compared to predictions utilizing a single parameter of the pad surface. Furthermore, it exhibits an error improvement exceeding 17 % relative to the existing method solely considering asperity. This study not only imparts insights for addressing MRR variations contingent on pad condition but also facilitates dependable material removal even on variable pad surfaces due to conditioner wear.

Autogenic shrinkage and channel destabilization of an overexpanded downstream alluvial system under steady rise of relative sea level: An experimental study

The dynamics of downstream alluvial systems undergoing relative sea level (RSL) rise exhibit significant variations depending on spatial size. According to autostratigraphy theory, such systems cannot sustain deltaic sedimentation under a steady RSL rise (rate Rslr), and are prone to non-deltaic transgression once their plain area A exceeds the critical limit Acrt. During this transgression, A decreases asymptotically toward Acrt, while the overall alluvial aggradation rate Ragg_overall increases toward Rslr. In this study, we investigated the behavior and morphodynamics of an overexpanded system through physical modeling, with a focus on the inherent area scale of the depositional system. In the early stages of non-deltaic transgression (A >> Acrt, Ragg_overall << Rslr), the alluvial channels experience minimal aggradation rate Ragg_channel (< Rslr), leading to stabilization and inundation. As the transgression progresses, the channels aggrade more rapidly, increasing the likelihood of lateral migration and avulsion. Eventually, a state of morphodynamic equilibrium is reached, characterized by A ∼ Acrt, Ragg_overall ∼ Rslr, and Ragg_channel ∼ constant > Rslr despite sustained non-deltaic transgression. During this equilibrium stage, the channels undergo rapid aggradation, resulting in complete destabilization with continuous lateral migration and frequent avulsion, forming system-wide subaqueous steps. The implications of overexpansion and autogenic shrinkage in response to RSL rise extend to stratigraphic convergence during RSL cycles and provide insights into Holocene non-deltaic transgression. Moreover, when combined with decelerating RSL rise, this process could have facilitated marine delta development. However, projected accelerated RSL may lead many modern marine deltas to transition into non-deltaic transgressive systems. Additionally, natural alluvial channels may exhibit varying behavior depending on the spatial size of the non-deltaic transgressive system. Furthermore, the autogenic shrinkage model may offer an explanation for the stepped surfaces observed on alluvial fans and deltas on Mars.

Variation of (001) surface structures of strontium titanate single crystals caused by flash event under direct/alternative current electric fields

Flash events, which are electric power spikes occurring under an electric field and temperature above the threshold, can significantly accelerate mass diffusion over short periods of time. This study investigated the surface structure of the (001) surface of strontium titanate single-crystal treated by flash events caused by direct current (DC) and alternating current (AC) electric fields from a viewpoint of surface-related mass diffusion. The surface structuring caused by flash events was significantly different among DC and AC electric fields. The DC-flash event destabilized surface steps, causing them to wander and form surface mounds with a height of several tens of nanometers. In addition, numerous two-dimensional (2D) nuclei with a size of several nanometers are formed on the terraces. In contrast, the AC-flash event stabilized surface steps without the formation of surface mounds, causing them nearly straight with uniform terrace width at approximately 500 nm. 2D nuclei with a size of a few 10 nm were formed at the step edges with round shapes. Both methods were confirmed as evidenced by the formation of two-dimensional nuclei on the surface after the flash events, to enhance surface-related mass diffusion.

Flapping dynamics of a flexible membrane attached to the leading edge of a forward-facing step

The flapping dynamics of a flexible membrane (FM) and its effect on the flow fields over and pressure fluctuations on a forward-facing step (FFS) have been investigated experimentally. The two-dimensional FM with 40 mm in length and 0.15 mm in thickness was vertically attached to the leading edge of a FFS with 40 mm in height. The deformation of the flapping FM was recorded by a high-speed camera. Velocity data in the vertical central plane and the pressure fluctuations on the step surface were measured by planar particle image velocimetry and pressure sensors, respectively. The results demonstrate that as the dimensionless bending rigidity (γ) of the FM decreases, the FM displayed two distinct modes, i.e., the bending mode and the flapping mode. In the bending mode, the bent FM is similar to a curved barrier, which elevates the shear layer and delays the reattachment of separation flow. In the flapping mode, the amplitude of the FM increases with the decrease in γ, which in turn effects the scale of flapping-induced vortices (FIVs). In proper orthogonal decomposition analysis, the results reveal a transition in the dominant flow structure from large-scale separation to FIVs with reducing γ. The FIVs significantly affect the pressure distribution on the step surface of the FFS, and the range where the coherent contribution dominates expands with the decreasing γ.

Room-Temperature Antisymmetric Magnetoresistance in Van Der Waals Ferromagnet Fe3GaTe2 Nanosheets.

Van der Waals (vdW) ferromagnetic materials have emerged as a promising platform for the development of 2D spintronic devices. However, studies to date are restricted to vdW ferromagnetic materials with low Curie temperature (Tc) and small magnetic anisotropy. Here, a chemical vapor transport method is developed to synthesize a high-quality room-temperature ferromagnet, Fe3GaTe2 (c-Fe3GaTe2), which boasts a high Tc = 356 K and large perpendicular magnetic anisotropy. Due to the planar symmetry breaking, an unconventional room-temperature antisymmetric magnetoresistance (MR) is first observed in c-Fe3GaTe2 devices with step features, manifesting as three distinctive states of high, intermediate, and low resistance with the sweeping magnetic field. Moreover, the modulation of the antisymmetric MR is demonstrated by controlling the height of the surface steps. This work provides new routes to achieve magnetic random storage and logic devices by utilizing the room-temperature thickness-controlled antisymmetric MR and further design room-temperature 2D spintronic devices based on the vdW ferromagnet c-Fe3GaTe2.

Experimental study on a solar-powered cogeneration system for freshwater and electricity production.

In this study, a photovoltaic/thermal (PVT) collector and a stepped solar still system were constructed and integrated. The PVT collector was used to improve the performance of a stepped solar still device. Saltwater enters into the PV-T system and the temperature of the solar panel declines, and then ultimately the efficiency of the PV-T collector increases. After leaving the PVT collector, the temperature of the saltwater increased and was used as a pre-heater for further evaporation in the solar still, which ultimately caused an increase in its efficiency. The more tremendous temperature difference generated between the stepped surface and the glass increases efficiency and produces more freshwater. A flow rate of 7.5 L/hour of saline water was used to study the efficiency of the solar still device and the PVT collector. The value of productivity of solar still system with photovoltaic/thermal collector was 0.76kg/m2 more than that of conventional solar still. Despite the PVT collector, the daily efficiency of the solar still system increased to 34.8%, which shows an increase of 13.9% compared to the passive solar still device. Also, by cooling the PV-T system, the average electrical efficiency has increased from 13.1 to 13.7%. Production power reached 72.46 W from 65.96 W in two consecutive days at 11:15.

Synthesis of Cd-Cu nanoparticles supported on HOPG for use as electrocatalytic material for nitrate reduction

Bimetallic nanoparticles application has attracted great attention in the field of electrocatalysis because they can enhance the catalytic properties toward certain reactions of technological interest, such as nitrate reduction. For this purpose, Cd-Cu bimetallic nanoparticles were prepared on highly oriented pyrolytic graphite substrates by sequential electrodeposition of both metals. The process was studied by conventional electrochemical techniques, and the generated deposits were characterized by scanning electron microscopy − energy dispersive X-ray spectroscopy analysis. Initially, Cu nanoparticles were prepared by a simple potentiostatic pulse applied to the carbonaceous substrate. Scanning electron microscopy images showed high density of mainly hemispherical-shaped Cu crystals distributed preferably on step edges and surface defects of the highly oriented pyrolytic graphite electrode. Subsequently, Cd particles were prepared in the same way by immersing the Cu nanoparticles / highly oriented pyrolytic graphite modified substrate in an electrolyte solution containing Cd2+ ions, exploiting the phenomenon of underpotential deposition. It was evidenced that the existing crystals grew in size, most of them showing the typical shapes of those for Cd nanoparticles. The application of the Cd-Cu nanoparticles / highly oriented pyrolytic graphite electrode as a feasible electrocatalyst material for nitrate reduction was investigated by cyclic voltammetry for different nitrate concentrations, also considering the possibility of using this procedure as a method for the anion detection.

Mechanisms of anisotropic fracture resistance of nacreous structure and design: Essential role of cracking modes of organic interfaces

Nacreous structure holds significant promise for biomimetic design applications due to its excellent mechanical properties. In this paper, the influence of loading direction on the mechanical properties of nacreous structure was investigated to understand its mechanisms of anisotropic fracture resistance. The results revealed significant anisotropy in the mechanical properties of nacre when loaded along different directions (perpendicular to y and z axes). When loaded perpendicular to the top face, nacre exhibits better mechanical properties and greater resistance to fracture compared to loading perpendicular to the side face. This distinction can be attributed to different cracking modes of organic interfaces in nacreous structure, where the nacreous structure loaded perpendicular to the top face exhibits more tortuous crack deflection, larger fracture stepped surface area and microcrack zones. Furthermore, the theoretical analysis indicates that the differences in the volume fraction of organic interfaces and the main crack deflection along organic interfaces are important factors leading to different cracking modes of organic interfaces in nacreous structure. Based on the analysis of the mechanisms of anisotropic fracture resistance, the critical parameters to characterize the anisotropic mechanical properties of the nacreous structure were proposed. The research results provide a reference and basis for future biomimetic application design.