Atomic Terraces Research Articles

Resistivity as a Witness of Local Crystal Growth Conditions

A detailed knowledge of the growth front geometry during physical vapor transport (PVT) growth of SiC single crystals is beneficial to achieve high quality n+ SiC substrates for power device applications. In this report we show how mapping of resistivity in SiC wafers can shed light on local growth conditions, which are very difficult-to-study in situ. We consider both thermodynamic quantities (absolute temperature T and partial pressure pN₂) and geometric characteristics of the growth surface relevant to growth kinetic parameters, namely atomic terrace width and atomic step velocity. Specifically, we show how an elevation map of the growth surface can be reconstructed from a spatially-resolved measurement of resistivity in a SiC wafer by integrating the spatial derivative of elevation with respect to the basal plane, which is assumed to be related to local resistivity through dependence of non-equilibrium nitrogen incorporation on the atomic step velocity.

Directional growth of iron oxide nanowires on a vicinal copper surface

Single-crystal magnetic nanostructures with well-defined shapes attract lots of interest due to their potential applications in magnetic and spintronic devices. However, development of methods allowing controlling their mutual crystallographic and geometric orientation constitutes a significant scientific challenge. One of the routes for obtaining such structures is to grow the materials epitaxially on naturally-structured supports, such as vicinal surfaces of single-crystal substrates. Iron oxides are among the most well-known magnetic materials which, depending on the phase, may exhibit ferro/ferri- or antiferromagnetic ordering. We have grown iron oxide nanowires on a Cu(410) single-crystal substrate faceted with molecular oxygen. Scanning tunneling microscopy and low energy electron diffraction revealed that the oxide grows in the [111] direction, along the step edges of the substrate and rotated by ±15° with respect to the [010] direction of copper atomic terraces (so that the the growing elongated structures are orientated parallel to each other). Notably, x-ray photoelectron spectroscopy confirmed that the nanowires represent the ferrimagnetic γ-Fe2O3 (maghemite) iron oxide phase, while micromagnetic simulations indicated that the wires are single-domain, with the easy magnetization axis orientated in-plane and along the long axis of the wire.

Bismuth surfactant enhancement of surface morphology and film quality of MBE-grown GaSb(100) thin films over a wide range of growth temperatures

We investigate the surface morphologies of two series of homoepitaxial GaSb(100) thin films grown on GaSb(100) substrates by molecular beam epitaxy in a Veeco GENxplor system. The first series was grown at temperatures ranging from 290 to 490°C and serves as a control. The second series was grown using the same growth parameters with bismuth used as a surfactant during growth. We compared the two series to examine the impacts of bismuth over the range of growth temperatures on the GaSb surface morphologies using atomic force microscopy and the film properties using Raman spectroscopy and scanning electron microscopy. High-resolution x-ray diffraction was performed to confirm that bismuth was not incorporated into the films. We found that the morphological evolution of the GaSb series grown without bismuth is consistent with the standard surface nucleation theory and identified the 2D-3D transition temperature as close to 290° C. In contrast, the presence of a Bi surfactant during growth was found to significantly alter the surface morphology and prevent undesired 3D islands at low temperatures. We also observed a preference for hillocks over step morphology at high growth temperatures, antistep bunching effects at intermediate temperatures, and the evolution from step-meandering to mound morphologies at low temperatures. This morphological divergence from the first series indicates that bismuth significantly increases in the 2D Erlich–Schwöebel potential barrier of the atomic terraces, inducing an uphill adatom flux that can smoothen the surface. Our findings demonstrate that bismuth surfactant can improve the surface morphology and film structure of low-temperature grown GaSb. Bismuth surfactant may also improve other homoepitaxial III-V systems grown in nonideal conditions.

An ultracompact scanning tunneling microscope within a Φ 10 piezo tube in a 20T superconducting magnet.

Low-temperature scanning tunneling microscopy and spectroscopy (STM/S) help to better understand the fundamental physics of condensed matter. We present an ultracompact STM within a Φ 10 piezo tube in a 20T superconducting magnet. The carefully cut piezo tube contains the STM's coarse-positioning assembly. Loading an STM tip-sample mechanical loop into the piezo tube with special cut openings enables an ultracompact pencil-size dimension down to Φ 10mm, in which fine-machined nonmagnetic parts are assembled to enable slide-stick motion and xyz-scanning procedures. The small size leads to a higher resonant frequency, a typical feature of a rigid STM instrument, increasing its vibration immunity. Scanning by moving the sample while keeping the tip stationary improves the stability of the tip-sample junction compared to moving the tip. Taking advantage of its high-field compatibility and rigid design, our STM captures the atomically resolved topography of highly oriented pyrolytic graphite (HOPG) at 1.5K and in magnetic fields up to 17T. The topography of graphene lattice and graphite is simultaneously recorded on an atomic terrace of HOPG, unveiling a modified local charge density at a surface defect. The superconducting energy gaps of layered type-II superconductors NbSe2 and PdBi2 are well resolved through dI/dV tunneling spectra at sub-2K. Our unique STM is highly suitable for potential STM/S applications in world-class high-field facilities where the strong magnetic field can exceed 30T.

Graphoepitaxially Side‐By‐Side Nanofins Along Atomic Terraces for Enhancement‐Mode FinFETs with 108 On/Off Ratio

AbstractThe innovation of 3D FinFETs using top‐down silicon nanofins represents a significant advancement toward scaling down microchip process nodes to the cutting‐edge 3‐nm level. While bottom‐up semiconductor nanofins also hold promise as building blocks for FinFETs, their controlled growth remains challenging. Drawing inspiration from the guided roots along brick gaps, this study shows that the aligned atomic terraces on an annealed miscut LaAlO3 surface can trigger an exceptional graphoepitaxial effect, encouraging the bottom‐up vapor‐phase growth of self‐aligned nanostructures such as CdS, CdSe, ZnSe, and ZnTe. Subsequently, the resultant CdS nanofins, characterized by narrow widths of ≈20 nm and large height‐to‐width ratios exceeding 16, can be seamlessly assembled into arrayed FinFETs on the insulating LaAlO3 substrate, obviating the need for post‐growth alignment steps. Unlike most nanostructure‐based planar transistors, which often operate in depletion mode characterized by negative thresholds, these FinFETs operate in enhancement mode with positive thresholds (≈5 V), ≈10−14‐A standby currents, and ≈108 on/off current ratios. The achieved ratio surpasses the record for planar enhancement‐mode CdS transistors by 4 orders of magnitude, primarily due to the enhanced electrostatic control over the nanofins. Overall, the graphoepitaxially side‐by‐side nanofins show tremendous potential to expand the repertoire of FinFETs based on non‐silicon semiconductors.

Site-specific reactivity of stepped Pt surfaces driven by stress release.

Heterogeneous catalysts are widely used to promote chemical reactions. Although it is known that chemical reactions usually happen on catalyst surfaces, only specific surface sites have high catalytic activity. Thus, identifying active sites and maximizing their presence lies at the heart of catalysis research1-4, in which the classic model is to categorize active sites in terms of distinct surface motifs, such as terraces and steps1,5-10. However, such a simple categorization often leads to orders of magnitude errors in catalyst activity predictions and qualitative uncertainties of active sites7,8,11,12, thus limiting opportunities for catalyst design. Here, using stepped Pt(111) surfaces and the electrochemical oxygen reduction reaction (ORR) as examples, we demonstrate that the root cause of larger errors and uncertainties is a simplified categorization thatoverlooks atomic site-specific reactivity driven by surface stress release. Specifically, surface stress release at steps introduces inhomogeneous strain fields, with up to 5.5% compression, leading to distinct electronic structures and reactivity for terrace atoms with identical local coordination, and resulting in atomic site-specific enhancement of ORR activity. For the terrace atoms flanking both sides of the step edge, the enhancement is up to 50 times higher than that of the atoms in the middle of the terrace, which permits control of ORR reactivity by either varying terrace widths or controlling external stress. Thus, the discovery of the above synergy provides a new perspective for both fundamental understanding of catalytically active atomic sites and design principles of heterogeneous catalysts.

Characterization of CO Adsorbed to Clean and Partially Oxidized Cu(211) and Cu(111).

Copper-based catalysts gain activity through the presence of poorly coordinated Cu atoms and incomplete oxidation at the surface. The catalytic mechanisms can in principle be observed by controlled dosing of reactants to single-crystal substrates. However, the interconnected influences of surface defects, partial oxidation, and adsorbate coverage present a large matrix of conditions that have not been fully explored in the literature. We recently characterized oxygen and carbon monoxide coadsorption on Cu(111), a nominally defect-free surface, and now extend our study to the stepped surface Cu(211). Temperature-programmed desorption of CO adsorbed to bare metal surfaces confirms that two sites dominate desorption from a saturated layer: atop terrace atoms of local (111) character and atop step edge atoms with CO bound more strongly to the latter. At low coverage, discrete CO resonances in reflection adsorption infrared spectra can be assigned to these sites: 2077 cm-1 for extended (111) terraces, 2093 cm-1 for step sites, and additional kink-adsorbed molecules at 2110 cm-1. With increasing coverage, in contrast to Cu(111), the infrared spectral features on Cu(211) evolve and shift as a consequence of dipole-dipole coupling between differentially occupied types of sites. Auger electron spectroscopy shows that exposure to background O2 oxidizes the (211) surface at a rate nearly 1 order of magnitude greater than (111); we argue that the resulting surface is stoichiometric Cu2O, as previously found for Cu(111). This oxide binds CO less strongly than the bare metal and the underlying crystal cut continues to influence the adsorption sites available to CO. On oxidized (111) terraces, broad absorption peaks at 2115-2120 cm-1; on oxidized Cu(211), CO adsorbed to step sites appears as a resolved secondary peak at 2144 cm-1. This suite of spectroscopic signatures, obtained under carefully controlled conditions, will help to determine the origin and fate of adsorbed species in future studies of reaction mechanisms on copper.

From Layer-by-Layer Growth to Nanoridge Formation: Selective Area Epitaxy of GaAs by MOVPE.

Selective area epitaxy at the nanoscale enables fabrication of high-quality nanostructures in regular arrays with predefined geometry. Here, we investigate the growth mechanisms of GaAs nanoridges on GaAs (100) substrates in selective area trenches by metal-organic vapor-phase epitaxy (MOVPE). It is found that pre-growth annealing results in the formation of valley-like structures of GaAs with atomic terraces inside the trenches. MOVPE growth of GaAs nanoridges consists of three distinct stages. Filling the trench in the first stage exhibits a step-flow growth behavior. Once the structure grows above the mask surface, it enters the second stage of growth by forming {101} side facets as the (100) flat top facet progressively shrinks. In the third stage, the fully formed nanoridge begins to overgrow onto the mask with a significantly reduced growth rate. We develop a kinetic model that accurately describes the width-dependent evolution of the nanoridge morphology through all three stages. MOVPE growth of fully formed nanoridges takes only about 1 min, which is 60 times faster than in our set of molecular beam epitaxy (MBE) experiments reported recently, and with a more regular, triangular cross-sectional geometry defined solely by the {101} facets. In contrast to MBE, no material loss due to Ga adatom diffusion onto the mask surface is observed in MOVPE until the third stage of growth. These results are useful for the fabrication of GaAs nanoridges of different dimensions on the same substrate for various applications and can be extended to other material systems.

CO2 reduction on adatom decorated platinum stepped surfaces.

The rate of CO formation from CO2 reduction on Pt(111) vicinal surfaces containing (100) steps, Pt(S)[n(111) × (100)], has been investigated using cyclic voltammetry. To obtain further information about the different roles of terrace and step atoms in this reaction, selective modification of step sites with either bismuth or copper has been performed. In this way, two different mechanistic regimes have been differentiated, depending on the potential range. In the high potential region, between 0.2 and 0.4V RHE, CO2 is activated on steps and proceeds to the formation of adsorbed CO even when there is no hydrogen adsorbed on the terrace. We suggest that protonation of the activated CO2 uses protons from the solution. In this potential range, the activity decreases after the selective blockage of step sites with bismuth, while the deposition of copper on steps increases the activity. Contrarily, in the low potential region, below 0.2V RHE, the presence of copper on the steps does not increase the amount of CO formed from CO2 reduction. In fact, the amount of CO formed attains the same saturation value with or without copper. In addition, the CO formed in this potential region remains adsorbed near step sites as shown in the voltammetric profile. We rationalize these observations considering that, in this potential region, activated CO2 reacts with adsorbed hydrogen and the reactions stop when hydrogen near the steps is depleted.

Effects of surface vacancy-adatom pair formation on PFC tungsten surface morphological response

We report a simulation study of the effect of He-irradiation-induced surface vacancy-adatom pair formation on the surface morphological evolution of plasma-facing component (PFC) tungsten and examine a number of factors that impact such evolution. Our analysis is based on self-consistent dynamical simulations according to an atomistically-informed, continuum-scale surface evolution model that has been developed following a hierarchical multiscale modeling strategy and can access the spatiotemporal scales of relevance to fuzz formation. The model accounts for the flux of surface adatoms generated as a result of the surface vacancy-adatom pair formation effect upon He implantation, which contributes to the anisotropic growth of surface nanostructural features due to the different rates of adatom diffusion along and across step edges of islands on the tungsten surface. We have carried out atomic-scale computations of optimal diffusion pathways along and across island step edges on the W(110) surface and calculated Ehrlich–Schwoebel (ES) barriers in adatom diffusion along and across such step edges. This aspect of surface adatom diffusion contributes to anisotropic surface atomic fluxes, terrace and step diffusive currents, and has been incorporated into our PFC surface evolution model, which predicts the formation of preferentially aligned nanoridge stripe patterns on the PFC surface. We establish that these anisotropic diffusive currents accelerate nanotendril growth on the PFC surface and the onset of surface nanostructure pattern formation. We also explore systematically the dependence of the PFC surface morphological response on the surface temperature and He ion incident flux, characterize in detail the resulting surface topographies and growth kinetics, and compare the predicted surface morphologies with experimental observations. Our simulation predictions for the emerging surface nanostructure patterns under certain plasma exposure conditions are consistent with experimental findings in the literature.

Influence of plasma kinetic energy during the pulsed laser deposition of borophene films on silicon (100).

Developing borophene films with good structural stability on non-metallic substrates to maximize their potential in photosensitivity, gas detection, photothermia, energy storage, and deformation detection, among others has been challenging in recent years. Herein, we succeeded in the pulsed laser deposition of multilayered borophene films on Si (100) with β12 or χ3 bonding by tuning the mean kinetic energy in the plasma during the deposition process. Raman and X-ray photoelectron spectroscopies confirm β12 and χ3 bonding in the films. Borophene films with β12 bonding were obtained by tuning a high mean kinetic energy in the plasma, while borophene with χ3 bonding required a relatively low mean kinetic energy. Atomic force microscopy (AFM) micrographs revealed a granular and directional growth of the multilayered borophene films following the linear atomic terraces from the (100) silicon substrate. AFM nanofriction was used to access the borophene surfaces and to reveal the pull-off force and friction coefficient of the films where the surface oxide showed a significant contribution. To summarize, we show that it is possible to deposit multilayered borophene thin films with different bondings by tuning the mean kinetic energy during pulsed laser deposition. The characterization of the plasma during borophene deposition accompanies our findings, providing support for the changes in kinetic energy.

New Alloy of an Al-Chalcogen System: AlSe Surface Alloys on Al(111).

Metal chalcogenides are a promising material for novel physical research and nanoelectronic device applications. Here, we systematically investigate the crystal structure and electronic properties of AlSe alloys on Al(111) using scanning tunneling microscopy, angle-resolved photoelectron spectrometry, and first-principle calculations. We reveal that the AlSe surface alloy possesses a closed-packed atomic structure. The AlSe surface alloy comprises two atomic sublayers (Se sublayer and Al sublayer) with a height difference of 1.16 Å. Our results indicate that the AlSe alloy hosts two hole-like bands, which are mainly derived from the in-plane orbital of AlSe (p x and p y ). These two bands located at about -2.22 ±0.01 eV around the Gamma point, far below the Fermi level, distinguished from other metal chalcogenides and binary alloys. AlSe alloys have the advantages of large-scale atomic flat terraces and a wide band gap, appropriate to serve as an interface layer for two-dimensional materials. Meanwhile, our results provide implications for related Al-chalcogen interfaces.

Core-level binding energy shifts between interior, terrace and edge atoms in MnO(001) thin films

Understanding the physical origin of core-level photoemission line shapes can offer valuable information about the chemical and physical properties of surfaces. For instance, in a large number of transition metals oxides, changes in the line shape allow the accurate determination of their oxidation states and cation site symmetry. Yet, despite this importance, experimental investigations on core-level shifts have been much neglected in recent years. In order to provide further evidence of the physical relevance, we have, in this contribution, introduced a new aspect of interior-, terrace- and edge- atom core-level binding energy shifts to describe monolayers of MnO(001) films grown on an Au(111) substrate. By this means we were able to distinguish the line shape contributions related to different types of atomic sites. We show that their relative intensities and energy shifts are able to provide information about the relative amount of under coordinated atoms on the surface and, thus give insights into their catalytic properties. Our findings reveal the importance of a detailed surface science characterization to provide the correct interpretation of distinct photoemission line shapes when considering thin film samples as well as nanostructures in general.

Shape-controlled and undercoordinated site-abundant Ru nanocrystals for low-temperature and additive-free benzene semi-hydrogenation

Shape manipulation of Ru nanocrystals (NCs) may afford the prominent enhancement in the catalytic performances and a well-defined catalytic model for mechanistic investigation in benzene semi-hydrogenation (BSH) by remolding the surface-atom arrangements. Herein, the Ru NCs with tailored shapes including irregular assemblies (IASs), nanospheres (NSPs), ultrathin triangle nanoplates (TNPs), and ultrathin irregular nanoplates (INPs) were fabricated, which were recognized to determine both the types and numbers of active sites. Ru IASs exposed few undercoordinated (unc) sites including atomic edges, vertexes, and defects as well as few coordinately saturated (csa) sites such as atomic terraces, while Ru NSPs primarily exposed csa sites, and Ru TNPs and Ru INPs exposed dominant and increased unc sites. Such difference contributed to a decreased order of turnover frequency (TOF) of benzene in Ru IASs > Ru INPs > Ru TNPs > Ru NSPs but an increased sequence of cyclohexene selectivity in Ru IASs < Ru NSPs < Ru TNPs < Ru INPs via manipulating the coordination configuration of benzene and so the net formation rate of cyclohexene. The initial selectivity toward cyclohexene (S0) attained to 90.6% on Ru INPs exposed most unc sites under green conditions, evidencing its high catalytic efficiency in BSH.

Nanoscale Electronic Transparency of Wafer-Scale Hexagonal Boron Nitride.

Monolayer hexagonal boron nitride (hBN) has attracted interest as an ultrathin tunnel barrier or environmental protection layer. Recently, wafer-scale hBN growth on Cu(111) was developed for semiconductor chip applications. For basic research and technology, understanding how hBN perturbs underlying electronically active layers is critical. Encouragingly, hBN/Cu(111) has been shown to preserve the Cu(111) surface state (SS), but it was unknown how tunneling into this SS through hBN varies spatially. Here, we demonstrate that the Cu(111) SS under wafer-scale hBN is homogeneous in energy and spectral weight over nanometer length scales and across atomic terraces. In contrast, a new spectral feature─not seen on bare Cu(111)─varies with atomic registry and shares the spatial periodicity of the hBN/Cu(111) moiré. This work demonstrates that, for some 2D electron systems, an hBN overlayer can act as a protective yet remarkably transparent window on fragile low-energy electronic structure below.

Uniform nucleation and epitaxy of bilayer molybdenum disulfide on sapphire

Two-dimensional transition-metal dichalcogenides (TMDs) are of interest for beyond-silicon electronics1,2. It has been suggested that bilayer TMDs, which combine good electrostatic control, smaller bandgap and higher mobility than monolayers, could potentially provide improvements in the energy-delay product of transistors3-5. However, despite advances in the growth of monolayer TMDs6-14, the controlled epitaxial growth of multilayers remains a challenge15. Here we report the uniform nucleation (>99%) of bilayer molybdenum disulfide (MoS2) on c-plane sapphire. In particular, we engineer the atomic terrace height on c-plane sapphire to enable an edge-nucleation mechanism and the coalescence of MoS2 domains into continuous, centimetre-scale films. Fabricated field-effect transistor (FET) devices based on bilayer MoS2 channels show substantial improvements in mobility (up to 122.6 cm2 V-1 s-1) and variation compared with FETs based on monolayer films. Furthermore, short-channel FETs exhibit an on-state current of 1.27 mA μm-1, which exceeds the 2028 roadmap target for high-performance FETs16.

Surface Engineering of Palladium Nanocrystals: Decoupling the Activity of Different Surface Sites on Nanocrystal Catalysts

AbstractThe existence of various surface active sites within a nanocrystal (NC) catalyst complicates understanding their respective catalytic properties and designing an optimal catalyst structure for a desired catalytic reaction. Here, we developed a novel approach that allows unequivocal investigation on the intrinsic catalytic reactivity of the edge and terrace atoms of NCs. Through the comparison of the catalytic behaviors of edge‐covered Pd NCs, which were prepared by the selective deposition of catalytically inactive Au atoms onto the edge sites of rhombic dodecahedral (RD) Pd NCs, with those of the pristine RD Pd NCs toward alkyne hydrogenation and Suzuki–Miyaura coupling reactions, we could decouple the activity of the edge and {110}‐plane atoms of the Pd NCs without uncertainties. We expect that this study will provide an opportunity to scrutinize the surface properties of various NC catalysts to a more precise level and devise ideal catalysts for intended catalytic reactions.

Surface Engineering of Palladium Nanocrystals: Decoupling the Activity of Different Surface Sites on Nanocrystal Catalysts.

The existence of various surface active sites within a nanocrystal (NC) catalyst complicates understanding their respective catalytic properties and designing an optimal catalyst structure for a desired catalytic reaction. Here, we developed a novel approach that allows unequivocal investigation on the intrinsic catalytic reactivity of the edge and terrace atoms of NCs. Through the comparison of the catalytic behaviors of edge-covered Pd NCs, which were prepared by the selective deposition of catalytically inactive Au atoms onto the edge sites of rhombic dodecahedral (RD) Pd NCs, with those of the pristine RD Pd NCs toward alkyne hydrogenation and Suzuki-Miyaura coupling reactions, we could decouple the activity of the edge and {110}-plane atoms of the Pd NCs without uncertainties. We expect that this study will provide an opportunity to scrutinize the surface properties of various NC catalysts to a more precise level and devise ideal catalysts for intended catalytic reactions.

Gold Atoms Promote Macroscopic Superconductivity in an Atomic Monolayer of Pb on Si(111).

Atomically thin superconductivity in Pb monolayers grown on Si(111) is affected by adding a tiny amount of Au atoms. In situ macroscopic electron transport measurements reveal that superconductivity develops at higher temperatures and manifests a sharper superconducting transition to zero resistance as compared to pristine Pb/Si(111). Scanning tunneling microscopy and spectroscopy show that Au atoms decorate atomic step edges of Pb/Si(111) and link the electronic reservoirs of neighboring atomic terraces. The propagation of superconducting correlations across the edges is enhanced, facilitating the coherence between terraces and promoting macroscopic superconductivity at higher temperatures. This finding opens new ways to design and control Josephson junctions at the atomic scale.

Surface Atomic Decoration of a Manganite to a Modulable Oxygen Evolution Reaction.

Aiming at the fundamental understanding of oxygen evolution reaction (OER) in epitaxial perovskite transition metal oxide (TMO) thin films, we evaluate the surface decoration conditions, including lattice orientation and surface morphology, of La2/3Sr1/3MnO3 (LSMO) related to its modulable OER performance. The LSMOs with orientations of (001), (110), and, (111) exhibit different OER activities owing to the discrepant surface density of Mn. Furthermore, tuning of the surface atomic terrace width of LSMO shows a more efficient path to modulate the OER performance by introducing a high-valence Mn state owing to the surface dangling bonds of LSMO. As the electrochemical process is dominated by the interface of the TMO surface and electrolyte, our investigation can approach the fundamental understanding of a perovskite-type TMO surface state and its OER performance while highlighting the role of the nonbulk electron state in a promising TMO electrocatalyst in abundant electrochemical processes.