Atomic Steps Research Articles

Interfacial Coupling Induced Discrete Orientation of Epitaxial Graphene on High‐Index Cu Substrates

AbstractControlled and precise synthesis of materials has been a central pursuit in academia and industry. With the rise of twistronics research, there is growing demand for synthesizing orientation‐controlled 2D materials with atomic precision. Previous theories for 2D materials can predict graphene (Gr) growth on low‐index metal substrates but fail to explain the discrete orientations on most high‐index substrates, inconsistent with experimental data. Using density functional theory (DFT) and ab‐initio molecular dynamics (AIMD), this study explores graphene growth on high‐index substrates, showing that atomic steps do not dominate in trapping C atoms or driving preferential graphene nucleation at high temperatures. Thus, the possibility of intrinsic atomic steps in inducing graphene orientation on high‐index substrates is ruled out. Interfacial coupling strength between graphene and substrates is quantified using a close contact index (CCI), linking atomic structure and electronic states. The coupling between graphene and high‐index Cu surfaces is generally weak, reducing substrate anchoring and increasing graphene orientation dispersion. The extension of this theory to bilayer graphene (BLG) reveals competition between Gr/Cu interfacial coupling and Gr/Gr interlayer coupling, offering insights for controlling twist angles. This theory explains the discrete orientations on high‐index substrates, providing a theoretical basis for synthesizing orientation‐controlled graphene.

Modification of Erroneous and Correct Digital Texts

The end-user paradox and the illusion of digital prosperity reveal the contradictory situation in which both non-professional and professional computer scientists and engineers seem satisfied with digital development but unaware of the magnitude of waste generated by end-users and their digital artifacts. To measure this waste and to reveal end-users’ problem-solving strategies, our research group set up an objective measuring system that can calculate the entropy of digital texts (EDT). To calculate EDT, a testing process of 53 participants was launched where erroneous and correct natural language digital texts were modified according to the requirements of the tasks. It was found that erroneous documents require more time and information to be modified, which implies that waste is generated by handling these documents. It was also found that when the problem-solving processes are broken down into atomic steps, EDT can reveal uncertainty and idleness, which further increases waste. The goals of the present paper are to call attention to (1) the hidden waste generated by billions of end-users and its consequences, (2) educational approaches and general ignorance which have led to these low-level results, and (3) the need to set up a standard evaluation system for further analyses.

Unconventional Near‐equilibrium Nucleation of Graphene on Si‐terminated SiC(0001) Surface

The transfer‐free character of graphene growth on Silicon Carbide (SiC) makes it compatible with state‐of‐the‐art Si semi‐conductor technologies for directly fabricating high‐end electronics. Although significant progress has been achieved in epitaxial growth of graphene on SiC recently, the underlying nucleation mechanism remains elusive. Here, we present a theoretical study to elucidate graphene near‐equilibrium nucleation on Si‐terminated hexagonal‐SiC(0001) surface. It is found that the ultra‐large lattice mismatch between SiC(0001) surface and graphene and the highly localized electron distribution on SiC(0001) surface lead to a distinctive nucleation process: (i) Most of the magic carbon clusters on SiC(0001) show only C1 symmetry and are mainly composed of pentagonal rings; (ii) Two possible nucleation pathways are revealed, i.e, longitudinal and circular modes; (iii) Carbon clusters are more stable on flat terraces than near atomic step edges. Based on above findings, a graphene nucleation diagram on SiC(0001) is established and experimentally observed contradictories for graphene growth on SiC(0001) are answered. Our in‐depth understanding on graphene nucleation on SiC(0001) extends nucleation mechanisms of 2D crystals and will benefit high‐quality graphene growth on SiC(0001).

Unconventional Near-Equilibrium Nucleation of Graphene on Si-Terminated SiC(0001) Surface.

The transfer-free character of graphene growth on Silicon Carbide (SiC) makes it compatible with state-of-the-art Si semiconductor technologies for directly fabricating high-end electronics. Although significant progress has been achieved in epitaxial growth of graphene on SiC recently, the underlying nucleation mechanism remains elusive. Here, we present a theoretical study to elucidate graphene near-equilibrium nucleation on Si-terminated hexagonal-SiC(0001) surface. It is found that the ultra-large lattice mismatch between SiC(0001) surface and graphene and the highly localized electron distribution on SiC(0001) surface lead to a distinctive nucleation process: (i) Most of the magic carbon clusters on SiC(0001) show only C1 symmetry and are mainly composed of pentagonal rings; (ii) Two possible nucleation pathways are revealed, i.e., longitudinal and circular modes; (iii) Carbon clusters are more stable on flat terraces than near atomic step edges. Based on above findings, a graphene nucleation diagram on SiC(0001) is established and experimentally observed contradictories for graphene growth on SiC(0001) are answered. Our in-depth understanding on graphene nucleation on SiC(0001) extends nucleation mechanisms of 2D crystals and will benefit high-quality graphene growth on SiC(0001).

Controllable Synthesis of Oxa‐/Thia‐Spirohydroquinolines by [3+(2+1)] Annulation of Aromatic Amines with Bimolecular O/S‐Heterocyclic Ketones

Abstract[3+(2+1)] Annulation represents the most straightforward and atom‐economical strategies in organic synthesis for the efficient construction of diverse cyclic structural units and complex molecules. Herein, we present a Lewis acid Sc(OTf)3‐catalyzed controlled synthesis of two different regioselective oxa/thia‐spirohydroquinolines (C=C at the α/β‐site of O/S‐atom) from aromatic amines and bimolecular O/S‐heterocyclic ketones via intermolecular [3+(2+1)] annulation. This method features mild reaction conditions, high step economy and atom utilization, and the O/S‐heterocyclic ketone can act as both two‐ and one‐carbon synthons. Furthermore, density functional theory (DFT) calculations indicate that the intrinsic cause of this unique regioselectivity is caused by the proton abstraction step.

Step‐Directed Epitaxy of Unidirectional Hexagonal Boron Nitride on Vicinal Ge(110)

Insulating hexagonal boron nitride (hBN) films with precisely controlled thickness are ideal dielectric components to modulate various interfaces in electronic devices. To achieve this, high‐quality hBN with controlled atomic configurations must be able to form pristine interfaces with various materials in devices. However, previously reported large‐scale hBN films with uniform thickness either are polycrystalline or are not suitable for atomically clean assembly via mechanical exfoliation, limiting their applications in device technology. Herein, the large‐scale growth of monolayer (ML) single crystalline hBN films on Ge(110) substrates by using chemical vapor deposition is reported. Vicinal Ge(110) substrates are used for the step‐directed epitaxial growth of hBN, where Ge atomic steps act as the hBN nucleation sites, guiding the unidirectional alignments of multiple hBN domains. Density functional theory calculations reveal that the optimum hydrogen passivations on both hBN edges and Ge surfaces enable the epitaxial coupling between hBN and the Ge step edges and the single crystallinity of the final hBN films. Using epitaxially grown ML hBN films, a few hBN films with controlled stacking orders and pristine interfaces through a layer‐by‐layer assembly process are fabricated. These films function as high‐quality dielectrics to enhance carrier transport in graphene and MoS2 channels.

Directional picoantenna behavior of tunnel junctions formed by an atomic-scale surface defect.

Plasmonic nanoantennas have attracted much attention lately, among other reasons because of the directionality of light emitted by fluorophores coupled to their localized surface plasmon resonances. Plasmonic picocavities, i.e., cavities with mode volumes below 1 nm3, could act as enhanced antennas due to their extreme field confinement, but the directionality on their emission is difficult to control. In this work, we show that the plasmonic picocavity formed between the tip of a scanning tunneling microscope and a metal surface with a monoatomic step shows directional emission profiles and, thus, can be considered as a realization of a picoantenna. Electromagnetic calculations demonstrate that the observed directionality arises from the reshaping and tilting of the surface charges induced at the scanning tip due to the atomic step. Our results pave the way to exploiting picoantennas as an efficient way for the far-field probing and control of light-matter interactions below the nanoscale.

(Invited) Selective Wet Etching of Semiconductor Materials by Novel Catalyst-assisted Modes

Since reports in the mid-1990s on metal-induced pitting on a Si surface in microelectronics, much attention has been paid to the positive use of corrosion of a semiconductor surface loaded with a metallic catalyst in solutions, known as metal-assisted chemical etching. This paper describes two novel modes of catalyst-assisted etching. The first involves the formation of nano trenches along the atomic step edges of a Si(111) surface with the help of self-assembled metallic nanowires, enabling the separation of neighboring terraces. The second discusses the science and application of nanocarbon-assisted etching, free from noble metals, of a Ge surface in water.

Perspective: imaging atomic step geometry to determine surface terminations of kagome materials and beyond

Here we review scanning tunneling microscopy research on the surface determination for various types of kagome materials, including 11-type (CoSn, FeSn, FeGe), 32-type (Fe3Sn2), 13-type (Mn3Sn), 135-type (AV3Sb5, A = K, Rb, Cs), 166-type (TbMn6Sn6, YMn6Sn6 and ScV6Sn6), and 322-type (Co3Sn2S2 and Ni3In2Se2). We first demonstrate that the measured step height between different surfaces typically deviates from the expected value of ±0.4 ∼0.8Å, which is owing to the tunneling convolution effect with electronic states and becomes a serious issue for Co3Sn2S2 where the expected Sn-S interlayer distance is 0.6Å. Hence, we put forward a general methodology for surface determination as atomic step geometry imaging, which is fundamental but also experimentally challenging to locate the step and to image with atomic precision. We discuss how this method can be used to resolve the surface termination puzzle in Co3Sn2S2. This method provides a natural explanation for the existence of adatoms and vacancies, and beyond using unknown impurity states, we propose and use designer layer-selective substitutional chemical markers to confirm the validity of this method. Finally, we apply this method to determine the surface of a new kagome material Ni3In2Se2, as a cousin of Co3Sn2S2, and we image the underlying kagome geometry on the determined Se surface above the kagome layer, which directly visualizes the p-d hybridization physics. We emphasize that this general method does not rely on theory, but the determined surface identity can provide guidelines for first-principles calculations with adjustable parameters on the surface-dependent local density of states and quasi-particle interference patterns.

Comparison of AlN/GaN heterojunctions grown by molecular beam epitaxy with Al and Ga assistance

Although conventional III-nitride molecular-beam-epitaxy growth theories indicate that high-quality AlN should be prepared in Al-assisted regimes, AlN/GaN heterojunctions grown in Ga-assisted regimes actually demonstrate superior performances. In this letter, we compared Al-assisted and Ga-assisted grown AlN/GaN heterojunctions and explored the underlying mechanisms. Aberration-corrected transmission electron microscope, energy dispersive spectrometer, and atomic force microscopy measurements indicate that the Al-assisted growth results in partly-relaxed AlN of high-density defects, deteriorating AlN/GaN interfaces, and surface morphology consisting of irregular and truncated atomic steps. The Ga-assisted growth produces high-quality pseudomorphic AlN with excellent AlN/GaN interfaces, surface morphology, and electrical properties. It is suggested that the better crystalline quality and higher performances of the Ga-assisted grown samples are attributed to a lower N subsurface diffusion barrier resulting from a higher energy of the fcc adsorption positions in the adlayer-enhanced-lateral-diffusion model and intense thermal motions of Ga adatoms. It helps to understand the kinetics of metal-adlayer-enhanced growth of AlN and AlN/GaN heterojunctions at atomic scale and optimize the growth processes. Meanwhile, it is demonstrated that amorphization and Al diffusion near the AlN surfaces occur due to Pt bombardment on highly tensile-strained AlN during focused-ion-beam fabrications. It implies that large strain in AlN/GaN heterojunctions might be an important issue to be considered for device reliability.

Impact of Atomic Defects on Water Contact Angle of 2D Molybdenum Disulfide Surfaces.

Interfacial dynamics within nanofluidic systems are crucial for applications like water desalination and osmotic energy harvesting. Understanding these dynamics can inform the rational optimization of two-dimensional (2D) materials and devices for such applications. This study explores the wetting behavior of realistic 2D MoS2 surfaces incorporating vacancies and atomic steps, known as atomic defects. We employ a combined density functional theory (DFT) and molecular dynamics (MD) computational approach to elucidate the influence of atomic defects on the MoS2-water interface. DFT calculations are utilized to determine the charge distribution within MoS2. Subsequently, free energy calculations are obtained through MD simulations of the MoS2-water interface. Our findings underscore the importance of incorporating atomic defects into MoS2 surfaces for accurate water contact angle (WCA) predictions in nanofluidic simulations, particularly when using Abal et al. force field parameters. However, the force field developed by Liu et al. yielded more accurate results for pristine MoS2 surfaces. While these parameters provide reliable outcomes for pristine MoS2 surfaces, their application to surfaces with defects may lead to underestimation of WCA. This highlights the critical need for realistic surface representations in nanofluidic modeling to accurately capture the complex interactions between water and MoS2 materials.

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.

Nucleation-Limited Kinetics of GaAs Nanostructures Grown by Selective Area Epitaxy: Implications for Shape Engineering in Optoelectronics Devices.

The growth kinetics of vertical III-V nanowires (NWs) were clarified long ago. The increasing aspect ratio of NWs results in an increase in the surface area, which, in turn, enhances the material collection. The group III adatom diffusion from the NW sidewalls to the top sustains a superlinear growth regime. In this work, we report on the growth of different GaAs nanostructures by selective area MOVPE on GaAs (111)B substrates. We show that the opening dimensions and geometry qualitatively alter the morphology and height evolution of the structures. We compare the time evolution of vertical GaAs NWs stemming from circular holes and horizontal GaAs nanomembranes (NMs) growing from one-dimensional (1D) rectangular slits on the same substrate. While NW heights grow exponentially with time, NMs surprisingly exhibit sublinear kinetics. The absence of visible atomic steps on the top facets of both NWs and NMs suggests layer-by-layer growth in the mononuclear mode. We interpret these observations within a self-consistent growth model, which links the diffusion flux of Ga adatoms to the position- and shape-dependent nucleation rate on top of NWs and NMs. Specifically, the island nucleation rate is lower on top of the NMs than that on the NWs, resulting in the total diffusion flux being directed from the top facet to the sidewalls. This gives a sublinear height evolution for the NMs. These results open innovative perspectives for shape engineering of III-V nanostructures and new avenues for the design of optoelectronics and photonic devices.

Coupling atomization, emulsification, and polymerization steps for creating gel microspheres

Coupling atomization, emulsification, and polymerization steps for creating gel microspheres

Regioselective Syntheses of 1,4- and 1,6-Dicarbonyl Compounds via Photoredox-Based Oxidative Heterocoupling of Enolsilanes with Oxygen as an Oxidant.

A photoredox-based oxidative heterocoupling of enolsilanes to the corresponding 1,4- and 1,6-dicarbonyl compounds was developed by using Mes-Acr+BF4- as the photocatalyst, and oxygen was used as the oxidant. This newly developed chemistry adheres to the principles of atom economy, step economy, and redox economy, making it a concise and efficient method.

Symmetry breaking induced asymmetric dislocation-planar fault interactions in ordered intermetallic alloys

In this study, we present the first comprehensive examination of symmetry breaking in the interactions between dislocation and superlattice planar faults, including anti-phase boundary (APB), complex stacking fault (CSF), superlattice intrinsic stacking fault (SISF), to reveal the underlying asymmetric dislocation reaction mechanisms depending on the sense of applied stress, employing both large-scale atomistic simulations and continuum dislocation theory. Four ordered intermetallic alloy systems including γ−Ni/γ′−Ni3Al and γ−Ni/γ′−Ni3Fe, γ−Al/γ−TiAl, and α−Ti/α2−Ti3Al were selected as the representative model systems, with two primary symmetry breaking effects, i.e., translational and three-fold rotational symmetry breaking considered. Detailed atomic steps of asymmetrical dislocation reactions and the corresponding asymmetrical dislocation bypassing mechanisms of precipitation have been elucidated, shown to be highly dependent on the geometrical configuration of the precipitate and the relative magnitudes of APB, CSF and SISF fault energies. A continuum model framework was then developed, which, for the first time, provides accurate and quantitative predictions of the threshold conditions triggering critical asymmetrical dislocation slips, verified to be in good agreement with the simulation results. Our study also successfully reproduced the experimentally observed dislocation-induced APB-SISF transformation, with a new dislocation reaction mechanism proposed to explain the transformation process. The findings are expected to be a key enabling stepstone for future innovation in intermetallic alloys strengthened through ordered phases for advanced applications in aeronautic and automotive industries.

High-index facets Pt concave nanocubes with small interface angles induced by N-defective sites in the integrated electrode for methanol oxidation

The construction of an integrated electrode with self-organized growth is of great significance in reducing the Pt loading and improving the performance of the membrane electrode assembly (MEA) in proton exchange membrane fuel cells (PEMFCs). Herein, the square-wave pulse electrodeposition method is used to grow Pt{510}CNC and Pt{720}CNC nanocrystals on carbon fiber paper (CFP)-based reduced graphene oxide (rGO/CFP) and nitrogen-doped reduced graphene oxide (N-rGO/CFP) supports, respectively. Experimental and density functional theory (DFT) calculations show that the introduction of N makes it easier for hydrogen to adsorb on Pt, and the arrangement order of more Pt atoms is disrupted by hydrogen, resulting in the formation of Pt concave nanocubes (Pt CNCs) with small interface angles (α), consisting of {720} facets with more atomic steps. Moreover, the catalytic activities of the prepared two catalysts for methanol oxidation are 3.17 and 2.35 times higher than that of commercial Pt/C, and the maximum power densities of direct methanol fuel cell (DMFC) are also better than that of commercial Pt/C. This work can provide important guidance for the future research of high-index facets noble metal nanocrystals for growth on the surface of defective carbon carriers as integrated electrodes in MEA.

Direct conversion of CO2 to CH4 on Pd/graphdiyne single-crystalline.

A major impediment to the development of the efficient use of artificial photosynthesis is the lack of highly selective and efficient photocatalysts toward the conversion of CO2 by sunlight energy at room temperature and ambient pressure. After many years of hard work, we finally completed the synthesis of graphdiyne-based palladium quantum dot catalysts containing high-density metal atom steps for selective artificial photosynthesis. The well-designed interface structure of the catalyst is composed of electron-donor and acceptor groups, resulting in the obvious incomplete charge-transfer phenomenon between graphdiyne and plasmonic metal nanostructures on the interface. These intrinsic characteristics are the origin of the high performance of the catalyst. Studies on its mechanism reveal that the synergism between 'hot electron' from local surface plasmon resonance and rapid photogenerated carrier separation at the ohmic contact interface accelerates the multi-electron reaction kinetics. The catalyst can selectively synthesize CH4 directly from CO2 and H2O with selectivity of near 100% at room temperature and pressure, and exhibits transformative performance, with an average CH4 yield of 26.2 μmol g-1 h-1 and remarkable long-term stability.

Atomic-Scale Distribution and Evolution of Strain in Pt Nanoparticles Grown on MoS2 Nanosheet.

Interface strain significantly affects the band structure and electronic states of metal-nanocrystal-2D-semiconductor heterostructures, impacting system performance. While transmission electron microscopy (TEM) is a powerful tool for studying interface strain, its accuracy may be compromised by sample overlap in high-resolution images due to the unique nature of the metal-nanocrystals-2D-semiconductors heterostructure. Utilizing digital dark-field technology, the substrate influence on metal atomic column contrasts is eliminated, improving the accuracy of quantitative analysis in high-resolution TEM images. Applying this method to investigate Pt on MoS2 surfaces reveals that the heterostructure introduces a tensile strain of ≈3% in Pt nanocrystal. The x-directional linear strain in Pt nanocrystals has a periodic distribution that matches the semi-coherent interface between Pt nanocrystals and MoS2, while the remaining strain components localize mainly on edge atomic steps. These results demonstrate an accurate and efficient method for studying interface strain and provide a theoretical foundation for precise heterostructure fabrication.

Remote epitaxy of single-crystal rhombohedral WS2 bilayers

Compared to transition metal dichalcogenide (TMD) monolayers, rhombohedral-stacked (R-stacked) TMD bilayers exhibit remarkable electrical performance, enhanced nonlinear optical response, giant piezo-photovoltaic effect and intrinsic interfacial ferroelectricity. However, from a thermodynamics perspective, the formation energies of R-stacked and hexagonal-stacked (H-stacked) TMD bilayers are nearly identical, leading to mixed stacking of both H- and R-stacked bilayers in epitaxial films. Here, we report the remote epitaxy of centimetre-scale single-crystal R-stacked WS2 bilayer films on sapphire substrates. The bilayer growth is realized by a high flux feeding of the tungsten source at high temperature on substrates. The R-stacked configuration is achieved by the symmetry breaking in a-plane sapphire, where the influence of atomic steps passes through the lower TMD layer and controls the R-stacking of the upper layer. The as-grown R-stacked bilayers show up-to-30-fold enhancements in carrier mobility (34 cm2V−1s−1), nearly doubled circular helicity (61%) and interfacial ferroelectricity, in contrast to monolayer films. Our work reveals a growth mechanism to obtain stacking-controlled bilayer TMD single crystals, and promotes large-scale applications of R-stacked TMD.