The electronic structure of a single layer graphene on Ru(0001) is compared with that of a single layer hexagonal boron nitride nanomesh on Ru(0001). Both are corrugated sp2 networks and display a pi-band gap at the K point of their 1 x 1 Brillouin zone. Graphene has a distinct Fermi surface which indicates that 0.1 electrons are transferred per 1 x 1 unit cell. Photoemission from adsorbed xenon identifies two distinct Xe 5p1/2 lines, separated by 240 meV, which reveals a corrugated electrostatic potential energy surface. These two Xe species are related to the topography of the system and have different desorption energies.
A hybrid structure of a graphene nanomesh with the gold nanodisks is studied to enhance the light absorption by localized surface plasmon resonance. From the reflection spectra of the visible range for graphene nanomesh samples without and with nanodisks, it is found that the absorption of graphene nanomesh structures is greatly enhanced in the presence of gold nanodisks around the resonance wavelength. Simulation results based on the finite-difference time-domain method support the experimental observations. This study demonstrates the potential of constructing graphene based photodetectors w…
Functional nano-templates enable self-assembly of otherwise impossible arrangements of molecules. A particular class of such templates is that of sp2 hybridized single layers of hexagonal boron nitride or carbon (graphene) on metal supports. If the substrate and the single layer have a lattice mismatch, superstructures are formed. On substrates like rhodium or ruthenium these superstructures have unit cells with ~3 nm lattice constant. They are corrugated and contain sub-units, which behave like traps for molecules or quantum dots, which are small enough to become operational at room temperatu…
Porous graphene structures, also termed graphene nanomeshes (GNMs), are garnering increasing interest due to their potential application to important technologies such as chemical sensing, ion-filtration, and nanoelectronics. Semiconducting GNMs designed to have fractional eV band gaps are good candidates for graphene-based electronics, provided that a mechanism for their stable and controlled doping is developed. Recent work has shown that controlled passivation of the edges of subnanometer pores and subsequent doping by atoms or molecules gives rise to {\it p}- and {\it n}-doped GNM structur…
A bottom-up chemical vapor deposition (CVD) process for the growth of graphene nanomesh films is demonstrated. The process relies on silicon nanospheres to block nucleation sites for graphene CVD on copper substrates. These spheres are formed in a self-organized way through silicon diffusion through a 5 $μ$m copper layer on a silicon wafer coated with 400 nm of silicon nitride. The temperature during the growth process disintegrates the $Si_3$$N_4$ layer and silicon atoms diffuse to the copper surface, where they form the nanospheres. After graphene nanomesh growth, the Si nanospheres can be r…
Hexagonal boron nitride (h-BN) nanomesh, a two-dimensional insulating monolayer, grown on the (111) surface of rhodium exhibits an intriguing hexagonal corrugation pattern with a lattice constant of 3.2 nm. Despite numerous experimental and theoretical studies no quantitative agreement has been found on some details of the adsorption geometry such as the corrugation amplitude. The issue highlights the differences in chemical and electronic environment in the strongly bound pore regions and the weakly bound wire regions of the corrugated structure. For reliable results it is important to probe …
Using first-principles calculations, we explore the electronic and magnetic properties of graphene nanomesh (GNM), a regular network of large vacancies, produced either by lithography or nanoimprint. When removing an equal number of A and B sites of the graphene bipartite lattice, the nanomesh made mostly of zigzag (armchair) type edges exhibit antiferromagnetic (spin unpolarized) states. In contrast, in situation of sublattice symmetry breaking, stable ferri(o)magnetic states are obtained. For hydrogen-passivated nanomesh, the formation energy is dramatically decreased, and ground state is fo…
Simulation of chemical activity of corrugated graphene within density functional theory predicts an enhancement of its chemical activity if the ratio of height of the corrugation (ripple) to its radius is larger than 0.07. Further growth of the curvature of the ripples results in appearance of midgap states which leads to an additional strong increase of chemisororption energy. These results open a way for tunable functionalization of graphene, namely, depending of curvature of the ripples one can provide both homogeneous (for small curvatures) and spot-like (for large curvatures) functionaliz…
Single sheets of hexagonal boron nitride on transition metals provide a model system for single layer dielectrics. The progress in the understanding of h-BN layers on transition metals of the last 10 years are shortly reviewed. Particular emphasis lies on the boron nitride nanomesh on Rh(111), which is a corrugated single sheet of h-BN, where the corrugation imposes strong lateral electric fields. Fermi surface maps of h-BN/Rh(111) and Rh(111) are compared. A h-BN layer on Rh(111) introduces no new bands at the Fermi energy, which is expected for an insulator. The lateral electric fields of h-…
We present a structural analysis of the graphene/Ru(0001) system obtained by surface x-ray diffraction. The data were fit using Fourier-series expanded displacement fields from an ideal bulk structure, plus the application of symmetry constraints. The shape of the observed superstructure rods proves a reconstruction of the substrate, induced by strong bonding of graphene to ruthenium. Both the graphene layer and the underlying substrate are corrugated, with peak-to-peak heights of (0.82 +/- 0.15) A and (0.19 +/- 0.02) A for the graphene and topmost Ru-atomic layer, respectively. The Ru-corruga…
The boron nitride nanomesh is a corrugated monolayer of hexagonal boron nitride (h-BN) on Rh(111), which so far has been studied mostly under ultrahigh vacuum conditions. Here, we investigate how copper underpotential deposition (upd) can be used to quantify defects in the boron nitride monolayer and to assess the potential window of the nanomesh, which is important to explore its functionality under ambient and electrochemical conditions. In dilute sulfuric acid, the potential window of h-BN/Rh(111) is close to 1 volt, i.e. larger than that of the Rh substrate, and is limited by molecular hyd…
The Moiré structure of epitaxial graphene mono layer grown on 6H-SiC(0001) has been investigated recently by grazing incidence fast atom diffraction, and the results were compared with the calculation of the structure \textit{ab initio} and exact diffraction codes. We review these results and present a complementary approach using the Hard Wall Model to extract information without any \textit{a priori}. Reversely, taking advantage of previous exact calculations we evaluate quantitatively the performance of this simplified approach by comparing predictions using the same potential energy surfac…
Free-standing exfoliated monolayer graphene is an ultra-thin flexible membrane, which exhibits out of plane deformation or corrugation. In this paper, a technique is described to measure the band structure of such free-standing graphene by angle-resolved photoemission. Our results show that photoelectron coherence is limited by the crystal corrugation. However, by combining surface morphology measurements of the graphene roughness with angle-resolved photoemission, energy dependent quasiparticle lifetime and bandstructure measurements can be extracted. Our measurements rely on our development …
It is shown that for monolayer graphene electrons are confined on a perfect two dimensional surface. The implications for the electronic properties of corrugated graphene are discussed in view of a derivation of the constrained relativistic dynamics for the massless carriers in two dimensions. Surface curvature is related to a series of phenomena with practical applications such as curvature induced p-n junctions, band gap opening and decoherence. We also establish a bending free energy by treating graphene as a soft electronic membrane.
Density functional theory (DFT) modeling of the physisorption of four different types of molecules (toluene, bromine dimmer, water and nitrogen dioxide) over and above graphene ripples has been performed. For all types of molecules changes of charge transfer and binding energies in respect to flat graphene is found. The changes in electronic structure of corrugated graphene and turn of π-orbitals of carbon atoms in combination with chemical structure of adsorbed molecules are proposed as the causes of difference with the perfect graphene case and variety of adsorption properties of different t…
The electromagnetic radiation of electrons in the corrugated graphene in the presence of the transport electric current in the ballistic regime is studied. Radiation of the similar nature can be observed in undulator and wiggler. We considered here an impact of the ripples in the monolayer graphene on its electromagnetic properties. The electromagnetic radiation was actually calculated with a use of the standard electromagnetic theory. Two cases, of regular and random structures are analyzed. Nonlinear relation between the random height function h(x,y) and the gauge field is shown to create th…
Recent studies show that periodic potentials can generate superlattice Dirac points at energies in graphene (is the Fermi velocity of graphene and G is the reciprocal superlattice vector). Here, we perform scanning tunneling microscopy and spectroscopy studies of a corrugated graphene monolayer on Rh foil. We show that the quasi-periodic ripples of nanometer wavelength in the corrugated graphene give rise to weak one-dimensional (1D) electronic potentials and thereby lead to the emergence of the superlattice Dirac points. The position of the superlattice Dirac point is space-dependent and show…
We study the changes induced by the effective gauge field due to ripples on the low energy electronic structure of graphene. We show that zero energy Landau levels will form, associated to the smooth deformation of the graphene layer, when the height corrugation, $h$, and the length of the ripple, $l$, are such that $h^2 / (l a) \gtrsim 1$, where $a$ is the lattice constant. The existence of localized levels gives rise to a large compressibility at zero energy, and to the enhancement of instabilities arising from electron-electron interactions including electronic phase separation. The combine…
In graphene based materials, the energy storage capacity is usually improved by rich porous structures with extremely high surface area. By utilizing surface corrugations, this work shows an alternative strategy to activate graphene materials for large capacitance. We demonstrate how to simply fabricate such activated graphene and how these surface structures helped to realize considerable specific capacitance (e.g., electrode capacitance of ~340 F g-1 at 5 mV s-1 and device capacitance of ~ 343 F g-1 at 1.7 A g-1) and power performance (e.g., power density of 50 and 2500 W kg-1 at the energy …
The ability to engineer the electronic band structure and, more strikingly, to access new exotic phase of matter has been the cornerstone of the advance of science and technology. Twisting van der Waals materials to form moiré superlattice is a powerful paradigm and can drive graphene from a normal metallic state into an insulating, superconducting, or ferromagnetic states. Here, we present a new route to create non-trivial band structure and consequently an exotic phase of matter via lithographically patterned strain (lattice deformation). This method is used to realize an artificially corrug…
Theoretical research has predicted that ripples of graphene generates effective gauge field on its low energy electronic structure and could lead to zero-energy flat bands, which are the analog of Landau levels in real magnetic fields. Here we demonstrate, using a combination of scanning tunneling microscopy and tight-binding approximation, that the zero-energy Landau levels with vanishing Fermi velocities will form when the effective pseudomagnetic flux per ripple is larger than the flux quantum. Our analysis indicates that the effective gauge field of the ripples results in zero-energy flat …
A generalized Dirac equation is derived in order to describe charge carriers moving in corrugated graphene, which is the case for temperatures above 10°K due to the presence of flexural phonons. Such interaction is taken into account by considering an induced metric, in the same spirit as the general relativity approach for the description of fermionic particle moving in a curved space-time. The resulting equation allows to include in a natural way the presence of other phonon branches as well as an external electromagnetic field. It also predicts non-linear effects which are not present in th…
Propagating edge and interfacial states in corrugated graphene: Robustness and configurability
University of Science and Technology Houari Boumediene（哈乌阿里·布麦迪内科技大学）；Ecole Supérieure des Sciences des Aliments et des Industries Agroalimentaires（食品科学与食品工业高等学院）；The University of Hong Kong（香港大学）；Ohio University（俄亥俄大学）
Periodically corrugated epitaxial graphene and hexagonal boron nitride (h-BN) on metallic substrates are considered as perspective templates for the self-assembly of nanoparticles arrays. By using first-principles calculations, we determine binding energies and diffusion activation barriers of metal adatoms on graphene and h-BN. The observed chemical trends can be understood in terms of the interplay between charge transfer and covalent bonding involving the adatom d electrons. We further investigate the electronic effects of the metallic substrate and find that periodically corrugated templat…
In this paper, a framework of {w_1, w_2, R} classification for constructing the graphene nanomesh (GNM) of zigzag-edged hexagonal nanohole is systematically built. The three integer indexes w_1, w_2, and R indicate the distances between two neighboring sides of nanoholes in two directions and the nanohole size respectively, which leading to a straightforward gap opening criteria, i.e., w_1+w_2-R=3n+1,n is integer, steered via DFT band structure calculations.The guiding rule indicates that the semimetallic and semiconducting variation is consistent with a peculiar sequence "010" and "100" ("0"/…
We report measurements of the electronic structure and surface morphology of exfoliated graphene on an insulating substrate using angle-resolved photoemission and low energy electron diffraction. Our results show that although exfoliated graphene is microscopically corrugated, the valence band retains a massless fermionic dispersion, with a Fermi velocity of ~10^6 m/s. We observe a close relationship between the morphology and electronic structure, which suggests that controlling the interaction between graphene and the supporting substrate is essential for graphene device applications.
The simultaneous combination of scanning probe methods (tunnelling and force microscopies, STM and AFM) is a unique way to get an information about crystallographic and electronic structure of the studied surface. Here we apply these methods accompanied by the state-of-the-art density functional theory (DFT) calculations to shed a light on the structure and electronic properties of the strongly-corrugated graphene/Rh(111) system. The atomically resolved images are obtained for both STM and AFM modes and compared with the DFT results showing good agreement between theory and experiment.
We investigate the electronic and transport properties of gated bilayer graphene with one corrugated layer, which results in a stacking AB/BA boundary. When a gate voltage is applied to one layer, topologically protected gap states appear at the corrugation, which reveal as robust transport channels along the stacking boundary. With increasing size of the corrugation, more localized, quantum-well-like states emerge. These finite-size states are also conductive along the fold, but in contrast to the stacking boundary states, which are gapless, they present a gap. We have also studied periodic c…
We report the structural and electronic properties of an artificial graphene/Ni(111) system obtained by the intercalation of a monoatomic layer of Ni in graphene/Ir(111). Upon intercalation, Ni grows epitaxially on Ir(111), resulting in a lattice mismatched graphene/Ni system. By performing Scanning Tunneling Microscopy (STM) measurements and Density Functional Theory (DFT) calculations, we show that the intercalated Ni layer leads to a pronounced buckling of the graphene film. At the same time an enhanced interaction is measured by Angle-Resolved Photo-Emission Spectroscopy (ARPES), showing a…
A new mechanism that induces charge density variations in corrugated graphene is proposed. Here it is shown how the interplay between lattice deformations and exchange interactions can induce charge separation, i.e., puddles of electrons and holes, for realistic deformation values of the graphene sheet. The induced charge density lies in the range of $10^{11}-10^{12}$ cm$^{-2}$, which is compatible with recent measurements.
The geometric and electronic properties of Bi-adsorbed monolayer graphene, enriched by the strong effect of substrate, are investigated by first-principles calculations. The six-layered substrate, corrugated buffer layer, and slightly deformed monolayer graphene are all simulated. Adatom arrangements are thoroughly studied by analyzing the ground-state energies, bismuth adsorption energies, and Bi-Bi interaction energies of different adatom heights, inter-adatom distance, adsorption sites, and hexagonal positions. A hexagonal array of Bi atoms is dominated by the interactions between the buffe…
Using highly controlled coverages of graphene on SiC(0001), we have studied the structure of the first graphene layer that grows on the SiC interface. This layer, known as the buffer layer, is semiconducting. Using x-ray reflectivity and x-ray standing waves analysis we have performed a comparative study of the buffer layer structure with and without an additional monolayer graphene layer above it. We show that no more than 26\% of the buffer carbon is covalently bonded to Si in the SiC interface. We also show that the top SiC bilayer is Si depleted and is the likely the cause of the incommens…
Graphene monolayers supported on oxide substrates have been demonstrated with superior charge mobility and thermal transport for potential device applications. Morphological corrugation can strongly influence the transport properties of the supported graphene. In this paper, we theoretically analyze the morphological stability of a graphene monolayer on an oxide substrate, subject to van der Waals interactions and in-plane mismatch strains. First, we define the equilibrium separation and the interfacial adhesion energy as the two key parameters that characterize the van der Waals interaction b…
Epitaxial graphene grown on metallic substrates presents, in several cases, a long-range periodic structure due to a lattice mismatch between the graphene and the substrate. For instance, graphene grown on Ir(111), displays a corrugated supercell with distinct adsorption sites due to a variation of its local electronic structure. This type of surface reconstruction represents a challenging problem for a detailed atomic surface structure determination for experimental and theoretical techniques. In this work, we revisited the surface structure determination of graphene on Ir(111) by using the u…
Graphene on copper is a system of high technological relevance, as Cu is one of the most widely used substrates for the CVD growth of graphene. However, very little is known about the details of their interaction. One approach to gain such information is studying the superlattices emerging due to the mismatch of the two crystal lattices. However, graphene on copper is a low-corrugated system making both their experimental and theoretical study highly challenging. Here, we report the observation of a new rotational Moire superlattice of CVD graphene on Cu (111), characterized by a periodicity o…
Friction-induced energy dissipation impedes the performance of nanoscale devices during their relative motion. Nevertheless, an ingeniously designed structure which utilizes graphene topping can tune the friction force signal by inducing local strain. The present work reports capping of graphene over Si grooved surfaces of different pitch lengths from sub-nanoscale (P=40 nm) to a quarter of a micron (P= 250 nm). The variation in the pitch lengths induces different strains in graphene revealed by scanning probe techniques, Raman spectroscopy and molecular dynamics (MD) simulation. The asymmetri…
The moiré superstructure of graphene grown on metals can drive the assembly of molecular architectures, as iron-phthalocyanine (FePc) molecules, allowing for the production of artificial molecular configurations. A detailed analysis of the Gr/Co interaction upon intercalation (including a modelling of the resulting moiré pattern) is performed here by density functional theory, which provides an accurate description of the template as a function of the corrugation parameters. The theoretical results are a preliminary step to describe the interaction process of the FePc molecules adsorption on t…
Topographic scanning tunneling microscopy (STM) images of epitaxial single layer graphene on the Rh(111) surface reveal that extended single crystalline graphene domains are produced without any defects on a large scale. High resolution imaging shows that the moiré structure resulting from the lattice mismatch between the Rh(111) substrate and graphene is highly corrugated, containing regions of an additional spatial modulation in the moiré supercell compared with those previously reported for graphene on Ir(111) or graphene on Ru(0001). These areas, which correspond to the "bridge" regions of…
While an increasing number of two-dimensional (2D) materials, including graphene and silicene, have already been realized, others have only been predicted. An interesting example is the two-dimensional form of silicon carbide (2D-SiC). Here, we present an observation of atomically thin and hexagonally bonded nanosized grains of SiC assembling temporarily in graphene oxide pores during an atomic resolution scanning transmission electron microscopy experiment. Even though these small grains do not fully represent the bulk crystal, simulations indicate that their electronic structure already appr…
Graphene on $L1_0$-FePd(001), which has been experimentally studied in recent years, is a heterogeneous interface with a significant lattice symmetry mismatch between the honeycomb structure of graphene and tetragonal alloy surface. In this work, we report on the density functional study of its atomic-scale configurations, electronic and magnetic properties, and adsorption mechanism, which have not been well understood in previous experimental studies. We propose various atomic-scale models, including simple nontwisted and low-strain twisted interfaces, and analyze their energetical stability …
