Local curvature, or bending, of a graphene sheet is known to increase the chemical reactivity presenting an opportunity for templated chemical functionalization. Using first principles calculations based on density functional theory (DFT) we investigate the reduction of the reaction barrier for adsorption of atomic hydrogen at linear bends in graphene. We find a significant lowering (15%) for realistic radii of curvature (20 Å), and that adsorption along the linear bend leads to a stable linear kink. We compute the electronic transport properties of individual and multiple kink-lines, and demonstrate how these act as efficient barriers for electron transport. In particular, two parallel kink-lines form a graphene pseudo-nanoribbon structure with a semi-metallic/semi-conducting electronic structure closely related to the corresponding isolated ribbons; the ribbon band gap translates into a transport gap for transport across the kink lines. We finally consider pseudo-ribbon based heterostructures, and propose that such structures present a novel approach for band gap engineering in nanostructured graphene.
We set up an evolutionary algorithm combined with density functional tight-binding (DFTB) calculations to investigate hydrogen adsorption on flat graphene and graphene monolayers curved over substrate steps. During the evolution, candidates for the new generations are created by adsorption of an additional hydrogen atom to the stable configurations of the previous generation, where a mutation mechanism is also incorporated. Afterwards a two-stage selection procedure is employed. Selected candidates act as the parents of the next generation. In curved graphene, the evolution follows a similar p…
Graphene, the two-dimensional form of carbon presents outstanding electronic and transport properties. This gives hope for the development of applications in nanoelectronics. However, for industrial purpose, graphene has to be supported by a substrate. We focus here on the graphene-on-SiC system to discuss how the SiC substrate interacts with the graphene layer and to show the effect of the interface on graphene atomic and electronic structures.
We probe the local inhomogeneities of the electronic properties of graphene at the nanoscale using scanning probe microscopy techniques. First, we focus on the study of the electronic inhomogeneities caused by the graphene-substrate interaction in graphene samples exfoliated on silicon oxide. We find that charged impurities, present in the graphene-substrate interface, perturb the carrier density significantly and alter the electronic properties of graphene. This finding helps to understand the observed device-to-device variation typically observed in graphene-based electronic devices. Second,…
Graphene revealed a number of unique properties beneficial for electronics, including exceptionally high electron mobility and widely tunable Fermi level. However, graphene does not have an electron energy band gap, which presents a serious hurdle for its applications in digital electronics. A possible route for practical use of graphene in electronics is utilization of its exceptionally high thermal conductivity and electron current conducting properties. This invited review outlines the thermal properties of graphene and describes prospective graphene technologies that are not affected by th…
Using full potential density functional theory calculations we have investigated the structural and electronic properties of graphene and some other graphene-like materials, viz., monolayer of SiC, GeC, BN, AlN, GaN, ZnO, ZnS and ZnSe. We hope, with the advancement of material synthesis techniques, some these new materials will be synthesized in the near future for potential applications in various nano-devices.
Engineering the electronic properties of graphene has triggered great interest for potential applications in electronics and opto-electronics. Here we demonstrate the possibility to tune the electronic transport properties of graphene monolayers and multilayers by functionalisation with fluorine. We show that by adjusting the fluorine content different electronic transport regimes can be accessed. For monolayer samples, with increasing the fluorine content, we observe a transition from electronic transport through Mott variable range hopping in two dimensions to Efros - Shklovskii variable ran…
We review progress in developing epitaxial graphene as a material for carbon electronics. In particular, improvements in epitaxial graphene growth, interface control and the understanding of multilayer epitaxial graphene's electronic properties are discussed. Although graphene grown on both polar faces of SiC is addressed, our discussions will focus on graphene grown on the (000-1) C-face of SiC. The unique properties of C-face multilayer epitaxial graphene have become apparent. These films behave electronically like a stack of nearly independent graphene sheets rather than a thin Bernal-stack…
We review thermal properties of graphene and few-layer graphene, and discuss applications of these materials in thermal management of advanced electronics. The intrinsic thermal conductivity of graphene - among the highest of known materials - is dominated by phonons near the room temperature. The examples of thermal management applications include the few-layer graphene heat spreaders integrated near the heat generating areas of the high-power density transistors. It has been demonstrated that few-layer graphene heat spreaders can lower the hot-spot temperature during device operation resulti…
The article presents the work on the investigation of the surface structure as well as electronic and magnetic properties of graphene layer on a lattice matched surface of a ferromagnetic material, Ni(111).
We study the electronic structure of multilayer graphene using a $π$-orbital continuum model with nearest-neighbor intralayer and interlayer tunneling. Using degenerate state perturbation theory, we show that the low-energy electronic structure of arbitrarily stacked graphene multilayers consists of chiral pseudospin doublets with a conserved chirality sum.
Here we report a facile method to generate a high density of point defects in graphene on metal foil and show how the point defects affect the electronic structures of graphene layers. Our scanning tunneling microscopy (STM) measurements, complemented by first principle calculations, reveal that the point defects result in both the intervalley and intravalley scattering of graphene. The Fermi velocity is reduced in the vicinity area of the defect due to the enhanced scattering. Additionally, our analysis further points out that periodic point defects can tailor the electronic properties of gra…
Decoupling of the graphene layer from the ferromagnetic substrate via intercalation of sp metal has recently been proposed as an effective way to realize single-layer graphene-based spin-filter. Here, the structural and electronic properties of the prototype system, graphene/Al/Ni(111), are investigated via combination of electron diffraction and spectroscopic methods. These studies are accompanied by state-of-the-art electronic structure calculations. The properties of this prospective Al-intercalation-like system and its possible implementations in future graphene-based devices are discussed…
The successful fabrication of single layer graphene has greatly stimulated the progress of the research on graphene. In this article, focusing on the basic electronic and transport properties of graphene nanoribbons (GNRs), we review the recent progress of experimental fabrication of GNRs, and the theoretical and experimental investigations of physical properties and device applications of GNRs. We also briefly discuss the research efforts on the spin polarization of GNRs in relation to the edge states.
The epitaxial-graphene/graphene-oxide junction, an essential step towards epitaxial graphene electronics
已经沉积氧化石墨烯（GO）薄片以桥接两个外延石墨烯电极之间的间隙以产生全石墨烯装置。电学测量表明，由于GO中的带隙，在石墨烯/氧化石墨烯结处存在肖特基势垒（SB）。发现势垒高度约为0.7 eV，并且在180 $^\circ$ C退火后降低，这意味着可以通过改变氧化程度来调节间隙。发现GO迁移率的下限为850 cm $^2$ /Vs，与硅相当。已经实现了图案化外延石墨烯的{ \it In situ}局部氧化。
As the thinnest atomic membrane, graphene presents an opportunity to combine geometry, elasticity and electronics at the limits of their validity. The availability of reliable atomistic potentials for graphene allows unprecedented precise simulations of the mechanical response of atomic membranes. Here we describe the transport and electronic structure in the neighbourhood of conical singularities, the elementary excitations of the ubiquitous wrinkled and crumpled graphene that occur in non-epitaxial suspended samples where shear stresses are unavoidable. We use a combination of atomistic mech…
Local electrical imaging using microwave impedance microscope is performed on graphene in different modalities, yielding a rich hierarchy of the local conductivity. The low-conductivity graphite oxide and its derivatives show significant electronic inhomogeneity. For the conductive chemical graphene, the residual defects lead to a systematic reduction of the microwave signals. In contrast, the signals on pristine graphene agree well with a lumped-element circuit model. The local impedance information can also be used to verify the electrical contact between overlapped graphene pieces.
Despite the structures and properties of tilt grain boundaries of graphite surface and graphene have been extensively studied, their effect on the structures and electronic spectra of graphene layers has not been fully addressed. Here we study effects of one-dimensional tilt grain boundaries on structures and electronic spectra of graphene multilayers by scanning tunneling microscopy and spectroscopy. A tilt grain boundary of a top graphene sheet in graphene multilayers leads to a twist between consecutive layers and generates superstructures (Moiré patterns) on one side of the boundary. Our r…
We study how phonon structure manifests itself in the electronic density of states of graphene. A procedure for extracting the value of the electron-phonon renormalization $λ$ is developed. In addition, we identify direct phonon structures. With increasing doping, these structures, along with $λ$, grow in amplitude and no longer display particle-hole symmetry.
We present results of tight binding calculations demonstrating existence of degenerate electronic shells of Dirac Fermions in narrow, charge neutral graphene quantum rings. We predict removal of degeneracy with finite magnetic field. We show, using a combination of tight binding and configuration interaction methods, that by filling a graphene ring with additional electrons this carbon based structure with half-filled shell acquires a finite magnetic moment.
We report first principles investigations of the nonequilibrium transport properties of a Cu(111)|graphene interface. The Cu(111) electrode is found to induce a transmission minimum (TM) located -0.68eV below the Fermi level, a feature originating from the Cu-induced charge transfer resulting in n-type doped graphene with the Dirac point coinciding with the TM. An applied bias voltage shifts the n-graphene TM relative to the pure graphene TM and leads to a distinctive peak in the differential conductance indicating the doping level, a characteristic not observed in pure graphene.
The fabrication of atomically precise structures with designer electronic properties is one of the emerging topics in condensed matter physics. The required level of structural control can either be reached through atomic manipulation using the tip of a scanning tunneling microscope (STM) or by bottom-up chemical synthesis. In this review, we focus on recent progress in constructing novel, atomically precise artificial materials: artificial lattices built through atom manipulation and graphene nanoribbons (GNRs) realized by on-surface synthesis. We summarize the required theoretical background…
First-principles calculation has been performed to investigate the stability and electronic properties of double-layer graphene heterostructure (DLGH). In this system, two graphene layers are separated by hexagonal boron-nitride (h-BN) layers which work as a insulating barrier. Our results show that the stability of the system is determined by the atomistic configurations between graphene and its adjacent h-BN layer. Among different stacking sequences, Ab-stacking is most stable. Since the inserted h-BN layers modulate the on-site energies for carbon atoms of graphene layers, the electronic st…
Graphene functionalization by hydrogen and fluorine has been proposed as a route to modulate its reactivity and electronic properties. However, until now, proposed systems present degradation and limited hydrogen adsorption capacity. In this study, combining first-principles calculations based on density functional theory (DFT) and reactive molecular dynamics, we analyze the tuning of hydrogen adsorption and electronic properties in fluorinated and hydrogenated monolayer graphenes. Our results indicate that fluorine adsorption promotes stronger carbon$-$hydrogen bonds. By changing the concentr…
The electronic structure and magnetic properties of the graphene/Fe/Ni(111) system were investigated via combination of the density functional theory calculations and electron-spectroscopy methods. This system was prepared via intercalation of thin Fe layer (1 ML) underneath graphene on Ni(111) and its inert properties were verified by means of photoelectron spectroscopy. Intercalation of iron in the space between graphene and Ni(111) changes drastically the magnetic response from the graphene layer that is explained by the formation of the highly spin-polarized $3d_{z^2}$ quantum-well state i…
We investigate electronic transport property of a graphene monolayer covered by a graphene nanoribbon. We demonstrate that electronic transmission of a monolayer can be reduced when covered by a nanoribbon. The transmission reduction occurs at different energies determined by the width of nanoribbon. We explain the transmission reduction by using interference between wavefunctions in the monolayer and the nanoribbon. Furthermore, we show the transmission reduction of a monolayer is combinable when covered by more than one nanoribbon and propose a concept of "combination of control" for nano-ap…
We report on electronic properties of graphene synthesized by chemical vapor deposition (CVD) on copper then transferred to SiO2/Si. Wafer-scale (up to 4 inches) graphene films have been synthesized, consisting dominantly of monolayer graphene as indicated by spectroscopic Raman mapping. Low temperature transport measurements are performed on micro devices fabricated from such CVD graphene, displaying ambipolar field effect (with on/off ratio ~5 and carrier mobilities up to ~3000 cm^2/Vs) and "half-integer" quantum Hall effect, a hall-mark of intrinsic electronic properties of monolayer graphe…
We present an orbital-resolved density functional theory study on the electronic properties of hydrogen and lithium intercalated graphene grown on the Si face of SiC. Starting from the $(6\sqrt3\times6\sqrt3)R30^{\circ}$ surface reconstruction of the graphene/SiC heterosystem, we find that both H and Li can restore the ideal structural characteristics of the two nonequivalent junction parts (i.e. graphene and the SiC substrate) when inserted at the interface. However, the chemical/electrostatic interactions remain different for the two cases. Hence, H-intercalated epitaxial graphene is subject…
Small-twist-angle bilayer graphene supports strongly correlated insulating states and superconductivity. Twisted few-layer graphene systems are likely to open up new directions for strong correlation physics in moiré superlattices. We derive and study moiré band models that describe the electronic structure of graphene trilayers in which one of the three layers is twisted by a small angle relative to perfect AAA, ABA, or ABC stacking arrangements. We find that the electronic structure depends very strongly on the starting stackings arrangement and on which layer is twisted. We identify ABA sta…
Tuning the Electronic Structure of Graphene by Controlling Spatial Confinement
Center for Advanced Systems Understanding (CASUS)（高级系统理解中心）；Helmholtz Zentrum Dresden-Rossendorf（德累斯顿-罗斯多夫亥姆霍兹中心）；Institute of Artificial Intelligence, Technische Universität Dresden（德累斯顿工业大学人工智能研究所）
Using first-principles calculations, we study the structural and electronic properties of the bilayer SnS/graphene, bilayer SnS/bilayer graphene (AA-stacked), bilayer SnS/bilayer graphene (AB-stacked) and monolayer SnS/graphene/monolayer SnS van der Waals (vdW) heterostructures. Electronic properties of all components of the vdW heterostructures are well preserved, which reflects the weakness of the vdW interaction. In the cases of bilayer SnS/graphene and bilayer SnS/bilayer graphene (AA-stacked), an Ohmic contact is formed which can be turned first into p-type and then into n-type Schottky c…
We achieve fine tuning of graphene effective doping by applying ultrahigh pressures (> 10 GPa) using Atomic Force Microscopy (AFM) diamond tips. Specific areas in graphene flakes are irreversibly flattened against a SiO2 substrate. Our work represents the first demonstration of local creation of very stable effective p-doped graphene regions with nanometer precision, as unambiguously verified by a battery of techniques. Importantly, the doping strength depends monotonically on the applied pressure, allowing a controlled tuning of graphene electronics. Through this doping effect, ultrahigh pres…
We discuss the chiral decomposition of non-symmetric stacking structures. It is shown that the low-energy electronic structure of Bernal stacked graphene multilayer deposited on h-BN consists of chiral pseudospin doublets. N-layer graphene stocks on h-BN layer have N/2 effective bilayer graphene systems and one effective h-BN layer if N is even or (N-1)/2 effective graphene bilayers plus one graphene monolayer modified by h-BN layer if N is odd. We present the decomposition procedure and we derive the recurrence relations for the effective parameters characterizing the chiral subsystems. The e…
Electronic properties of bilayer graphene are distinct from both the conventional two dimensional electron gas and monolayer graphene due to its particular chiral properties and excitation charge carrier dispersions. We study the effect of strain on the electronic structure, the edge-states and charge transport of bilayer graphene nanoribbon at zero-temperature. We demonstrate a valley polarized quantum Hall effect in biased bilayer graphene when the system is subjected to a perpendicular magnetic field. In this system a topological phase transition from a quantum valley Hall to a valley polar…
In this paper, the electronic properties of 30° twisted double bilayer graphene, which loses the translational symmetry due to the incommensurate twist angle, are studied by means of the tight-binding approximation. We demonstrate the interlayer decoupling in the low-energy region from various electronic properties, such as the density of states, effective band structure, optical conductivity and Landau level spectrum. However, at Q points, the interlayer coupling results in the appearance of new Van Hove singularities in the density of states, new peaks in the optical conductivity and importa…
Electronic properties of quantum dots (QDs) depend sensitively on their parent materials. Therefore, confined electronic states in graphene QDs (GQDs) of monolayer and Bernal-stacked bilayer graphene are quite different. Twisted bilayer graphene (TBG) is distinct from monolayer and Bernal-stacked bilayer graphene because of the new degree of freedom: twist angle. In the past few years, numerous efforts have been made to realize the GQDs of monolayer and Bernal-stacked bilayer graphene and achieved great success. Thus far, however, strategies for realizing GQDs of TBG have been elusive. Here, w…
We present electronic structure calculations of few-layer epitaxial graphene nanoribbons on SiC(0001). Trough an atomistic description of the graphene layers and the substrate within the extended Hückel Theory and real/momentum space projections we argue that the role of the heterostructure's interface becomes crucial for the conducting capacity of the studied systems. The key issue arising from this interaction is a Fermi level pinning effect introduced by dangling interface bonds. Such phenomenon is independent from the width of the considered nanostructures, compromising the importance of c…
We unveil the nature of the structural disorder in bottom-up zigzag graphene nanoribbons along with its effect on the magnetism and electronic transport on the basis of scanning probe microscopies and first-principles calculations. We find that edge-missing m-xylene units emerging during the cyclodehydrogenation step of the on-surface synthesis are the most common point defects. These "bite'' defects act as spin-1 paramagnetic centers, severely disrupt the conductance spectrum around the band extrema, and give rise to spin-polarized charge transport. We further show that the electronic conduct…
We report an atomically-resolved scanning tunneling microscopy (STM) investigation of the edges of graphene grains synthesized on Cu foils by chemical vapor deposition (CVD). Most of the edges are macroscopically parallel to the zigzag directions of graphene lattice. These edges have microscopic roughness that is found to also follow zigzag directions at atomic scale, displaying many ~120 degree turns. A prominent standing wave pattern with periodicity ~3a/4 (a being the graphene lattice constant) is observed near a rare-occurring armchair-oriented edge. Observed features of this wave pattern …
Realization of graphene moiré superstructures on the surface of 4d and 5d transition metals offers templates with periodically modulated electron density, which is responsible for a number of fascinating effects, including the formation of quantum dots and the site selective adsorption of organic molecules or metal clusters on graphene. Here, applying the combination of scanning probe microscopy/spectroscopy and the density functional theory calculations, we gain a profound insight into the electronic and topographic contributions to the imaging contrast of the epitaxial graphene/Ir(111) syste…
This work analyzes carrier transport, the relaxation of non-equilibrium charge, and the electronic structure of fluorinated graphene (FG) films with graphene quantum dots (GQDs). The FG films with GQDs were fabricated by means of chemical functionalization in an aqueous solution of hydrofluoric acid. High fluctuations of potential relief inside the FG barriers have been detected in the range of up to 200 mV. A phenomenological expression that describes the dependence of the time of non-equilibrium charge emission from GQDs on quantum confinement levels and film thickness (potential barrier par…
We probe the local inhomogeneities in the electronic properties of exfoliated graphene due to the presence of charged impurities in the SiO2 substrate using a combined scanning tunneling and electrostatic force microscope. Contact potential difference measurements using electrostatic force microscopy permit us to obtain the average charge density but it does not provide enough resolution to identify individual charges. We find that the tunneling current decay constant, which is related to the local tunneling barrier height, enables one to probe the electronic properties of graphene distorted a…
We have systematically investigated the effect of oxidation on the structural and electronic properties of graphene based on first-principles calculations. Energetically favorable atomic configurations and building blocks are identified, which contain epoxide and hydroxyl groups in close proximity with each other. Different arrangements of these units yield an LDA band gap over a range of a few eV. These results suggest the possibility of creating and tuning the band gap in graphene by varying the oxidation level and the relative amount of epoxide and hydroxyl functional groups on the surface.
Graphene with excellent 2D characters has been required to expand their potentials for meeting applicational demands in recent years. As one avenue, several approaches for fablicating 3D porous graphene network structures have been developed to realize multi-functional graphene materials with 2D graphene. Here we overview characteristics of 3D porous graphene for future electronic device applications along with physical insights into "2D to 3D graphene", where the characters of 2D graphene such as massless Dirac fermions are well preserved. The present review thus summarizes recent 3D porous g…
Discoveries of graphene and graphane possessing unique electronic and magnetic properties offer a bright future for carbon based electronics, with future prospects of superseding silicon in the semiconductor industry.
The direct growth of graphene on semiconducting or insulating substrates might help to overcome main drawbacks of metal-based synthesis, like metal-atom contaminations of graphene, transfer issues, etc. Here we present the growth of graphene on n-doped semiconducting Ge(110) by using an atomic carbon source and the study of the structural and electronic properties of the obtained interface. We found that graphene interacts weakly with the underlying Ge(110) substrate that keeps graphene's electronic structure almost intact promoting this interface for future graphene-semiconductor applications…
The electronic and magnetic properties of the graphene/Eu/Ni(111) intercalation-like system are studied in the framework of the GGA+U approach with dispersive interactions taken into account. Intercalation of monoatomic Eu layer underneath graphene on Ni(111) leads to the drastic changes of the electronic structure of graphene compared to free-standing graphene as well as graphene/Ni(111). The strong influence of the spin-polarised Eu 4f states, crossing the graphene-derived $π$ states, on magnetic properties of graphene and on spin-filtering properties of the graphene/Eu/Ni(111) trilayer is d…
Using the density-functional-based tight-binding method we performed a systematic comparative study of stability, structural and electronic properties for 12 various types of graphene allotropes, which are likely candidates for engineering of novel graphene-like materials.
Combining the electronic structures of two-dimensional monolayers in ultrathin hybrid nanocomposites is expected to display new properties beyond their simplex components. Here, first-principles calculations are performed to study the structural, electronic and optical properties of hybrid graphene and phosphorene nanocomposite. It turns out that weak van der Waals interactions dominate between graphene and phosphorene with their intrinsic electronic properties preserved. Hybrid graphene and phosphorene nanocomposite shows tunable band gaps at graphene's Dirac point and a transition from hole …
Most materials in available macroscopic quantities are polycrystalline. Graphene, a recently discovered two-dimensional form of carbon with strong potential for replacing silicon in future electronics, is no exception. There is growing evidence of the polycrystalline nature of graphene samples obtained using various techniques. Grain boundaries, intrinsic topological defects of polycrystalline materials, are expected to dramatically alter the electronic transport in graphene. Here, we develop a theory of charge carrier transmission through grain boundaries composed of a periodic array of dislo…
Graphene is a promising contender to succeed the throne of silicon in electronics. To this goal, large-scale epitaxial growth of graphene on substrates should be developed. Among various methods along this line, epitaxial growth of graphene on SiC substrates by thermal decomposition of surface layers has proved itself quite satisfactory both in quality and in process reliability. Even modulation of structural and hence electronic properties of graphene is possible by tuning the graphene/SiC interface structure. The challenges for this graphene-on-SiC technology, however, are the abdication of …
The electronic and optical properties of graphene monoxide, a new type of semiconductor materials, are first theoretically studied based on density functional theory. Electronic calculations show that the band gap is 0.952 eV which indicate that graphene monoxide is a direct band gap semiconductor. The density of states of graphene monoxide and the partial density of states for C and O are given to understand the electronic structure. In addition, we calculate the optical properties of graphene monoxide including the complex dielectric function, absorption coefficient, the complex refractive i…
By using the first-principles method based on density of functional theory, we study the electronic properties of twisted bilayer graphene with some specific twist angles and interlayer spacings. With the decrease of the twist angle(the unit cell becomes larger), the energy band becomes narrower and Coulomb repulsion increases, leading to the enhancement of electronic correlation; On the other hand, as the interlayer spacing decreases and the interlayer coupling becomes stronger, the correlation becomes stronger. By tuning the interlayer coupling, we can realize the strongly correlated state w…
