It has been shown that the first C layer on the SiC(0001)(2{\times}2)C surface already exhibits graphene-like electronic structure, with linear pi bands near the Dirac point. Indeed, the (2{\times}2)C reconstruction, with a Si adatom and C restatom structure, efficiently passivates the SiC(0001) surface thanks to an adatom/restatom charge transfer mechanism. Here, we study the effects of interface modifications on the graphene layer using density functional theory calculations. The modifications we consider are inspired from native interface defects observed by scanning tunneling microscopy. One H atom per 4 {\times} 4 SiC cell (5 {\times} 5 graphene cell) is introduced in order to saturate a restatom dangling bond and hinder the adatom/restatom charge transfer. As a consequence, the graphene layer is doped with electrons from the substrate and the interaction with the adatom states slightly increases. Native interface defects are therefore likely to play an important role in the doping mechanism on the C terminated SiC substrates. We also conclude that an efficient passivation of the C face of SiC by H requires a complete removal of the reconstruction. Otherwise, at variance with the Si terminated SiC substrates, the presence of H at the interface would increase the graphene/substrate interaction.
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…
We present a study of quasi-free-standing monolayer graphene obtained by intercalation of Au atoms at the interface between the carbon buffer layer (Bu-L) and the silicon-terminated face (0001) of 4H-silicon carbide. Au intercalation is achieved by deposition of atomically thin Au on the Bu-L followed by annealing at 850 °C in an Argon atmosphere. We explore the intercalation of Au and decoupling of the Bu-L into quasi-free-standing monolayer graphene by surface science characterizations and electron transport in top-gated electronic devices. By gate-dependent magnetotransport we find that the…
We show using scanning tunneling microscopy, spectroscopy, and ab initio calculations that several intercalation structures exist for Na in epitaxial graphene on SiC(0001). Intercalation takes place at room temperature and Na electron-dopes the graphene. It intercalates in-between single-layer graphene and the carbon-rich interfacial layer. It also penetrates beneath the interfacial layer and decouples it to form a second graphene layer. This decoupling is accelerated by annealing and is verified by direct Na deposition onto the interface layer. Our observations show that intercalation in grap…
Intercalation of Au can produce giant Rashba-type spin-orbit splittings in graphene but this has not yet been achieved on a semiconductor substrate. For graphene/SiC(0001), Au intercalation yields two phases with different doping. Here, we report the preparation of an almost pure p-type graphene phase after Au intercalation. We observe a 100 meV Rashba-type spin-orbit splitting at 0.9 eV binding energy. We show that this giant splitting is due to hybridization and much more limited in energy and momentum space than for Au-intercalated graphene on Ni.
Graphene on silicon carbide (SiC) bears great potential for future graphene electronic applications because it is available on the wafer-scale and its properties can be custom-tailored by inserting various atoms into the graphene/SiC interface. It remains unclear, however, how atoms can cross the impermeable graphene layer during this widely used intercalation process. Here we demonstrate that, in contrast to the current consensus, graphene layers on SiC are not homogeneous, but instead composed of domains of different crystallographic stacking. We show that these domains are intrinsically for…
Electronic devices based on graphene technology are catching on rapidly and the ability to engineer graphene properties at the nanoscale is becoming, more than ever, indispensable. Here, we present a new procedure of graphene functionalization on SiC(0001) that paves the way towards the fabrication of complex graphene electronic chips. The procedure resides on the well-known ion-implantation technique. The efficiency of the working principle is demonstrated by the intercalation of the epitaxial graphene layer on SiC(0001) with Bi atoms, which was not possible following standard procedures. Our…
In this work we use LEEM, XPEEM and XPS to study how the excess Si at the graphene-vacuum interface reorders itself at high temperatures. We show that silicon deposited at room temperature onto multilayer graphene films grown on the SiC(000[`1]) rapidly diffuses to the graphene-SiC interface when heated to temperatures above 1020. In a sequence of depositions, we have been able to intercalate ~ 6 ML of Si into the graphene-SiC interface.
Previous experimental observations for H intercalation under graphene on SiC surfaces motivate clarification of configuration stabilities and kinetic processes related to intercalation. From first-principles density-functional-theory (DFT) calculations, we analyze H adsorption and intercalation for graphene on a 6H-SiC(0001) surface, where the system includes two single-atom-thick graphene layers: the top-layer graphene (TLG) and the underling buffer-layer graphene (BLG) above the terminal Si layer. Our chemical potential analysis shows that, in the low-H coverage regime (described by a single…
We present a systematical study via scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) on the effect of the exposure of Lithium (Li) on graphene on silicon carbide (SiC). We have investigated Li deposition both on epitaxial monolayer graphene and on buffer layer surfaces on the Si-face of SiC. At room temperature, Li immediately intercalates at the interface between the SiC substrate and the buffer layer and transforms the buffer layer into a quasi-free-standing graphene. This conclusion is substantiated by LEED and STM evidence. We show that intercalation occurs th…
Based on ab initio calculations, we study the effect of intercalating twisted bilayer graphene with carbon. Surprisingly, we find that the intercalant pulls the atoms in the two layers closer together locally when placed in certain regions in between the layers, and the process is energetically favorable as well. This arises because in these regions of the supercell, the local environment allows the intercalant to form tetrahedral bonding with nearest atoms in the layers. Intercalating AB- or AA-bilayer graphene with carbon does not produce this effect; therefore, the nontrivial effect owes it…
Gold intercalation between the buffer layer and a graphene monolayer of epitaxial graphene on SiC(0001) leads to the formation of quasi free standing small aggregates of clusters. Angle Resolved Photoemission Spectroscopy measurements reveal that these clusters preserve the linear dispersion of the graphene quasiparticles and surprisingly increase their Fermi velocity. They also strongly modify the band structure of graphene around the Van Hove singularities (VHs) by a strong extension without charge transfer. This result gives a new insight on the role of the intercalant in the renormalizatio…
Ca-intercalation has opened a way for superconductivity in graphene on SiC. However, the atomic and electronic structures being critical for superconductivity are still under discussion. We find the essential role of the interface between monolayer graphene and the SiC substrate for superconductivity. In the Ca-intercalation process, at the interface a carbon layer terminating SiC changes to graphene by Ca-termination of SiC (monolayer graphene becomes bilayer) with inducing more carriers than a free-standing model. Then, Ca is intercalated in-between graphene layers, which shows superconducti…
On the SiC(0001) surface (the silicon face of SiC), epitaxial graphene is obtained by sublimation of Si from the substrate. The graphene film is separated from the bulk by a carbon-rich interface layer (hereafter called the buffer layer) which in part covalently binds to the substrate. Its structural and electronic properties are currently under debate. In the present work we report scanning tunneling microscopy (STM) studies of the buffer layer and of quasi-free-standing monolayer graphene (QFMLG) that is obtained by decoupling the buffer layer from the SiC(0001) substrate by means of hydroge…
We address the energetic stability of the graphene/SiC(0001) interface and the associated binding mechanism by studying a series of low-strain commensurate interface structures within a density functional scheme. Among the structures with negligible strain, the 6\surd3\times6\surd3 R30° SiC periodicity shows the lowest interface energy, providing a rationale for its frequent experimental observation. The interface stability is driven by the enhanced local reactivity of the substrate-bonded graphene atoms undergoing sp2-to-sp3 rehybridization (pyramidalization). By this mechanism, relaxed struc…
We investigate the magnetotransport properties of quasi-free standing epitaxial graphene bilayer on SiC, grown by atmospheric pressure graphitization in Ar, followed by H$_2$ intercalation. At the charge neutrality point the longitudinal resistance shows an insulating behavior, which follows a temperature dependence consistent with variable range hopping transport in a gapped state. In a perpendicular magnetic field, we observe quantum Hall states (QHSs) both at filling factors ($ν$) multiple of four ($ν=4, 8, 12$), as well as broken valley symmetry QHSs at $ν=0$ and $ν=6$. These results unamb…
Principal structural defects in graphene layers, synthesized on a carbon-terminated face, i.e. the SiC(000) face of a 4H-SiC substrate, are investigated using microscopic methods. Results of high-resolution transmission electron microscopy (HRTEM) reveal their atomic arrangement. Mechanism of such defects creation, directly related to the underlying crystallographic structure of the SiC substrate, is elucidated. The connection between the 4H-SiC(000) surface morphology, including the presence of the single atomic steps, the sequences of atomic steps, and also the macrosteps, and the correspond…
Intercalation of rare earth metals ($RE$ = Eu, Dy, and Gd) is achieved by depositing the $RE$ metal on graphene that is grown on silicon-carbide (SiC) and by subsequent annealing at high temperatures to promote intercalation. STM images of the films reveal that the graphene layer is defect free and that each of the intercalated metals has a distinct nucleation pattern. Intercalated Eu forms nano-clusters that are situated on the vertices of a Moir{è} pattern, while Dy and Gd form randomly distributed nano-clusters. X-ray magnetic circular dichroism (XMCD) measurements of intercalated films rev…
Effects of gold cluster intercalation in graphene: stationary waves and modified QPI features
Université Paris Saclay, CNRS, CEA, Institut de Physique Théorique（巴黎萨克雷大学）；Institut de Sciences des Matériaux de Mulhouse, CNRS-UMR 7361 Université de Haute Alsace（米卢斯材料科学研究所）；Université Paris Saclay, CNRS, Laboratoire de Physique des Solides（巴黎萨克雷大学）
Our first-principles calculations show that an energy gap around 0.12-0.25 eV can be engineered in epitaxial graphene on SiC(0001) through the non-covalent intercalation of transition- or alkali-metals, yet originated from the distinct mechanisms. The former is attributed to the combined effects of metal induced perpendicular electric field and interaction while the latter is solely attributed to the built-in electric field. A great advantage of this scheme is that the gap size is almost independent of the gate voltage up to 1 V/nm, thus reserving the electric means to tune the Fermi level of …
We investigate the morphology of quasi-free-standing monolayer graphene (QFMLG) formed at several temperatures by hydrogen intercalation and discuss its relationship with transport properties. Features corresponding to incomplete hydrogen intercalation at the graphene-substrate interface are observed by scanning tunneling microscopy on QFMLG formed at 600 and 800°C. They contribute to carrier scattering as charged impurities. Voids in the SiC substrate and wrinkling of graphene appear at 1000°C, and they decrease the carrier mobility significantly.
Time-resolved study of carbonization and growth of ultrathin 3C-SiC on Si(111) under ultra-high vacuum
Central European Institute of Technology, Brno University of Technology（中欧技术研究所，布尔诺理工大学）；Institute of Physical Engineering, Brno University of Technology（物理工程学院，布尔诺理工大学）
Structured growth of high quality graphene is necessary for technological development of carbon based electronics. Specifically, control of the bunching and placement of surface steps under epitaxial graphene on SiC is an important consideration for graphene device production. We demonstrate lithographically patterned evaporated amorphous carbon corrals as a method to pin SiC surface steps. Evaporated amorphous carbon is an ideal step-flow barrier on SiC due to its chemical compatibility with graphene growth and its structural stability at high temperatures, as well as its patternability. The …
The potential of graphene to impact the development of the next generation of electronics has renewed interest in its growth and structure. The graphitization of hexagonal SiC surfaces provides a viable alternative for the synthesis of graphene, with wafer-size epitaxial graphene on SiC(0001) now possible. Despite this recent progress, the exact nature of the graphene-SiC interface and whether the graphene even has a semiconducting gap remain controversial. Using scanning tunneling microscopy with functionalized tips and density functional theory calculations, here we show that the interface i…
We proposed a new way, adding intertube atoms, to enhance interfacial thermal conductance (ITC) between SiC-carbon nanotube (CNT) array structure. Non-equilibrium molecular dynamics method was used to study the ITC. The results show that the intertube atoms can significantly enhance the ITC. The dependence of ITC on both the temperature and the number of intertube atoms are shown. The mechanism is analyzed by calculating probability distributions of atomic forces and vibrational density of states. Our study may provide some guidance on enhancing the ITC of CNT-based composites.
We show the successful intercalation of large area (1 cm$^2$) epitaxial few-layer graphene grown on 4H-SiC with FeCl$_3$. Upon intercalation the resistivity of this system drops from an average value of $\approx 200 \ Ω/sq$ to $\approx 16 \ Ω/sq$ at room temperature. The magneto-conductance shows a weak localization feature with a temperature dependence typical of graphene Dirac fermions demonstrating the decoupling into parallel hole gases of each carbon layer composing the FeCl$_3$ intercalated structure. The phase coherence length ($\approx 1.2 μ$m at 280 mK) decreases rapidly only for temp…
Intercalation is an established technique for tailoring the electronic structure of epitaxial graphene. Moreover, it enables the synthesis of otherwise unstable two-dimensional (2D) layers of elements with unique physical properties compared to their bulk versions due to interfacial quantum confinement. In this work, we present uniformly Pb-intercalated quasi-freestanding monolayer graphene on SiC, which turns out to be essentially charge neutral with an unprecedented $p$-type carrier density of only $(5.5\pm2.5)\times10^9$ cm$^{-2}$. Probing the low-energy electronic structure throughout the …
In recent times, trilayer graphene has attracted wide attention owing to its stacking and electric field dependent electronic properties. However, a direct and well-resolved experimental visualization of its band structure has not yet been reported. In this work, we present angle resolved photoemission spectroscopy (ARPES) data which show with high resolution the electronic band structure of trilayer graphene obtained on α-SiC(0001) and β-SiC(111) via hydrogen intercalation. Electronic bands obtained from tight-binding calculations are fitted to the experimental data to extract the interatomic…
Single-crystal carbon nanomaterials have led to great advances in nanotechnology. The first single-crystal carbon nanomaterial, fullerene, was fabricated in a zero-dimensional form. One-dimensional carbon nanotubes and two-dimensional graphene have since followed and continue to provide further impetus to this field. In this study, we fabricated designed three-dimensional (3D) single-crystal carbon architectures by using silicon carbide templates. For this method, a designed 3D SiC structure was transformed into a 3D freestanding single-crystal carbon structure that retained the original SiC s…
In this study, we first show that the argon flow during epitaxial graphene growth is an important parameter to control the quality of the buffer and the graphene layer. Atomic force microscopy (AFM) and low-energy electron diffraction (LEED) measurements reveal that the decomposition of the SiC substrate strongly depends on the Ar mass flow rate while pressure and temperature are kept constant. Our data are interpreted by a model based on the competition of the SiC decomposition rate, controlled by the Ar flow, with a uniform graphene buffer layer formation under the equilibrium process at the…
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.
Dispersionless energy bands are a peculiar property gathering increasing attention for the emergence of novel photonic, magnetic and electronic properties. Here we report the first observation of a graphene superstructure n-doped up to the Lifshitz transition and exhibiting a flat band, obtained by ordered Erbium intercalation between a single layer graphene and SiC(0001). STM experiments reveal large graphene areas characterized by a long-range ordered hexagonal superstructure with a lattice parameter of 1.40 nm, rotated by 19 degrees with respect to the original lattice. Angle Resolved Photo…
We use angle-resolved photoemission spectroscopy to investigate the electronic structure of bilayer graphene at high n-doping and extreme displacement fields, created by intercalating epitaxial monolayer graphene on silicon carbide with magnesium to form quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide. Angle-resolved photoemission spectroscopy reveals that upon magnesium intercalation, the single massless Dirac band of epitaxial monolayer graphene is transformed into the characteristic massive double-band Dirac spectrum of quasi-freestanding bilayer graphene. Analys…
X-ray magnetic circular dichroism (XMCD) reveal the magnetic properties of intercalated europium metal under graphene on SiC(0001). Intercalation of Eu nano-clusters (average size 2.5 nm) between graphene and SiC substate are formed by deposition of Eu on epitaxially grown graphene that is subsequently annealed at various temperatures while keeping the integrity of the graphene layer. Using sum-rules analysis of the XMCD of Eu M$_{4,5}$ edges at $T = 15$ K, our samples show paramagnetic-like behavior with distinct anomaly at T $\approx$ 90 K which may be related to the N{è}el transition, T$_N$…
Classical molecular-dynamics simulations were carried out to study epitaxial growth of graphene on 6H-SiC(0001) substrate. It was found that there exists a threshold annealing temperature above which we observe formation of graphitic structure on the substrate. To check the sensitivity of the simulation results, we tested two empirical potentials and evaluated their reliability by the calculated characteristics of graphene, its carbon-carbon bond-length, pair correlation function, and binding energy.
Quasi free standing monolayer graphene (QFMLG) grown on SiC by selective Si evaporation from the Si-rich SiC(0001) face and H intercalation displays irregularities in STM and AFM analysis, appearing as localized features, which we previously identified as vacancies in the H layer coverage [Y Murata, et al. Nano Res, in press, DOI: 10.1007/s12274-017-1697-x]. The size, shape, brightness, location, and concentration of these features, however, are variable, depending on the hydrogenation conditions. In order to shed light on the nature of these features, in this work we perform a systematic Dens…
Growth of epitaxial graphene on the C-face of SiC has been investigated. Using a confinement controlled sublimation (CCS) method, we have achieved well controlled growth and been able to observe propagation of uniform monolayer graphene. Surface patterns uncover two important aspects of the growth, i.e. carbon diffusion and stoichiometric requirement. Moreover, a new "stepdown" growth mode has been discovered. Via this mode, monolayer graphene domains can have an area of hundreds of square micrometers, while, most importantly, step bunching is avoided and the initial uniformly stepped SiC surf…
Top-gated, few-layer graphene field-effect transistors (FETs) fabricated on thermally-decomposed semi-insulating 4H-SiC substrates are demonstrated. Physical vapor deposited SiO2 is used as the gate dielectric. A two-dimensional hexagonal arrangement of carbon atoms with the correct lattice vectors, observed by high-resolution scanning tunneling microscopy, confirms the formation of multiple graphene layers on top of the SiC substrates. The observation of n-type and p-type transition further verifies Dirac Fermions unique transport properties in graphene layers. The measured electron and hole …
The interaction of metals with carbon materials, specifically with graphene, is of importance for various technological applications. In particular, intercalation of alkali metals is believed to provide a means for tuning the electronic properties of graphene for device applications. While the macroscopic effects of such intercalation events can readily be studied, following the related processes at an atomic scale in detail and under well-defined experimental conditions constitutes a challenge. Here, we investigate in situ the adsorption and nucleation of the alkali metals K, Cs, and Li on fr…
We investigate the magneto-transport properties of epitaxial graphene single-layer on 4H-SiC(0001), grown by atmospheric pressure graphitization in Ar, followed by H2 intercalation. We directly demonstrate the importance of saturating the Si dangling bonds at the graphene/SiC(0001) interface to achieve high carrier mobility. Upon successful Si dangling bonds elimination, carrier mobility increases from 3 000 cm^2/Vs to > 11 000 cm^2/Vs at 0.3 K. Additionally, graphene electron concentration tends to decrease from a few 10^12 cm^-2 to less than 10^12 cm^-2. For a typical large (30x280 um^2) Hal…
Epitaxial graphene grown on SiC by the confinement controlled sublimation method is reviewed, with an emphasis on multilayer and monolayer epitaxial graphene on the carbon face of 4H-SiC and on directed and selectively grown structures under growth-arresting or growth-enhancing masks. Recent developments in the growth of templated graphene nanostructures are also presented, as exemplified by tens of micron long very well confined and isolated 20-40nm wide graphene ribbons. Scheme for large scale integration of ribbon arrays with Si wafer is also presented.
Monolayer graphene epitaxially grown on SiC(0001) was etched by H-plasma and studied by scanning tunneling microscopy and spectroscopy. The etching created partly hexagonal nanopits of monatomic depth as well as elevated regions with a height of about 0.12 nm which are stable at $T$ = 78 K. The symmetric tunnel spectrum about the Femi energy and the absence of a $6\times6$ corrugation on the elevated regions suggest that in these regions the carbon buffer layer is decoupled from the SiC substrate and quasi-free-standing bilayer graphene appears at originally monolayer graphene on the buffer la…
