Frédéric Joucken

Localized state and charge transfer in nitrogen-doped graphene

Nitrogen-doped epitaxial graphene grown on SiC(0001) was prepared by exposing the surface to an atomic nitrogen flux. Using scanning tunneling microscopy and scanning tunneling spectroscopy (STS), supported by density functional theory (DFT) calculations, the simple substitution of carbon with nitrogen atoms has been identified as the most common doping configuration. High-resolution images reveal a reduction of local charge density on top of the nitrogen atoms, indicating a charge transfer to the neighboring carbon atoms. Local STS spectra clearly evidenced the energy levels associated with the chemical doping by nitrogen, localized in the conduction band. Various other nitrogen-related defects have been observed. The bias dependence of their topographic signatures demonstrates the presence of structural configurations more complex than substitution as well as hole doping.

Charge transfer and electronic doping in nitrogen-doped graphene.

Understanding the modification of the graphene’s electronic structure upon doping is crucial for enlarging its potential applications. We present a study of nitrogen-doped graphene samples on SiC(000) combining angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and spectroscopy and X-ray photoelectron spectroscopy (XPS). The comparison between tunneling and angle-resolved photoelectron spectra reveals the spatial inhomogeneity of the Dirac energy shift and that a phonon correction has to be applied to the tunneling measurements. XPS data demonstrate the dependence of the N 1s binding energy of graphitic nitrogen on the nitrogen concentration. The measure of the Dirac energy for different nitrogen concentrations reveals that the ratio usually computed between the excess charge brought by the dopants and the dopants’ concentration depends on the latter. This is supported by a tight-binding model considering different values for the potentials on the nitrogen site and on its first neighbors.

Electronic Interaction between Nitrogen Atoms in Doped Graphene

Many potential applications of graphene require either the possibility of tuning its electronic structure or the addition of reactive sites on its chemically inert basal plane. Among the various strategies proposed to reach these objectives, nitrogen doping, i.e., the incorporation of nitrogen atoms in the carbon lattice, leads in most cases to a globally n-doped material and to the presence of various types of point defects. In this context, the interactions between chemical dopants in graphene have important consequences on the electronic properties of the systems and cannot be neglected when interpreting spectroscopic data or setting up devices. In this report, the structural and electronic properties of complex doping sites in nitrogen-doped graphene have been investigated by means of scanning tunneling microscopy and spectroscopy, supported by density functional theory and tight-binding calculations. In particular, based on combined experimental and simulation works, we have systematically studied the electronic fingerprints of complex doping configurations made of pairs of substitutional nitrogen atoms. Localized bonding states are observed between the Dirac point and the Fermi level in contrast with the unoccupied state associated with single substitutional N atoms. For pyridinic nitrogen sites (i.e., the combination of N atoms with vacancies), a resonant state is observed close to the Dirac energy. This insight into the modifications of electronic structure induced by nitrogen doping in graphene provides us with a fair understanding of complex doping configurations in graphene, as it appears in real samples.

Electronic Interaction between Nitrogen-Doped Graphene and Porphyrin Molecules

The chemical doping of graphene is a promising route to improve the performances of graphene-based devices through enhanced chemical reactivity, catalytic activity, or transport characteristics. Understanding the interaction of molecules with doped graphene at the atomic scale is therefore a leading challenge to be overcome for the development of graphene-based electronics and sensors. Here, we use scanning tunneling microscopy and spectroscopy to study the electronic interaction of pristine and nitrogen-doped graphene with self-assembled tetraphenylporphyrin molecules. We provide an extensive measurement of the electronic structure of single porphyrins on Au(111), thus revealing an electronic decoupling effect of the porphyrins adsorbed on graphene. A tip-induced switching of the inner hydrogen atoms of porphyrins, first identified on Au(111), is observed on graphene, allowing the identification of the molecular conformation of porphyrins in the self-assembled molecular layer. On nitrogen-doped graphene, a local modification of the charge transfer around the nitrogen sites is evidenced via a downshift of the energies of the molecular elecronic states. These data show how the presence of nitrogen atoms in the graphene network modifies the electronic interaction of organic molecules with graphene. These results provide a basic understanding for the exploitation of doped graphene in molecular sensors or nanoelectronics.

Grain boundaries in graphene on SiC(0001̅) substrate.

Grain boundaries in epitaxial graphene on the SiC(0001̅) substrate are studied using scanning tunneling microscopy and spectroscopy. All investigated small-angle grain boundaries show pronounced out-of-plane buckling induced by the strain fields of constituent dislocations. The ensemble of observations determines the critical misorientation angle of buckling transition θc = 19 ± 2°. Periodic structures are found among the flat large-angle grain boundaries. In particular, the observed θ = 33 ± 2° highly ordered grain boundary is assigned to the previously proposed lowest formation energy structural motif composed of a continuous chain of edge-sharing alternating pentagons and heptagons. This periodic grain boundary defect is predicted to exhibit strong valley filtering of charge carriers thus promising the practical realization of all-electric valleytronic devices.

Grain Boundaries in Graphene on SiC(000

Grain boundaries in epitaxial graphene on the SiC(0001̅) substrate are studied using scanning tunneling microscopy and spectroscopy. All investigated small-angle grain boundaries show pronounced out-of-plane buckling induced by the strain fields of constituent dislocations. The ensemble of observations determines the critical misorientation angle of buckling transition θc = 19 ± 2°. Periodic structures are found among the flat large-angle grain boundaries. In particular, the observed θ = 33 ± 2° highly ordered grain boundary is assigned to the previously proposed lowest formation energy structural motif composed of a continuous chain of edge-sharing alternating pentagons and heptagons. This periodic grain boundary defect is predicted to exhibit strong valley filtering of charge carriers thus promising the practical realization of all-electric valleytronic devices.

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Appropriate conditions for direct growth of graphitic films on Si(111) 7 × 7 are investigated. The structural and electronic properties of the samples are studied by Auger electron spectroscopy, X-ray photoemission spectroscopy, low energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy (STM). In particular, we present STM images of a carbon honeycomb lattice grown directly on Si(111). Our results demonstrate that the quality of graphene films formed depends not only on the substrate temperature but also on the carbon buffer layer at the interface. This method might be very promising for graphene-based electronics and its integration into the silicon technology.

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The growth of graphene on oriented (111) copper films has been achieved by atmospheric pressure chemical vapor deposition. The structural properties of as-produced graphene have been investigated by scanning tunneling microscopy. Anomalous moiré superstructures composed of well-defined linear periodic modulations have been observed. We report here on comprehensive and detailed studies of these particular moiré patterns present in the graphene topography revealing that, in certain conditions, the growth can occur on the oxygen-induced reconstructed copper surface and not directly on the oriented (111) copper film as expected.

Direct growth of graphitic carbon on Si(111)

We propose an innovative, easy-to-implement approach to synthesize aligned large-area single-crystalline graphene flakes by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.

Anomalous moiré pattern of graphene investigated by scanning tunneling microscopy: Evidence of graphene growth on oxidized Cu(111)

Due to the need of integrated circuit in the current silicon technology, the formation of graphene on Si wafer is highly desirable, but is still a challenge for the scientific community. In this context, we report the direct growth of graphene on Si(111) wafer under appropriate conditions using an electron beam evaporator. The structural quality of the material is investigated in detail by reflection high energy electron diffraction, Auger electron spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, high resolution scanning electron microscopy, atomic force microscopy, and scanning tunneling microscopy. Our experimental results confirm that the quality of graphene is strongly dependent on the growth time during carbon atoms deposition.