50 research outputs found

    Localized state and charge transfer in nitrogen-doped graphene

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    Nitrogen-doped epitaxial graphene grown on SiC(000?1) was prepared by exposing the surface to an atomic nitrogen flux. Using Scanning Tunneling Microscopy (STM) and Spectroscopy (STS), supported by Density Functional Theory (DFT) calculations, the simple substitution of carbon by 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. For the first time, 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.Comment: 5 pages, accepted in PR

    Giant tunnel-electron injection in nitrogen-doped graphene

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    International audienceScanning tunneling microscopy experiments have been performed to measure the local electron injection in nitrogen-doped graphene on SiC(000ÂŻ1) and were successfully compared to ab initio calculations. In graphene, a gaplike feature is measured around the Fermi level due to a phonon-mediated tunneling channel. At nitrogen sites, this feature vanishes due to an increase of the elastic channel that is allowed because of symmetry breaking induced by the nitrogen atoms. A large conductance enhancement by a factor of up to 500 was measured at the Fermi level by comparing local spectroscopy at nitrogen sites and at carbon sites. Nitrogen doping can therefore be proposed as a way to improve tunnel-electron injection in graphene

    Grain Boundaries in Graphene on SiC(0001ˉ\bar{1}) Substrate

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    Grain boundaries in epitaxial graphene on the SiC(0001ˉ\bar{1}) 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 allows to determine the critical misorientation angle of buckling transition Ξc=19± 2∘\theta_c = 19 \pm~2^\circ. Periodic structures are found among the flat large-angle grain boundaries. In particular, the observed Ξ=33±2∘\theta = 33\pm2^\circ 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

    Charge transfer and electronic doping in nitrogen-doped graphene

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    cited By 21International audienceUnderstanding 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(0001) 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. © 2015, Nature Publishing Group. All rights reserved

    3D Ruthenium Nanoparticle Covalent Assemblies from Polymantane Ligands for Confined Catalysis

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    The synthesis of metal nanoparticle (NP) assemblies stabilized by functional molecules is an important research topic in nanoscience, and the ability to control interparticle distances and positions in NP assemblies is one of the major challenges in designing and understanding functional nanostructures. Here, two series of functionalized adamantanes, bis-adamantanes, and diamantanes, bearing carboxylic acid or amine functional groups, were used as building blocks to produce, via a straightforward method, networks of ruthenium NPs. Both the nature of the ligand and the Ru/ligand ratio affect the interparticle distance in the assemblies. The use of 1,3-adamantanedicarboxylic acid allows the synthesis of three-dimensional (3D) networks of 1.7–1.9 nm Ru NPs presenting an interparticle distance of 2.5–2.7 nm. The surface interaction between Ru NPs and the ligands was investigated spectroscopically using a 13C-labeled ligand, as well as theoretically with density functional theory (DFT) calculations. We found that Ru species formed during the NP assembly are able to partially decarbonylate carboxylic acid ligands at room temperature. Decarbonylation of a carboxylic acid at room temperature in the presence of dihydrogen usually occurs on catalysts at much higher temperatures and pressures. This result reveals a very high reactivity of ruthenium species formed during the network assembly. The Ru NP networks were found to be active catalysts for the selective hydrogenation of phenylacetylene, reaching good selectivity toward styrene. Overall, we demonstrated that catalyst activity, selectivity, and NP network stability are significantly affected by Ru NP interparticle distance and electronic ligand effects. As such, these materials constitute a unique set that should allow a better understanding of the complex surface chemistry in carbon-supported metal catalysts
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