Impact of local stacking on the graphene-impurity interaction: theory and experiments

We investigate the graphene-impurity interaction problem by combining experimental - scanning tunneling microscopy (STM) and spectroscopy (STS) - and theoretical - Anderson impurity model and density functional theory (DFT) calculations - techniques. We use graphene on the SiC(000-1)(2x2)_C reconstruction as a model system. The SiC substrate reconstruction is based on silicon adatoms. Graphene mainly interacts with the dangling bonds of these adatoms which act as impurities. Graphene grown on SiC(000-1)(2x2)_C shows domains with various orientations relative to the substrate so that very different local graphene/Si adatom stacking configurations can be probed on a given grain. The position and width of the adatom (impurity) state can be analyzed by STM/STS and related to its local environment owing to the high bias electronic transparency of graphene. The experimental results are compared to Anderson's model predictions and complemented by DFT calculations for some specific local environments. We conclude that the adatom resonance shows a smaller width and a larger shift toward the Dirac point for an adatom at the center of a graphene hexagon than for an adatom just on top of a C graphene atom.Comment: 13 pages, 6 figures, Accepted for publication in Phys. Rev.

Graphene on the C-terminated SiC (000 1ˉ\bar{1}) surface: An ab initio study

The atomic and electronic structures of a graphene layer on top of the $(2\times2)$ reconstruction of the SiC (000$\bar{1}$) surface are studied from ab initio calculations. At variance with the (0001) face, no C bufferlayer is found here. Si adatoms passivate the substrate surface so that the very first C layer presents a linear dispersion characteristic of graphene. A small graphene-substrate interaction remains in agreement with scanning tunneling experiments (F.Hiebel et al. {\it Phys. Rev. B} {\bf 78} 153412 (2008)). The stacking geometry has little influence on the interaction which explains the rotational disorder observed on this face.Comment: 4 pages, 3 figures, additional materia

Quasiparticle scattering off phase boundaries in epitaxial graphene

We investigate the electronic structure of terraces of single layer graphene (SLG) by scanning tunneling microscopy (STM) on samples grown by thermal decomposition of 6H-SiC(0001) crystals in ultra-high vacuum. We focus on the perturbations of the local density of states (LDOS) in the vicinity of edges of SLG terraces. Armchair edges are found to favour intervalley quasiparticle scattering, leading to the (\surd3\times\surd3)R30{\deg} LDOS superstructure already reported for graphite edges and more recently for SLG on SiC(0001). Using Fourier transform of LDOS images, we demonstrate that the intrinsic doping of SLG is responsible for a LDOS pattern at the Fermi energy which is more complex than for neutral graphene or graphite, since it combines local (\surd3\times\surd3)R30{\deg} superstructure and long range beating modulation. Although these features were already reported by Yang et al. Nanoletters 10, 943 (2010), we propose here an alternative interpretation based on simple arguments classically used to describe standing wave patterns in standard two-dimensional systems. Finally, we discuss the absence of intervalley scattering off other typical boundaries: zig-zag edges and SLG/bilayer graphene junctions

Electron states of mono- and bilayer graphene on SiC probed by STM

We present a scanning tunneling microscopy (STM) study of a gently-graphitized 6H-SiC(0001) surface in ultra high vacuum. From an analysis of atomic scale images, we identify two different kinds of terraces, which we unambiguously attribute to mono- and bilayer graphene capping a C-rich interface. At low temperature, both terraces show $(\sqrt{3}\times \sqrt{3})$ quantum interferences generated by static impurities. Such interferences are a fingerprint of $\pi$-like states close to the Fermi level. We conclude that the metallic states of the first graphene layer are almost unperturbed by the underlying interface, in agreement with recent photoemission experiments (A. Bostwick et al., Nature Physics 3, 36 (2007))Comment: 4 pages, 3 figures submitte

Quasiparticle Chirality in Epitaxial Graphene Probed at the Nanometer Scale

Graphene exhibits unconventional two-dimensional electronic properties resulting from the symmetry of its quasiparticles, which leads to the concepts of pseudospin and electronic chirality. Here we report that scanning tunneling microscopy can be used to probe these unique symmetry properties at the nanometer scale. They are reflected in the quantum interference pattern resulting from elastic scattering off impurities, and they can be directly read from its fast Fourier transform. Our data, complemented by theoretical calculations, demonstrate that the pseudospin and the electronic chirality in epitaxial graphene on SiC(0001) correspond to the ones predicted for ideal graphene.Comment: 4 pages, 3 figures, minor change

Single 3dd transition metal atoms on multi-layer graphene systems: electronic configurations, bonding mechanisms and role of the substrate

The electronic configurations of Fe, Co, Ni, and Cu adatoms on graphene and graphite have been studied by x-ray magnetic circular dichroism and charge transfer multiplet theory. A delicate interplay between long-range interactions and local chemical bonding is found to influence the adatom equilibrium distance and magnetic moment. The results for Fe and Co are consistent with purely physisorbed species having, however, different 3$d$-shell occupancies on graphene and graphite ($d^{n+1}$ and $d^n$, respectively). On the other hand, for the late 3$d$ metals Ni and Cu a trend towards chemisorption is found, which strongly quenches the magnetic moment on both substrates.Comment: 7 pages, 4 figure

Hydrogen physisorption channel on graphene: A highway for atomic H diffusion

We study the adsorption of atomic hydrogen on graphene by combining scanning tunneling microscopy experiments and first principle calculations. Our results reveal the existence of a physisorption channel over the graphene layer, dominated by van der Waals forces and thus homogeneous over the whole atomic lattice, where atomic hydrogen can move freely. Such physisorption channel is essential to understand the final configuration of hydrogen atoms chemisorbed on graphene. We find that ∼95% of chemisorbed H atoms form non-magnetic dimers even for very dilute concentrationsThis work was supported by Spain’s Ministerio de Economía y Competitividad under grants; PCIN-2015-030; FIS2015-64886-C5-5-P, MDM-2014-0377 and FIS2016-80434-P, by AEI and FEDER under projects MAT2016-80907-P and MAT2016-77852-C2-2-R (AEI/FEDER, UE), by the Fundación Ramón Areces, by the European Union through the FLAG ERA program and structural funds and by the Comunidad de Madrid MAD2D-CM program under grant S2013/MIT-3007

Unraveling the intrinsic and robust nature of van hove singularities in twisted bilayer graphene by scanning tunneling microscopy and theoretical analysis

Extensive scanning tunneling microscopy and spectroscopy experiments complemented by first-principles and parametrized tight binding calculations provide a clear answer to the existence, origin, and robustness of vanHove singularities (vHs) in twisted graphene layers. Our results are conclusive: vHs due to interlayer coupling are ubiquitously present in a broad range (from 1º to 10º) of rotation angles in our graphene on 6H-SiC(000-1) samples. From the variation of the energy separation of the vHs with the rotation angle we are able to recover the Fermi velocity of a graphene monolayer as well as the strength of the interlayer interaction. The robustness of the vHs is assessed both by experiments, which show that they survive in the presence of a third graphene layer, and by calculations, which test the role of the periodic modulation and absolute value of the interlayer distance. Finally, we clarify the role of the layer topographic corrugation and of electronic effects in the apparent moiré contrast measured on the STM imagesThis work was supported by Spain’s MICINN under Grants No. MAT2010-14902, No. CSD2010-00024, and No. CSD2007-00050, and by Comunidad de Madrid under Grant No. S2009/MAT-1467. M. M. U., I. B., P. M, J.-Y.V., L. M., and J. M. G.-R. also acknowledge the PHC Picasso program for financial support (Project No. 22885NH). I. B. was supported by a Ramón y Cajal project of the Spanish MEC. L. M., P. M., and J.-Y.V. acknowledge support from Fondation Nanosciences (Dispograph project