Peculiar covalent bonding of C60/6H-SiC(0 0 0 1)-(3 × 3) probed by photoelectron spectroscopy.

High resolution photoemission with synchrotron radiation was used to study the interface formation of a thin layer of C60 on 6H-SiC(0 0 0 1)-(3 × 3), characterized by protruding Si-tetramers. The results show that C60 is chemisorbed by orbital hybridization between the highest-occupied molecular orbital (HOMO) and the p z orbital of Si adatom at the apex of the tetramers. The covalent nature of the bonding was inferred from core level as well as valence band spectra. The Si 2p spectra reveal that a large fraction (at least 45%) of the Si adatoms remain unbound despite the reactive character of the associated dangling bonds. This is consistent with a model in which each C60 is attached to the substrate through a single covalent C60-Si bond. A binding energy shift of the core levels associated with sub-surface Si or C atoms indicates a decrease of the SiC band bending caused by a charge transfer from the C60 molecules to the substrate via the formation of donor-like interface states.

Combined AFM and STM measurements of a silicene sheet grown on the Ag(111) surface.

In this paper, we present the first non-contact atomic force microscopy (nc-AFM) of a silicene on a silver (Ag) surface, obtained by combining non-contact atomic force microscopy and scanning tunneling microscopy (STM). STM images over large areas of silicene grown on the Ag(111) surface show both (√13 × âˆš13)R13.9° and (4 × 4) superstructures. For the widely observed (4 × 4) structure, the observed nc-AFM image is very similar to the one recorded by STM. The structure resolved by nc-AFM is compatible with only one out of two silicon atoms being visible. This indicates unambiguously a strong buckling of the silicene honeycomb layer.

STM imaging, spectroscopy and manipulation of a self-assembled PTCDI monolayer on epitaxial graphene.

Scanning Tunneling Microscopy (STM), Scanning Tunneling Spectroscopy (STS), and manipulation studies were performed on an ordered self-assembled monolayer (SAM) of N,N'-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) molecules on epitaxial graphene on hexagonal silicon carbide - SiC(0001). Four novel aspects of the molecular SAM on graphene are presented. Molecules adsorb in both armchair and zig-zag configurations, giving rise to six orientations of the molecular layer with respect to the underlying substrate. The interaction between the molecules and the graphene surface shifts the LUMO towards the Fermi level, inducing a charge transfer and the opening of a band gap in the graphene, with the LUMO inside. This decouples the LUMO from the surface rendering it invisible in the dI/dV spectroscopy. The HOMO only becomes visible at short tip-surface distances, as its energy lies within the band gap of the SiC substrate. Finally, the observed molecular defects are very particular, being composed exclusively of molecular dimers. These molecular dimers have a stronger interaction with the graphene than other molecules.

The paradox of an insulating contact between a chemisorbed molecule and a wide band gap semiconductor surface.

Controlling the intrinsic optical and electronic properties of a single molecule adsorbed on a surface requires electronic decoupling of some molecular orbitals from the surface states. Scanning tunneling microscopy experiments and density functional theory calculations are used to study a perylene molecule derivative (DHH-PTCDI), adsorbed on the clean 3 × 3 reconstructed wide band gap silicon carbide surface (SiC(0001)-3 × 3). We find that the LUMO of the adsorbed molecule is invisible in I(V) spectra due to the absence of any surface or bulk states and that the HOMO has a very low saturation current in I(z) spectra. These results present a paradox that the molecular orbitals are electronically isolated from the surface of the wide band gap semiconductor even though strong chemical bonds are formed.

Theoretical simulations of the tip-induced configuration changes of the 4,4(')-diacetyl-p-terphenyl molecule chemisorbed on Si(001).

We have investigated from a theoretical point of view modifications of the 4,4(')-diacetyl-p-terphenyl molecule chemisorbed on Si(001) induced by the scanning tunneling microscope (STM). In previous experiments, these modifications were observed to occur preferentially at the end of the molecule after a +4.0 V voltage pulse and at the center after a +4.5 V voltage pulse. In the framework of ab initio simulations, we have realized a systematic energetic study of the dissociative chemisorption of one, two, or three phenyl rings of the substituted p-terphenyl molecule. Charge densities were then calculated for the investigated configurations and compared to the STM topographies. Before manipulation with the STM tip, the substituted p-terphenyl molecule is preferentially adsorbed without phenyl ring dissociation, allowing a partial rotation of the central phenyl ring. Our results show that the STM induced modifications observed at the end of the molecule might originate from the dissociation of two phenyl rings (one central and one external ring), while the modifications occurring at the central part of the molecule can be interpreted as a dissociation of the two external rings.

Difficulty for oxygen to incorporate into the silicon network during initial O2 oxidation of Si(100)-(2x1).

First principles calculations and scanning tunneling microscopy studies of the oxidation of Si(100)-(2x1) surfaces by molecular oxygen reveal that the surface silanone (O)(Si=O) species is remarkably stable, constituting the key intermediate for initial oxidation. The propensity for oxygen to remain within the top surface layer as opposed to incorporating within Si-Si backbonds is surprisingly high. This resistance to incorporation into a cubic lattice even at higher coverages could be a factor to facilitate surface amorphization in subsequent steps.

Atomic-scale STM experiments on semiconductor surfaces: towards molecular nanomachines.

The electronic or quantum control of individual molecules with the scanning tunnelling microscope offers exciting perspectives on operating molecular nanomachines. This implies the use of semiconductor surfaces rather than metallic surfaces which would rapidly quench the electronic excitations. We review recent results illustrating the state of the art and the main problems which need to be solved: the choice, design and properties of functionalized organic molecules on semiconductor surfaces; the control of the inelastic electronic channels through a single molecule; and the search for well-controlled atomic-scale wide-band-gap semiconductor surfaces.

Atomic-scale imaging of insulating diamond through resonant electron injection.

The electronic properties of insulators such as diamond are of interest not only for their passive dielectric capabilities for use in electronic devices, but also for their strong electron confinement on atomic scales. However, the inherent lack of electrical conductivity in insulators usually prevents the investigation of their surfaces by atomic-scale characterization techniques such as scanning tunnelling microscopy (STM). And although atomic force microscopy could in principle be used, imaging diamond surfaces has not yet been possible. Here, we demonstrate that STM can be used in an unconventional resonant electron injection mode to image insulating diamond surfaces and to probe their electronic properties at the atomic scale. Our results reveal striking electronic features in high-purity diamond single crystals, such as the existence of one-dimensional fully delocalized electronic states and a very long diffusion length for conduction-band electrons. We expect that our method can be applied to investigate the electronic properties of other insulating materials and so help in the design of atomic-scale electronic devices.

Atomic scale oxidation of a complex system: O2/alpha-SiC(0001)-( 3 x 3).

The atomic scale oxidation of the alpha-SiC(0001)-(3 x 3) surface is investigated by atom-resolved scanning tunneling microscopy, core level synchrotron radiation based photoemission spectroscopy, and infrared absorption spectroscopy. The results reveal that the initial oxidation takes place through the relaxation of lower layers, away from the surface dangling bond, in sharp contrast to silicon oxidation.