Lucia Vitali

Electronic structure of surface-supported bis(phthalocyaninato) terbium(III) single molecular magnets.

The electronic structure of isolated bis(phthalocyaninato) terbium(III) molecules, a novel single-molecular-magnet (SMM), supported on the Cu(111) surface has been characterized by density functional theory and scanning tunneling spectroscopy. These studies reveal that the interaction with the metal surface preserves both the molecular structure and the large spin magnetic moment of the metal center. The 4f electron states are not perturbed by the adsorption while a strong molecular/metal interaction can induce the suppression of the minor spin contribution delocalized over the molecular ligands. The calculations show that the inherent spin magnetic moment of the molecule is only weakly affected by the interaction with the surface and suggest that the SMM character might be preserved.

Spin and Orbital Magnetic Moment Anisotropies of Monodispersed Bis(Phthalocyaninato)Terbium on a Copper Surface

The magnetic properties of isolated TbPc(2) molecules supported on a Cu(100) surface are investigated by X-ray magnetic circular dichroism at 8 K in magnetic fields up to 5 T. The crystal field and magnetic properties of single molecules are found to be robust upon adsorption on a metal substrate. The Tb magnetic moment has Ising-like magnetization; XMCD spectra combined with multiplet calculations show that the saturation orbital and spin magnetic moment values reach 3 and 6 mu(B), respectively.

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.

Kondo temperature of magnetic impurities at surfaces

Based on the experimental observation that only the close vicinity of a magnetic impurity at metal surfaces determines its Kondo behavior, we introduce a simple model which explains the Kondo temperatures observed for cobalt adatoms at the (111) and (100) surfaces of Cu, Ag, and Au. Excellent agreement between the model and scanning tunneling spectroscopy experiments is demonstrated. The Kondo temperature is shown to depend on the occupation of the d level determined by the hybridization between the adatom and the substrate with a minimum around single occupancy.

Portrait of the potential barrier at metal-organic nanocontacts

Electron transport through metal-molecule contacts greatly affects the operation and performance of electronic devices based on organic semiconductors and is at the heart of molecular electronics exploiting single-molecule junctions. Much of our understanding of the charge injection and extraction processes in these systems relies on our knowledge of the potential barrier at the contact. Despite significant experimental and theoretical advances a clear rationale of the contact barrier at the single-molecule level is still missing. Here, we use scanning tunnelling microscopy to probe directly the nanocontact between a single molecule and a metal electrode in unprecedented detail. Our experiments show a significant variation on the submolecular scale. The local barrier modulation across an isolated 4-[trans-2-(pyrid-4-yl-vinyl)] benzoic acid molecule bound to a copper(111) electrode exceeds 1 eV. The giant modulation reflects the interaction between specific molecular groups and the metal and illustrates the critical processes determining the interface potential. Guided by our results, we introduce a new scheme to locally manipulate the potential barrier of the molecular nanocontacts with atomic precision.

Phonon and plasmon excitation in inelastic electron tunneling spectroscopy of graphite

The inelastic electron tunneling spectrum ~IETS! of highly oriented pyrolitic graphite has been measured with scanning tunneling spectroscopy ~STS! at 6 K. The observed spectral features are in very good agreement with the vibrational density of states of graphite calculated from first principles. We discuss the enhancement of certain phonon modes by phonon-assisted tunneling in STS based on the restrictions imposed by the electronic structure of graphite. We also demonstrate the local excitation of surface plasmons in IETS, which

Image potential states as a quantum probe of graphene interfaces

Image potential states (IPSs) are electronic states localized in front of a surface in a potential well, formed by the surface projected bulk band gap on one side and the image potential barrier on the other. In the limit of a two-dimensional solid, a double Rydberg series of IPSs has been predicted, which is in contrast to a single series present in three-dimensional solids. Here, we confirm this prediction experimentally for mono- and bilayer graphene. The IPSs of epitaxial graphene on SiC are measured by scanning tunneling spectroscopy and the results are compared with ab-initio band structure calculations. Despite the presence of the substrate, both calculations and experimental measurements show that the first pair of the double series of IPSs survives and eventually evolves into a single series for graphite. Thus, IPSs provide an elegant quantum probe of the interfacial coupling in graphene systems.

Kondo Effect in Single Atom Contacts: The Importance of the Atomic Geometry

Co single atom junctions on copper surfaces are studied by scanning tunneling microscopy and ab initio calculations. The Kondo temperature of single cobalt atoms on the Cu(111) surface has been measured at various tip-sample distances ranging from tunneling to the point contact regime. The experiments show a constant Kondo temperature for a whole range of tip-substrate distances consistently with the predicted energy position of the spin-polarized d levels of Co. This is in striking difference to experiments on Co/Cu(100) junctions, where a substantial increase of the Kondo temperature has been found. Our calculations reveal that the different behavior of the Co adatoms on the two Cu surfaces originates from the interplay between the structural relaxations and the electronic properties in the near-contact regime.

Local pressure-induced metallization of a semiconducting carbon nanotube in a crossed junction.

The electronic and vibrational density of states of a semiconducting carbon nanotube in a crossed junction was investigated by elastic and inelastic scanning tunneling spectroscopy. The strong radial compression of the nanotube at the junction induces local metallization spatially confined to a few nm. The local electronic modifications are correlated with the observed changes in the radial breathing and G-band phonon modes, which react very sensitively to local mechanical deformation. In addition, the experiments reveal the crucial contribution of the image charges to the contact potential at nanotube-metal interfaces.

Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires

The tunable properties of molecular materials place them among the favorites for a variety of future generation devices. In addition, to maintain the current trend of miniaturization of those devices, a departure from the present top-down production methods may soon be required and self-assembly appears among the most promising alternatives. On-surface synthesis unites the promises of molecular materials and of self-assembly, with the sturdiness of covalently bonded structures: an ideal scenario for future applications. Following this idea, we report the synthesis of functional extended nanowires by self-assembly. In particular, the products correspond to one-dimensional organic semiconductors. The uniaxial alignment provided by our substrate templates allows us to access with exquisite detail their electronic properties, including the full valence band dispersion, by combining local probes with spatial averaging techniques. We show how, by selectively doping the molecular precursors, the product’s energy level alignment can be tuned without compromising the charge carrier’s mobility.