L. Petaccia

Metal-organic coordination interactions in Fe-Terephthalic acid networks on Cu(100)

Metal-organic coordination interactions are prime candidates for the formation of self-assembled, nanometer-scale periodic networks with room-temperature structural stability. We present X-ray photoelectron spectroscopy measurements of such networks at the Cu(100) surface which provide clear evidence for genuine metal-organic coordination. This is evident as binding energy shifts in the O 1s and Fe 3p photoelectron peaks, corresponding to O and Fe atoms involved in the coordination. Our results provide the first clear evidence for charge-transfer coordination in metal-organic networks at surfaces and demonstrate a well-defined oxidation state for the coordinated Fe ions.

Sensing gases with carbon nanotubes: a review of the actual situation

Here we review the possible application of carbon nanotubes (CNTs) as chemiresistor and field-effect transistor chemical sensors. The endeavor of this paper is to understand the key facts emerging from the literature that seem to demonstrate the high sensitivity of CNTs to several molecular species, with the effort to catch the results in a correct manner.

Observation of a universal donor-dependent vibrational mode in graphene

Electron-phonon coupling and the emergence of superconductivity in intercalated graphite have been studied extensively. Yet, phonon-mediated superconductivity has never been observed in the 2D equivalent of these materials, doped monolayer graphene. Here we perform angle-resolved photoemission spectroscopy to try to find an electron donor for graphene that is capable of inducing strong electron-phonon coupling and superconductivity. We examine the electron donor species Cs, Rb, K, Na, Li, Ca and for each we determine the full electronic band structure, the Eliashberg function and the superconducting critical temperature Tc from the spectral function. An unexpected low-energy peak appears for all dopants with an energy and intensity that depend on the dopant atom. We show that this peak is the result of a dopant-related vibration. The low energy and high intensity of this peak are crucially important for achieving superconductivity, with Ca being the most promising candidate for realizing superconductivity in graphene.

Mesoscopic donor-acceptor multilayer by ultrahigh-vacuum codeposition of Zn-tetraphenyl-porphyrin and C70.

The peculiar electrochemical and photophysical properties of porphyrin and fullerene molecules make them promising candidates for the construction of two- and three-dimensional organic-based materials. An important question is how pristine fullerene and porphyrin will organize when deposited on surfaces via in vacuum molecular beam evaporation. Here we show that codeposition of C(70) and Zn-tetraphenyl-porphyrin (ZnTPP) induces the self-assembly of electron-rich flat aromatic molecules at the curved surface of C(70), thus enhancing the chromophore interaction and forming a supramolecular multilayer donor-acceptor structure. While the ground-state electronic spectra almost reflect a simple summation of ZnTPP and C(70) components, the excited-state electrons at the porphyrin macrocycle can rapidly delocalize to the fullerene. The excited charge transfer time scale is faster than 1-2 fs, as shown by resonant photoemission for the core-excited charges.

Core level shifts of undercoordinated Pt atoms

We present the results of high-energy resolution core level photoelectron spectroscopy experiments paralleled by density functional theory calculations to investigate the electronic structure of highly undercoordinated Pt atoms adsorbed on Pt(111) and its correlation with chemical activity. Pt4f(7/2) core level binding energies corresponding to atoms in different configurations are shown to be very sensitive not only to the local atomic coordination number but also to the interatomic bond lengths. Our results are rationalized by introducing an indicator, the effective coordination, which includes both contributions. The calculated energy center of the valence 5d-band density of states, which is a well known depicter of the surface chemical reactivity, shows a noteworthy correlation with the Pt4f(7/2) core level shifts and with the effective coordination.

Highly under-coordinated atoms at Rh surfaces: interplay of strain and coordination effects on core level shift

The electronic structure of highly under-coordinated Rh atoms, namely adatoms and ad-dimers, on homo-metallic surfaces has been probed by combining high-energy resolution core level photoelectron spectroscopy and density functional theory calculations. The Rh3d5/2 core level shifts are shown to be proportional to the number of Rh nearest-neighbours (n = 3, 4 and 5). A more refined analysis shows that the energy position of the different core level components is correlated with the calculated changes of the individual inter-atomic bond length and to the energy changes of the d-band centre, which is known to be a reliable descriptor of local chemical reactivity.

NH3 adsorption and decomposition on Ir(110): A combined temperature programmed desorption and high resolution fast x-ray photoelectron spectroscopy study

The adsorption and decomposition of NH3 on Ir(110) has been studied in the temperature range from 80 K to 700 K. By using high-energy resolution x-ray photoelectron spectroscopy it is possible to distinguish chemically different surface species. At low temperature a NH3 multilayer, which desorbs at approximately 110 K, was observed. The second layer of NH3 molecules desorbs around 140 K, in a separate desorption peak. Chemisorbed NH3 desorbs in steps from the surface and several desorption peaks are observed between 200 and 400 K. A part of the NH3ad decomposes into NH(ad) between 225 and 300 K. NH(ad) decomposes into N(ad) between 400 K and 500 K and the hydrogen released in this process immediately desorbs. N2 desorption takes place between 500 and 700 K via N(ad) combination. The steady state decomposition reaction of NH3 starts at 500 K. The maximum reaction rate is observed between 540 K and 610 K. A model is presented to explain the occurrence of a maximum in the reaction rate. Hydrogenation of N(ad) below 400 K results in NH(ad). No NH2ad or NH3ad/NH3 were observed. The hydrogenation of NH(ad) only takes place above 400 K. On the basis of the experimental findings an energy scheme is presented to account for the observations.

Spin–Orbit Coupling Induced Gap in Graphene on Pt(111) with Intercalated Pb Monolayer

Graphene is one of the most promising materials for nanoelectronics owing to its unique Dirac cone-like dispersion of the electronic state and high mobility of the charge carriers. However, to facilitate the implementation of the graphene-based devices, an essential change of its electronic structure, a creation of the band gap should controllably be done. Brought about by two fundamentally different mechanisms, a sublattice symmetry breaking or an induced strong spin-orbit interaction, the band gap appearance can drive graphene into a narrow-gap semiconductor or a 2D topological insulator phase, respectively, with both cases being technologically relevant. The later case, characterized by a spin-orbit gap between the valence and conduction bands, can give rise to the spin-polarized topologically protected edge states. Here, we study the effect of the spin-orbit interaction enhancement in graphene placed in contact with a lead monolayer. By means of angle-resolved photoemission spectroscopy, we show that intercalation of the Pb interlayer between the graphene sheet and the Pt(111) surface leads to formation of a gap of ∼200 meV at the Dirac point of graphene. Spin-resolved measurements confirm the splitting to be of a spin-orbit nature, and the measured near-gap spin structure resembles that of the quantum spin Hall state in graphene, proposed by Kane and Mele [ Phys. Rev. Lett. 2005 , 95 , 226801 ]. With a bandstructure tuned in this way, graphene acquires a functionality going beyond its intrinsic properties and becomes more attractive for possible spintronic applications.

Probing Local Hydrogen Impurities in Quasi-Free-Standing Graphene

We report high-resolution scanning tunneling microscopy and spectroscopy of hydrogenated, quasi-free-standing graphene. For this material, theory has predicted the appearance of a midgap state at the Fermi level, and first angle-resolved photoemission spectroscopy (ARPES) studies have provided evidence for the existence of this state in the long-range electronic structure. However, the spatial extension of H defects, their preferential adsorption patterns on graphene, or local electronic structure are experimentally still largely unexplored. Here, we investigate the shapes and local electronic structure of H impurities that go with the aforementioned midgap state observed in ARPES. Our measurements of the local density of states at hydrogenated patches of graphene reveal a hydrogen impurity state near the Fermi level whose shape depends on the tip position with respect to the center of a patch. In the low H concentration regime, we further observe predominantly single hydrogenation sites as well as extended multiple C-H sites in parallel orientation to the lattice vectors, indicating an adsorption at the same graphene sublattice. This is corroborated by ARPES measurements showing the formation of a dispersionless hydrogen impurity state which is extended over the whole Brillouin zone.

Reversible Phase Transformation and Doubly Charged Anions at the Surface of Simple Cubic RbC(60)

The simple cubic phase of a RbC60 thin film has been studied using photoelectron spectroscopy. The simple cubic-to-dimer transition is found to be reversible at the film surface. A sharp Fermi edge is observed and a lower limit of 0.5 eV is found for the surface Hubbard U, pointing to a strongly correlated metallic character of thin-film simple cubic RbC60. A molecular charge state is identified in the valence band and core-level photoemission spectra which arises from C60(2-) anions and contributes to the spectral intensity at the Fermi level.