Search

Wideband gap diamond-based materials are attracting huge interest for energy harvesting and quantum applications. We have used density functional theory code (DFT) to explore tin (Sn) as a potential negative electron affinity (NEA) imparting termination on the oxygen terminated diamond (OTD) surface. Large adsorption energies (~−6 eV) were obtained for half monolayer of Sn atoms on oxygen (O) terminated diamond surface with an NEA of up to −1.37 eV. We are also demonstrating experimentally, the formation of SnO nano cluster layer on the surface of diamond which resulted in NEA and reduction in the work function (WF) by 1.8 eV. The SnO termination, clearly distinguishable from more stable and widely known SnO2, was found to be stable in ambient conditions, a crucial point for device application. A comparison of lithium (Li) and Li/Sn oxide terminations of single crystal diamond (1 0 0) is presented in terms of the stability of the surface layer and the electronic properties thus induced, using the photoemission spectroscopic techniques. The intercalation of Li into SnO planes results in the increased stability of LiO on the surface of diamond and WF reduction by 2.3 eV which paves way for a more efficient termination on the diamond surface.

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

Graphene-h-BN hybrid nanostructures are grown in one step on the Pt(111) surface by ultra-high vacuum chemical vapor deposition using a single precursor, the dimethylamino borane complex. By varying the deposition conditions, different nanostructures ranging from a fully continuous hybrid monolayer to well-separated Janus nanodots can be obtained. The growth starts with heterogeneous nucleation on morphological defects such as Pt step edges and proceeds by the addition of small clusters formed by the decomposition of the dimethylamino borane complex. Scanning tunneling microscopy measurements indicate that a sharp zigzag in-plane boundary is formed when graphene grows aligned with the Pt substrate and consequently with the h-BN layer as well. When graphene is rotated by 30°, the graphene armchair edges are seamlessly connected to h-BN zigzag edges. This is confirmed by a thorough density functional theory (DFT) study. Angle resolved photoemission spectroscopy (ARPES) data suggests that both h-BN and graphene present the typical electronic structure of self-standing non-interacting materials.[Figure not available: see fulltext.].

The surface-assisted synthesis of gold-organometallic hybrids on the Au(111) surface both by thermo- and light-initiated dehalogenation of bromo-substituted tetracene is reported. Combined X-ray photoemission (XPS) and scanning tunneling microscopy (STM) data reveal a significant increase of the surface order when mild reaction conditions are combined with 405 nm light irradiation.

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

We demonstrate that graphene oxide can be efficiently reduced by evaporating metal Titanium in high vacuum. A detailed description of this reaction is provided by combining in situ photoemission spectroscopy measurements and DFT calculations: the titanium atoms readily react with the oxygenated groups of graphene oxide, disrupting the C-O bonds, with the consequent formation of titania and the recovery of the se hybridized carbon atoms. When all surface oxygen is consumed, titanium can react with the carbon substrate and form carbidic species. Resonant photoemission spectroscopy measurements allow identifying the presence and exact energy position in the valence band of the Ti-C and Ti-O-C states, which are supposed to control the electron and energy transfer across the TiO2/graphene interface. Therefore with this study we provide a versatile method and the rationale for controlling, at the atomic level, the nature of the interface of graphene/metal oxide nanocomposites. (C) 2013 Elsevier Ltd. All rights reserved.

We have investigated the electronic response of single crystals of indium selenide by means of angle-resolved photoemission spectroscopy, electron energy loss spectroscopy and density functional theory. The loss spectrum of indium selenide shows the direct free exciton at ~1.3 eV and several other peaks, which do not exhibit dispersion with the momentum. The joint analysis of the experimental band structure and the density of states indicates that spectral features in the loss function are strictly related to single-particle transitions. These excitations cannot be considered as fully coherent plasmons and they are damped even in the optical limit, i.e. for small momenta. The comparison of the calculated symmetry-projected density of states with electron energy loss spectra enables the assignment of the spectral features to transitions between specific electronic states. Furthermore, the effects of ambient gases on the band structure and on the loss function have been probed.