Andrea Gerbi

A simple and compact mechanical velocity selector of use to analyze/select molecular alignment in supersonic seeded beams

A light and compact mechanical velocity selector, of novel design, for applications in supersonic molecular-beam studies has been developed. It represents a simplified version of the traditional, 50 year old, slotted disks velocity selector. Taking advantage of new materials and improved machining techniques, the new version has been realized with only two rotating slotted disks, driven by an electrical motor with adjustable frequency of rotation, and thus has a much smaller weight and size with respect to the original design, which may allow easier implementation in most of the available molecular-beam apparatuses. This new type of selector, which maintains a sufficiently high velocity resolution, has been developed for sampling molecules with different degrees of rotational alignment, like those emerging from a seeded supersonic expansion. This sampling is the crucial step to realize new molecular-beam experiments to study the effect of molecular alignment in collisional processes.

Selective Production of Reactive and Nonreactive Oxygen Atoms on Pd(001) by Rotationally Aligned Oxygen Molecules

Sticking together: The occupation of different sites by oxygen atoms that are produced by the dissociation of O(2) on Pd(100) is determined by the initial rotational alignment of the parent molecules. The atom locations are characterized by different chemical reactivities in the reaction with CO to form CO(2) (see picture), which are followed by synchrotron radiation (SR) experiments with a supersonic molecular beam (SMB).

New insights on the stereodynamics of ethylene adsorption on an oxygen-precovered silver surface

The control of spatial orientation of molecules has a great influence on the stereodynamics of elementary processes occurring both in homogeneous and heterogeneous phases. Nonpolar molecules have so far escaped direct experimental investigations because of their poor sensitivity to several external constraints. Recently, it has been shown that the collisional alignment produced in supersonic expansions coupled with molecular-beam velocity selection can help solve such problems. Here we show that the sticking probability of ethylene, a nonpolar molecule prototypical of unsaturated hydrocarbons, on an O(2)-precovered Ag(001) surface is larger for molecules approaching in a helicopter-like motion than for those cartwheeling. A mechanism involving a weakly bound precursor state is suggested, with helicopter molecules having a lower chance of being scattered back into the gas phase than cartwheels when colliding with preadsorbed ethylene.

Dynamics of propene adsorption on Ag(001)

The interaction of propene with Ag(001) is investigated by high resolution electron energy loss spectroscopy and supersonic molecular beam methods under ultra high vacuum conditions. Propene adsorbs molecularly at 110 K and desorbs intact leaving a clean surface after annealing to 160 K. Two adsorption sites, characterized by slightly different vibrational modes, exist. The low frequency species is observed already at low coverage for molecules impinging at strongly hyperthermal energies while at lower translational energy it appears only at high coverage. The initial sticking probability S(0) decreases with increasing translational energy, as appropriate for nonactivated adsorption systems. The angle and energy dependence of S(0) indicate that scaling is intermediate between total and normal energy. From the coverage dependence of the sticking probability we infer that both a nonthermal intrinsic and a thermal extrinsic precursor exist.

Broadband plasmonic response of self-organized aluminium nanowire arrays

We investigated the plasmonic response of arrays of Al nanowires fabricated in high-vacuum and embedded within a transparent protective medium. The nanostructures exhibited a strongly-birefringent plasmonic response which, depending on the mutual orientation of the incident-field polarization and the nanowire axis, allowed the plasmon resonance to span the whole spectral range from the visible to the deep-ultraviolet regime. Comparing the experimental data with theoretical calculations allowed to rationalize the optical response in terms of non-ideal nanowire morphologies arising from the bottom-up character of the nanofabrication method. The broadband plasmonic response suggests the potential application of these systems in plasmon-enhanced photovoltaics, exploiting the great advantage of the low-cost of aluminium.

Collisionally aligned molecular beams: a tool for stereodynamical studies in the gas phase and at surfaces

Production, characterization and control of alignment degree of molecules are of importance for investigating in detail the stereodynamics of elementary processes involving elastic, inelastic and reactive events and also to prepare gas-phase species for selective surface scattering investigations. The focus here is on collisional alignment in supersonic seeded molecular beams, a technique which shows perspectives on the applications, offering appealing features for ‘duty cycle’ and intensity characteristics. Attention will be addressed to recent stereodynamical studies carried out on hydrocarbon molecules in the gas phase and on applications of such aligned beams to surface scattering studies.

Ballistic electron and photocurrent transport in Au/organic/Si(001) diodes with PDI8-CN2 interlayers

The authors use ballistic electron emission microscopy (BEEM) to probe hot-electron and photocurrent transport in Au/organic/n-Si(001) diodes incorporating the n-type perylene diimide semiconductor PDI8-CN2. For the case of an ultrathin organic interlayer, hot-electron injection is weak and can be detected only at randomly distributed nanosized domains, where BEEM provides electronic barrier heights of ∼0.67 and ∼0.94 eV, respectively. No ballistic transport is detected for devices with a 10 nm-thick interlayer. Regardless of the organic layer thickness, BEEM reveals laterally uniform contributions due to scanning tunneling microscopy-induced photocurrent (STM-PC), with a characteristic energy onset at ∼1.2 eV and a broad intensity peak in the 2–4 eV range. The authors give insight on such spectroscopic features by examination of temperature-dependent spectra and of literature data. This study shows that PDI8-CN2 limits the penetration of Au toward Si, likely due to stiff intermolecular interactions and r...

Subnanometer Resolution and Enhanced Friction Contrast at the Surface of Perylene Diimide PDI8-CN2 Thin Films in Ambient Conditions

We report high-resolution surface morphology and friction force maps of polycrystalline organic thin films derived by deposition of the n-type perylene diimide semiconductor PDI8-CN2. We show that the in-plane molecular arrangement into ordered, cofacial slip-stacked rows results in a largely anisotropic surface structure, with a characteristic sawtooth corrugation of a few Ångstroms wavelength and height. Load-controlled experiments reveal different types of friction contrast between the alternating sloped and stepped regions, with transitions from atomic-scale dissipative stick-slip to smooth sliding with ultralow friction within the surface unit cell. Notably, such a rich phenomenology is captured under ambient conditions. We demonstrate that friction contrast is well reproduced by numerical simulations assuming a reduced corrugation of the tip-molecule potential nearby the step edges. We propose that the side alkyl chains pack into a compact low-surface-energy overlayer, and friction modulation reflects periodic heterogeneity of chains bending properties and subsurface anchoring to the perylene cores.

Atomic-scale distortions and temperature-dependent large pseudogap in thin films of the parent iron-chalcogenide superconductor Fe1+yTe

We investigate with scanning tunneling microscopy/spectroscopy (STM/STS) and density functional theory (DFT) calculations the surface structures and the electronic properties of Fe1+y Te thin films grown by pulsed laser deposition. Contrary to the regular arrangement of antiferromagnetic nanostripes previously reported on cleaved single-crystal samples, the surface of Fe1+y Te thin films displays a peculiar distribution of spatially inhomogeneous nanostripes. Both STM and DFT calculations show the bias-dependent nature of such features and support the interpretation of spin-polarized tunneling between the FeTe surface and an unintentionally magnetized tip. In addition, the spatial inhomogeneity is interpreted as a purely electronic effect related to changes in hybridization and Fe-Fe bond length driven by local variations in the concentration of excess interstitial Fe cations. Unexpectedly, the surface density of states measured by STS strongly evolves with temperature in close proximity to the antiferromagnetic-paramagnetic first-order transition, and reveals a large pseudogap of 180-250 meV at about 50-65 K. We believe that in this temperature range a phase transition takes place, and the system orders and locks into particular combinations of orbitals and spins because of the interplay between excess interstitial magnetic Fe and strongly correlated d-electrons.