S. Pagliara

Enhancing the sensitivity of chemiresistor gas sensors based on pristine carbon nanotubes to detect low-ppb ammonia concentrations in the environment

The possibility of using novel architectures based on carbon nanotubes (CNTs) for a realistic monitoring of the air quality in an urban environment requires the capability to monitor concentrations of polluting gases in the low-ppb range. This limit has been so far virtually neglected, as most of the testing of new ammonia gas sensor devices based on CNTs is carried out above the ppm limit. In this paper, we present single-wall carbon nanotube (SWCNT) chemiresistor gas sensors operating at room temperature, displaying an enhanced sensitivity to NH3. Ammonia concentrations in air as low as 20 ppb have been measured, and a detection limit of 3 ppb is demonstrated, which is in the full range of the average NH3 concentration in an urban environment and well below the sensitivities so far reported for pristine, non-functionalized SWCNTs operating at room temperature. In addition to careful preparation of the SWCNT layers, through sonication and dielectrophoresis that improved the quality of the CNT bundle layers, the low-ppb limit is also attained by revealing and properly tracking a fast dynamics channel in the desorption process of the polluting gas molecules.

Experimental evidence of above-threshold photoemission in solids

Nonlinear photoemission from a silver single crystal is investigated by femtosecond laser pulses in a perturbative regime. A clear observation of above-threshold photoemission in solids is reported for the first time. The ratio between the three-photon above-threshold and the two-photon Fermi edges is found to be 10(-4). This value constitutes the only available benchmark for theories aimed at understanding the mechanism responsible for above-threshold photoemission in solids.

C70 adsorbed on Cu(111): Metallic character and molecular orientation

We investigated the interaction of C70 with the Cu(111) surface using x-ray photoelectron spectroscopy and x-ray absorption spectroscopy. The data point to a net charge transfer from the Cu substrate to the C70 molecules directly bonded to the Cu atoms, providing a metallic character for a single layer of C70 (monolayer) adsorbed on this surface. A strong dependence of the x-ray absorption spectra from the light polarization is also observed. By comparing these experimental data with density-functional calculations of the contribution to the x-ray absorption spectral line shape of the five inequivalent carbon atoms in the C70 cage, we observed that the molecules are mainly oriented with the C5V axis perpendicular to the Cu surface.

Steering the efficiency of carbon nanotube-silicon photovoltaic cells by acid vapor exposure: a real-time spectroscopic tracking.

Hybrid carbon nanotube-silicon (CNT-Si) junctions have been investigated by angle resolved photoemission spectroscopy (AR-XPS) with the aim to clarify the effects of a nonstoichiometric silicon oxide buried interface on the overall cell efficiency. A complex silicon oxide interface has been clearly identified and its origin and role in the heterojunction have been probed by exposing the cells to hydrofluoric (HF) and nitric (HNO3) acid. Real-time monitoring of the cell efficiencies during the steps following acid exposure (up to 1 week after etching) revealed a correlation between the thickness and chemical state of the oxide layer and the cell efficiencies. By matching the AR-XPS and Raman spectroscopy with the electrical response data it has been possible to discriminate the effects on the cell efficiency of the buried SiO(x) interface from those related to CNT acid doping. The overall cell behavior recorded for different thicknesses of the SiO(x) interface indicates that the buried oxide layer is likely acting as a passivating/inversion layer in a metal-insulator-semiconductor junction.

Melting of nanostructured Sn probed by in-situ x-ray diffraction

In-situ x-ray diffraction allowed us to track the melting process of nanosized Sn droplets obtained by Sn evaporation on a substrate heated above the Sn melting temperature. We provide further evidence that the melting temperature of nanosized Sn particles is dramatically decreased with respect to the bulk value. The results, obtained by the analysis of in-situ x-ray diffraction patterns, indicate that thermal expansion of lattice parameters is anisotropic, the differences being related to the tetragonal crystal structure of β-Sn. Moreover, the behavior of Sn–Sn distance against the temperature suggests that the melting temperature is related to a critical Sn–Sn distance.

Photoinduced π- π* Band Gap Renormalization in Graphite

As is well-known, the character of the π orbitals is of paramount importance for the chemical properties of the carbon allotropes and their derived compounds. While at equilibrium the nature of these orbitals is well understood, their photoinduced nonequilibrium behavior is under investigation. Here, we demonstrate that when a UV-laser pulse excites a carrier density larger than 10% of the π* density of state in graphite, a renormalization of the π-π* band gap takes place. This result has been achieved by detecting the transient reflectivity and the associated decay time of an infrared probe following the excitation of a UV pump pulse tuned across the π-π* absorption resonance. The pump photon energy at which both the transient reflectivity and the decay time are maximum is downshifted by 500 meV with respect to the relative absorption maximum at equilibrium. This finding is interpreted as a transient π-π* band gap shrinking of similar magnitude, near the M point of the Brillouin zone.

Evidence of vectorial photoelectric effect on copper

Quantum Efficiency (QE) measurements of single photon photoemission from a Cu(111) single crystal and a Cu polycrystal photocathodes, irradiated by 150 fs-6.28 eV laser pulses, are reported over a broad range of incidence angle, both in s and p polarizations. The maximum QE (approx. = 4x10-4) for polycrystalline Cu is obtained in p polarization at an angle of incidence theta = 65 deg. We observe a QE enhancement in p polarization which can not be explained in terms of optical absorption, a phenomenon known as vectorial photoelectric effect. Issues concerning surface roughness and symmetry considerations are addressed. An explanation in terms of non local conductivity tensor is proposed.

Effect of disorder on the Raman scattering of CdSxSe1−x films deposited by laser ablation

Abstract We present micro-Raman spectra at room temperature of CdS x Se 1− x ternary films deposited on Si(111)-oriented substrates by means of the laser ablation technique. The lineshape of the LO phonon structure is characterized by significant asymmetry and broadening induced by disorder in the alloy. The asymmetric line profile can be described as a composite of two phonon modes, one ascribed to zone-center and the other to zone-edge phonons. Attempts to fit the experimental data to the spatial correlation model result in a poor agreement. We discuss the possibility to include into the lineshape analysis the contribution from the disorder-activated phonon density of states.

Mechanics of two pendulums coupled by a stressed spring

The mechanics of two pendulums coupled by a stressed spring is discussed, and the behavior for small oscillations is described. When the system is in its highest symmetry configuration, the pendulums are independent and the normal frequencies are degenerate.

Surface and bulk contribution to Cu(111) quantum efficiency

The quantum efficiency (QE) of Cu(111) is measured for different impinging light angles with photon energies just above the work function. We observe that the vectorial photoelectric effect, an enhancement of the QE due to illumination with light with an electric vector perpendicular to the sample surface, is stronger in the more surface sensitive regime. This can be explained by a contribution to photoemission due to the variation in the electromagnetic potential at the surface. The contributions of bulk and surface electrons can then be determined.