Giovanni Drera

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.

Enhancement of room temperature ferromagnetism in N-doped TiO2−x rutile: Correlation with the local electronic properties

The magnetic and electronic properties of ferromagnetic undoped and N-doped TiO2−x rutile have been probed by soft x-ray spectroscopies. Upon N doping, a fivefold enhancement of the saturation magnetization is observed. Apparently, this enhancement is not related to an increase in oxygen vacancies, rather to additional in-gap states, arising from the replacement of O with N atoms in the rutile structure that can provide more favorable conditions for the onset of ferromagnetic ordering.The magnetic and electronic properties of ferromagnetic undoped and N-doped TiO2−x rutile have been probed by soft x-ray spectroscopies. Upon N doping, a fivefold enhancement of the saturation magnetization is observed. Apparently, this enhancement is not related to an increase in oxygen vacancies, rather to additional in-gap states, arising from the replacement of O with N atoms in the rutile structure that can provide more favorable conditions for the onset of ferromagnetic ordering.

Band offsets and density of Ti3+ states probed by x-ray photoemission o LaAlO3/SrTiO3 heterointerfaces and their LaAlO3 and SrTiO3 bulk precursors

A set of LaAlO3/SrTiO3 (LAO-STO) interfaces has been probed by x-ray photoemission spectroscopy in order to contrast and compare the effects of LAO overlayer thickness and of the growth conditions on the electronic properties of these heterostructures. These effects are tracked by considering the band offset and the density of Ti+3 states, respectively. It is shown that the dominant effects on the local electronic properties are determined by the O2 partial pressure during the growth. In particular, a low PO2 yields Ti+3 states with higher density and lower binding energy compared to the sample grown at high PO2 or to the bare STO reference sample. Band-offset effects are all below about 0.7 eV, but a careful analysis of Ti 2p and Sr 3d peaks shows that valence-band offsets can be at the origin of the observed peak width. In particular, the largest offset is shown by the conducting sample, which displays the largest Ti 2p and Sr 3d peak widths

Spectroscopic evidence of in-gap states at the SrTiO3/LaAlO3 ultrathin interfaces

Experimental evidence of differences in the electronic properties of an insulating and a conducting SrTiO3/LaAlO3 interface is provided by soft x-ray spectroscopies. While core level photoemission measurements show that only at the conducting interface Ti ions with 3+ ionization state are present, by using resonant photoemission and x-ray absorption spectroscopies, it is shown that in both samples in-gap states with a Ti 3d character are present, but their density is higher at the conducting interface.

Correlation between Deposition Parameters and Hydrogen Production in CuO Nanostructured Thin Films.

In this article, we report a systematic investigation of the role of (i) substrate temperature, (ii) oxygen partial pressure, and (iii) radio frequency (rf) power on the crystal structure and morphology of CuO nanostructured thin films prepared by means of rf-magnetron sputtering starting from a Cu metal target. On selected films, photocatalytic tests have been carried out in order to correlate the structural and morphological properties of the thin films prepared under different conditions with the photocatalytic properties and to find out the key parameters to optimize the CuO nanostructured films. All of the synthesized films were single-phase CuO nanorods of variable diameter between 80 and 200 nm. Better-aligned rods were obtained at relatively low substrate temperatures and from low to intermediate oxygen partial pressures, resulting in more efficient photocatalytic activities. Our investigation suggests a relevant role of the crystallographic orientation of the CuO tenorite film on the photocatalytic activity, as demonstrated by the significant improvement in H2 evolution for highly oriented films.

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.

An ultrathin TiO2 blocking layer on Cd stannate as highly efficient front contact for dye-sensitized solar cells

An engineered multilayer structure of platinum-cadmium stannate-titanium oxide (Pt-CTO-TO), with different TO layer thickness (in the range 1-5 nm), has been grown at 400 °C on glass substrates by RF magnetron sputtering, following a 2-step procedure without breaking vacuum. To produce an alternative and reliable front contact for dye sensitized solar cells (DSCs), morphology and composition of a TO blocking layer have been studied, paying particular attention to the oxide-oxide (CTO-TO) interface characteristics. The influence of the metallic mesh on the transparent conductive oxide sheet resistance has also been considered. A sputtered CTO layer shows a high average transmittance, over 90%. The Pt mesh yields a drastic reduction in the series resistance, almost one order, without affecting the optical properties. The ultrathin blocking layer of Ti oxide prevents charge recombination, improving the overall performance of the solar cells: +86% in efficiency, +50% in short circuit current, with respect to bare CTO.

Labeling interacting configurations through an analysis of excitation dynamics in a resonant photoemission experiment: the case of rutile TiO2

A detailed study of resonant photoemission at Ti L(2,3) edges of insulating rutile TiO(2-x) thin film is presented. Pure TiO(2) resonating structures, defect-related resonances, resonant Raman-Auger and normal LVV Auger emissions are tracked, including an unpredicted two-hole correlated satellite below the non-bonding part of the valence band. The analysis of excitation dynamics unambiguously addresses the origin of these features and, in particular, the extent of charge transfer effects on the Ti-O bonding in the valence band of rutile, disclosing further applications to the more general case of, formally, d(0) oxides.

Layer-Resolved Cation Diffusion and Stoichiometry at the LaAlO3/SrTiO3 Heterointerface Probed by X-ray Photoemission Experiments and Site Occupancy Modeling

The layer-resolved cation occupancy for different conducting and insulating interfaces of LaAlO3 (LAO) thin films on SrTiO3 (STO) has been determined by angle-resoled X-ray photoelectron spectroscopy (AR-XPS). Three STO interfaces with LAO have been considered, namely, a conducting interface with a 5 unit cell (u.c.) LAO layer, an insulating interface with a 5 u.c. LAO layer, and an insulating interface with a 3 u.c. LAO layer. Considering inelastic and elastic scattering processes in the transport approximation, the core-level signal attenuation has been modeled on the basis of Monte Carlo calculations of the electron trajectories across the heterostructures. Different effects involving cation stoichiometry and diffusion through the interface have been considered to interpret data. Beyond a mere abrupt interface modeling, the LaAlO3/SrTiO3 heterojunction is shown to host cation diffusion processes within 3-4 unit cells in the bulk layer, along with a clear Sr substoichiometry, an issue so far virtually neglected in the analysis of these systems. The present results show the capability of the AR-XPS modeling to explore element-sensitive properties at the oxide interfaces, matching and completing the information that can be provided by probes based on electron microscopy or X-ray scattering.

Gas sensing at the nanoscale: engineering SWCNT-ITO nano-heterojunctions for the selective detection of NH3 and NO2 target molecules

The gas response of single-wall carbon nanotubes (SWCNT) functionalized with indium tin oxide (ITO) nanoparticles (NP) has been studied at room temperature and an enhanced sensitivity to ammonia and nitrogen dioxide is demonstrated. The higher sensitivity in the functionalized sample is related to the creation of nano-heterojunctions at the interface between SWCNT bundles and ITO NP. Furthermore, the different response of the two devices upon NO2 exposure provides a way to enhance also the selectivity. This behavior is rationalized by considering a gas sensing mechanism based on the build-up of space-charge layers at the junctions. Finally, full recovery of the signal after exposure to NO2 is achieved by UV irradiation for the functionalized sample, where the ITO NP can play a role to hinder the poisoning effects on SWCNT due to NO2 chemisorption.