Pulsed Laser Deposition of two-dimensional ZnO nanocrystals on Au(111): Growth, surface structure and electronic properties

Two-dimensional (2D) ZnO structures have been deposited on the Au(111) surface by means of the pulsed laser deposition (PLD) technique. In situ scanning tunneling microscopy (STM) and spectroscopy (STS) measurements have been performed to characterize morphological, structural and electronic properties of 2D ZnO at the nanoscale. Starting from a sub-monolayer coverage, we investigated the growth of ZnO, identifying different atomic layers (up to the 5th). At low coverage, we observed single- and bi-layer nanocrystals, characterized by a surface moire pattern that is associated to a graphene-like ZnO structure. By increasing the coverage, we revealed a morphological change starting from the 4th layer, which was attributed to a transition toward a bulk-like structure. Investigation of the electronic properties revealed the semiconducting character of 2D ZnO. We observed a dependence of the density of states (DOS) and, in particular, of the conduction band (CB) on the ZnO thickness, with a decreasing of the CB onset energy for increasing thickness. The CB DOS of 2D ZnO shows a step-like behaviour which may be interpreted as due to a 2D quantum confinement effect in ZnO atomic layer

Fabrication and Characterization of Molybdenum Tips for Scanning Tunneling Microscopy and Spectroscopy

We present a method for the preparation of bulk molybdenum tips for scanning Tunneling Microscopy and Spectroscopy (STM - STS) and we assess their potential in performing high resolution imaging and local spectroscop by measurements on different single crystal surfaces in UHV, namely Au(111), Si(111)-7x7 and titanium oxide 2D ordered nanostructures supported on Au(111). The fabrication method is versatile and can be extended to other metals, e.g. cobalt

Vibrational - Electrical Properties Relationship in Donor Doped TiO2 by Raman Spectroscopy

Transparent conducting TiO2, obtained by Nb or Ta doping of the anatase structure, is gaining increasing attention for the development of transparent electrodes. Usually, regardless the deposition technique, a crystallization process in reducing atmosphere is necessary to achieve large mobility; in addition, electrical and optical properties are also strongly sensitive to the oxygen deposition pressure. These facts reveal that the defect chemistry of donor doped TiO2 is not trivial and involves a strict interplay among extrinsic dopant atoms, oxygen vacancies and ‘electron killer’ defects such as Ti vacancies and O interstitials. We here present a Raman characterization of donor-doped TiO2 films synthesized under several deposition and post-annealing conditions, employing different doping levels and dopant elements (i.e. Ta and Nb). Correlations between structure, crystallinity, shift and width of Raman peaks and electrical properties are shown and discussed. In particular, a clear relationship between the shift of the Eg(1) anatase Raman mode and the charge carrier density is found, while the B1g(1) mode connected to Ti-Ti vibrations is significantly affected by the extrinsic doping level. In this complex framework Raman spectroscopy can provide an invaluable contribution towards understanding the material structure and its influence on the functional properties

Scanning tunneling microscopy and Raman spectroscopy of polymeric sp-sp2 carbon atomic wires synthesized on the Au(111) surface

Long linear carbon nanostructures based on sp-hybridization can be synthesized by exploiting on-surface synthesis of halogenated precursors evaporated on Au(111), thus opening a way to investigations by surface-science techniques. By means of an experimental approach combining scanning tunneling microscopy and spectroscopy (STM and STS) with ex situ Raman spectroscopy we investigate the structural, electronic and vibrational properties of polymeric sp-sp2 carbon atomic wires composed by sp-carbon chains connected through phenyl groups. Density-functional-theory (DFT) calculations of the structure and the electronic density of states allow us to simulate STM images and to compute Raman spectra. The comparison of experimental data with DFT simulations unveil the properties and the formation stages as a function of the annealing temperature. Atomic-scale structural information from STM complement the Raman sensitivity to the single molecular bond to open the way to detailed understanding of these novel carbon nanostructures

Investigation of sp carbon chain interaction with silver nanoparticles by Surface Enhanced Raman Scattering

Surface Enhanced Raman Spectroscopy (SERS) is exploited here to investigate the interaction of isolated sp carbon chains (polyynes) in a methanol solution with silver nanoparticles. Hydrogen-terminated polyynes show a strong interaction with silver colloids used as the SERS active medium revealing a chemical SERS effect. SERS spectra after mixing polyynes with silver colloids show a noticeable time evolution. Experimental results, supported by density functional theory (DFT) calculations of the Raman modes, allow us to investigate the behavior and stability of polyynes of different lengths and the overall sp conversion towards sp2 phase.Comment: 19 pages, 7 figures, 1 table

Chemical Bond and Charge Transfer Dynamics of a Dye-Hierarchical TiO2 Hybrid Interface

The adsorption of Zn-Tetra-Phenyl-Porphyrin (ZnTPP) on nanoporous hierarchically organized anatase TiO2 structures, and the properties of the corresponding hybrid interface were studied by synchrotron radiation experiments. The molecular structure, electronic properties and the bonding with nanostructured TiO2 surfaces were analyzed by photoemission (XPS and UPS) and x-ray absorption spectroscopy (XAS). The charge transfer at the interface was investigated by means of valence band resonant photoemission experiments (ResPES) at the C K edge. We show that the charge transfer dynamics between the photo-excited ZnTPP and TiO2 is strongly influenced by the presence of defects on the TiO2 surface. On a stoichiometric anatase nanostructure, ZnTPP bonding occurs primarily via carbon atoms belonging to the molecular phenyl rings and this creates a preferential channel for the charge transfer. This phenomenon is reduced in the case of defective TiO2 surface, where ZnTPP interacts mainly through the molecule macrocycle. Our results represent a surface science study of the dye molecule behavior on a nanoporous TiO2 photoanode relevant to dye-sensitized or hybrid solar cell applications and it shows the importance of the surface oxidation state for the charge transfer proces

Different W cluster deposition regimes in pulsed laser ablation observed by in situ Scanning Tunneling Microscopy

We report on how different cluster deposition regimes can be obtained and observed by in situ Scanning Tunneling Microscopy (STM) by exploiting deposition parameters in a pulsed laser deposition (PLD) process. Tungsten clusters were produced by nanosecond Pulsed Laser Ablation in Ar atmosphere at different pressures and deposited on Au(111) and HOPG surfaces. Deposition regimes including cluster deposition-diffusion-aggregation (DDA), cluster melting and coalescence and cluster implantation were observed, depending on background gas pressure and target-to-substrate distance which influence the kinetic energy of the ablated species. These parameters can thus be easily employed for surface modification by cluster bombardment, deposition of supported clusters and growth of films with different morphologies. The variation in cluster mobility on different substrates and its influence on aggregation and growth mechanisms has also been investigated.Comment: 12 pages (3 figures); Surface Science (accepted

Autoantibodies against type I IFNs in patients with life-threatening COVID-19

Interindividual clinical variability in the course of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection is vast. We report that at least 101 of 987 patients with life-threatening coronavirus disease 2019 (COVID-19) pneumonia had neutralizing immunoglobulin G (IgG) autoantibodies (auto-Abs) against interferon-w (IFN-w) (13 patients), against the 13 types of IFN-a (36), or against both (52) at the onset of critical disease; a few also had auto-Abs against the other three type I IFNs. The auto-Abs neutralize the ability of the corresponding type I IFNs to block SARS-CoV-2 infection in vitro. These auto-Abs were not found in 663 individuals with asymptomatic or mild SARS-CoV-2 infection and were present in only 4 of 1227 healthy individuals. Patients with auto-Abs were aged 25 to 87 years and 95 of the 101 were men. A B cell autoimmune phenocopy of inborn errors of type I IFN immunity accounts for life-threatening COVID-19 pneumonia in at least 2.6% of women and 12.5% of men