Emanuele Cavaliere

Healing of structural defects in the topmost layer of graphite by chemical vapor deposition.

Very recently, Lahiri et al. reported the controlled production of extended line defects in graphene and suggested that such structures might function as metallic wires. [ 16 ] Studies such as these have demonstrated that defect engineering in graphitic systems is a promising approach towards controlling a variety of material properties. Despite this, defects are well-known for their ability to scatter charge carriers and phonons, thereby decreasing the ballistic transport path length and adversely affecting carrier mobility and thermal conductivity. The detrimental effects of defects are particularly pronounced in graphene fi lms. For example, defects were held responsible for a dramatic reduction in charge carrier mobility in graphene fi lms obtained by micromechanical cleavage. [ 17 ] The transport properties of graphene fi lms produced by chemical methods, such as the exfoliation and chemical reduction of graphene oxide platelets, have also been ascribed to defects (introduced by the chemical treatments used). [ 18 ] In this respect, defects are undesirable, and the ability to “heal” them is important for generating carbon nanostructures with high electrical and thermal conductivities and, potentially, enhanced mechanical strength. Improvements in these characteristics are of central importance because the successful realization of graphene-based electronic devices

Directed assembly of Au and Fe nanoparticles on a TiOx/Pt(111) ultrathin template: the role of oxygen affinity

The essential role of O affinity in the directed assembly of size-selected Au and Fe nanoparticles (NPs) on a TiO(x)/Pt(111) ultrathin oxide phase, an effective template for size selected metal NP growth, is revealed through scanning tunneling microscopy and density-functional calculations. A weakly interacting element (Au) diffuses rapidly and gets trapped in the vacancy defects (picoholes) located inside parallel rows (troughs, spaced 1.44 nm apart) peculiar to the film structure, producing size-selected NPs arranged in regular linear arrays aligned along the troughs. In contrast, an element with greater O affinity (Fe) experiences higher diffusion barriers, and the growth is dominated by kinetic effects, with a less effective preferential nucleation and the appearance of irregular NP morphologies.

Au nanoparticles on a templating TiOx/Pt(111) ultrathin polar film: a photoemission and photoelectron diffraction study

We present an in-depth investigation of Au nanoparticles self-assembled on a zigzag-like TiO(x)/Pt(111) ultrathin polar film, whose structure is known in great detail. The peculiar pattern of defects (picoholes) templates a linear array of size-selected (ca. 1 nm) Au nanoparticles without disruption of the titania layer, as observed by scanning tunneling microscopy. Their structure and electronic properties have been investigated by several large-area spectroscopic tools, i.e. high-resolution core and valence level photoemission and angle-scanned and energy-scanned photoelectron diffraction. The comparison between experimental data and density functional theoretical calculations indicates that the Au atoms landing on the oxide film are rather mobile, and that the picoholes can act as effective trapping and nucleation centers for the growth of the Au nanoparticles. All the experimental results are in concord in indicating that the Au NPs are flat islands with a maximum thickness of 2-3 layers exposing the (111) surface.

Highly bactericidal Ag nanoparticle films obtained by cluster beam deposition

UNLABELLED The recent emergence of bacterial pathogens resistant to most or all available antibiotics is among the major global public health problems. As indirect transmission through contaminated surfaces is a main route of dissemination for most of such pathogens, the implementation of effective antimicrobial surfaces has been advocated as a promising approach for their containment, especially in the hospital settings. However, traditional wet synthesis methods of nanoparticle-based antimicrobial materials leave a number of key points open for metal surfaces: such as adhesion to the surface and nanoparticle coalescence. Here we demonstrate an alternative route, i.e. supersonic cluster beam deposition, to obtain antimicrobial Ag nanoparticle films deposited directly on surfaces. The synthesized films are simple to produce with controlled density and thickness, are stable over time, and are shown to be highly bactericidal against major Gram positive and Gram negative bacterial pathogens, including extensively drug-resistant strains. FROM THE CLINICAL EDITOR The use of silver nanoparticle in health care is getting more widespread. The authors here describe the technique of cluster beam deposition for spraying silver on surfaces used in health care sectors. This may open a new avenue for future anti-bacterial coatings.

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. ...

Stability and chemisorption properties of ultrathin TiOx/Pt(111) films and Au/TiOx/Pt(111) model catalysts in reactive atmospheres

The stability of three ultrathin TiO(x)/Pt(111) films with different stoichiometry and defectivity and the corresponding Au/TiO(x)/Pt(111) model catalysts in CO or a CO-O(2) (1 : 1) gas mixture up to a pressure of 100 mbar has been investigated. According to previous studies, the ultrathin films proved to be effective substrates to deposit in UHV Au nanoparticles with specific morphologies and lateral sizes ranging between 1 and 6 nm. The films have been characterized before and after the exposure using X-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). Additional in situ measurements of the CO chemisorption behavior were performed using polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS). A fully oxidized film is stable in CO and CO-O(2) (1 : 1) ambient, while the reduced films undergo an oxidative dewetting process at RT in the latter atmosphere. This process ultimately produces a nano-composite surface, where very tiny (from 0.5 to 3 nm lateral sizes) titania nanograins are mixed with open, uncovered areas of the Pt substrate. IRAS measurements on the corresponding Au/TiO(x)/Pt(111) model catalysts demonstrated that the CO chemisorption strongly depends on the Au nanoparticle size and morphology, while the actual Ti oxidation state of the oxide support does not seem to play a significant role.

Exploring the Optical and Morphological Properties of Ag and Ag/TiO2 Nanocomposites Grown by Supersonic Cluster Beam Deposition

Nanocomposite systems and nanoparticle (NP) films are crucial for many applications and research fields. The structure-properties correlation raises complex questions due to the collective structure of these systems, often granular and porous, a crucial factor impacting their effectiveness and performance. In this framework, we investigate the optical and morphological properties of Ag nanoparticles (NPs) films and of Ag NPs/TiO2 porous matrix films, one-step grown by supersonic cluster beam deposition. Morphology and structure of the Ag NPs film and of the Ag/TiO2 (Ag/Ti 50-50) nanocomposite are related to the optical properties of the film employing spectroscopic ellipsometry (SE). We employ a simple Bruggeman effective medium approximation model, corrected by finite size effects of the nano-objects in the film structure to gather information on the structure and morphology of the nanocomposites, in particular porosity and average NPs size for the Ag/TiO2 NP film. Our results suggest that SE is a simple, quick and effective method to measure porosity of nanoscale films and systems, where standard methods for measuring pore sizes might not be applicable.

The nature of the Fe-graphene interface at the nanometer level

The emerging fields of graphene-based magnetic and spintronic devices require a deep understanding of the interface between graphene and ferromagnetic metals. This work reports a detailed investigation at the nanometer level of the Fe–graphene interface carried out by angle-resolved photoemission, high-resolution photoemission from core levels, and scanning tunnelling microscopy. Quasi-freestanding graphene was grown on Pt(111), and the iron film was either deposited atop or intercalated beneath graphene. Calculations and experimental results show that iron strongly modifies the graphene band structure and lifts its π band spin degeneracy.

Graphene nanoribbons synthesized from molecular precursor polymerization on Au(110)

A spectroscopic study of 10,10-dibromo-9,9 bianthracene (DBBA) molecules deposited on the Au(110) surface is presented, by means of ultraviolet and X-ray photoemission, and X-ray absorption spectroscopy. Through a thermally activated procedure, these molecular precursors polymerize and eventually form graphene nanoribbons (GNRs) with atomically controlled shape and width, very important building blocks for several technological applications. The GNRs observed by scanning tunneling microscopy (STM) appear as short segments on top of the gold surface reconstruction, pointing out the delicate balance among surface diffusion and surface corrugation in their synthesis on the Au(110) surface.

Self-assembled Transition Metal Nanoparticles on Oxide Nanotemplates

In this work we present some significant paradigmatic examples of directed self-assembling of transition metals deposited on ultrathin oxide layers grown on single crystal metal surfaces. Two major driving factors are considered in the description of the self-assembling process on these systems, giving rise to ordered arrays of metal nanoparticles (NPs): the presence of defects in the oxide layer and the metal–oxide interaction. We first summarize the structure of different oxide layers, and we discuss the role of geometric and electronic factors in the formation of ordered Au and Fe NP arrays on the selected systems. The discussion suggests that the defective oxide template can drive the self-organization of NPs, if the defects are accessible through the diffusion of metal adatoms on the surface, which in turn, is determined by the metal–oxide interaction.