Lucrezia Aversa

Enhancement of the core near-band-edge emission induced by an amorphous shell in coaxial one-dimensional nanostructure: the case of SiC/SiO2 core/shell self-organized nanowires

We report the influence of the native amorphous SiO(2) shell on the cathodoluminescence emission of 3C-SiC/SiO(2) core/shell nanowires. A shell-induced enhancement of the SiC near-band-edge emission is observed and studied as a function of the silicon dioxide thickness. Since the diameter of the investigated SiC cores rules out any direct bandgap optical transitions due to confinement effects, this enhancement is ascribed to a carrier diffusion from the shell to the core, promoted by the alignment of the SiO(2) and SiC bands in a type I quantum well. An accurate correlation between the optical emission and structural and SiO(2)-SiC interface properties is also reported.

Epitaxy of Nanocrystalline Silicon Carbide on Si(111) at Room Temperature

Silicon carbide (SiC) has unique chemical, physical, and mechanical properties. A factor strongly limiting SiC-based technologies is the high-temperature synthesis. In this work, we provide unprecedented experimental and theoretical evidence of 3C-SiC epitaxy on silicon at room temperature by using a buckminsterfullerene (C(60)) supersonic beam. Chemical processes, such as C(60) rupture, are activated at a precursor kinetic energy of 30-35 eV, far from thermodynamic equilibrium. This result paves the way for SiC synthesis on polymers or plastics that cannot withstand high temperatures.

Electronic properties of tetrakis(pentafluorophenyl)porphyrin

We studied in detail the electronic properties of C44H10F20N4 (tetrakis(pentafluorophenyl)porphyrin, hereafter H2TPP(F)) via a combined study by photoelectron spectroscopy (PES) and density functional (DF) calculations, shedding new light on the role of the halide in this very interesting molecule for organic electronics. Valence and core levels have been investigated by means of PES on H2TPP(F) thin films deposited on the SiO2/Si(100) native oxide surface by supersonic molecular beam deposition (SuMBD). These experiments have been carefully interpreted on the basis of DF results pertaining to the isolated H2TPP(F). Non-relativistic calculations have been run to investigate valence states, whereas a two component relativistic approach within the zeroth-order regular approximation has been adopted to study core levels. The present results, in conjunction with those obtained previously on the H2TPP parent compound [M. Nardi, R. Verucchi, C. Corradi, M. Pola, M. Casarin, A. Vittadini and S. Iannotta, Phys. Chem. Chem. Phys., 2010, 12, 871], pave the way towards designing fully organic p–n junctions by using these macrocycles.

Non-adiabatic ab initio molecular dynamics of supersonic beam epitaxy of silicon carbide at room temperature

In this work, we investigate the processes leading to the room-temperature growth of silicon carbide thin films by supersonic molecular beam epitaxy technique. We present experimental data showing that the collision of fullerene on a silicon surface induces strong chemical-physical perturbations and, for sufficient velocity, disruption of molecular bonds, and cage breaking with formation of nanostructures with different stoichiometric character. We show that in these out-of-equilibrium conditions, it is necessary to go beyond the standard implementations of density functional theory, as ab initio methods based on the Born-Oppenheimer approximation fail to capture the excited-state dynamics. In particular, we analyse the Si-C(60) collision within the non-adiabatic nuclear dynamics framework, where stochastic hops occur between adiabatic surfaces calculated with time-dependent density functional theory. This theoretical description of the C(60) impact on the Si surface is in good agreement with our experimental findings.

Carbon-doped SiO x nanowires with a large yield of white emission

The growth of SiOx nanowires (NWs) with intense white emission is reported. Due to carbon monoxide gas being used as a dopant precursor, carbon-doped under-stoichiometric silicon dioxide NWs are obtained. The doping of the NWs is studied by means of x-ray photoelectron spectroscopy, which allows to assess the presence of carbon atoms in the silicon oxide amorphous structure. The light emission properties are studied by means of cathodoluminescence spectroscopy, which shows three main emission bands set at 2.7 eV (blue), 2.3 eV (green) and 1.9 eV (red), resulting in the white emission.

The Interaction of C60 on Si(111) 7 × 7 Studied by Supersonic Molecular Beams: Interplay between Precursor Kinetic Energy and Substrate Temperature in Surface Activated Processes

Buckminsterfullerene (C60) is a molecule fully formed of carbon that can be used, owing to its electronic and mechanical properties, as “clean” precursor for the growth of carbon-based materials, ranging from -conjugated systems (graphenes) to synthesized species, e.g. carbides such as silicon carbide (SiC). To this goal, C60 cage rupture is the main physical process that triggers material growth. Cage breaking can be obtained either thermally by heating up the substrate to high temperatures (630°C), after C60 physisorption, or kinetically by using Supersonic Molecular Beam Epitaxy (SuMBE) techniques. In this work, aiming at demonstrating the growth of SiC thin films by C60 supersonic beams, we present the experimental investigation of C60 impacts on Si(111) 7x7 kept at 500°C for translational kinetic energies ranging from 18 to 30 eV. The attained kinetically activated synthesis of SiC submonolayer films is probed by in-situ surface electron spectroscopies (XPS and UPS). Furthermore, in these experimental conditions the C60-Si(111) 7×7 collision has been studied by computer simulations based on a tight-binding approximation to Density Functional Theory, DFT. Our theoretical and experimental findings point towards a kinetically driven growth of SiC on Si, where C60 precursor kinetic energy plays a crucial role, while temperature is relevant only after cage rupture to enhance Si and carbon reactivity. In particular, we observe a counterintuitive effect in which for low kinetic energy (below 22 eV), C60 bounces back without breaking more effectively at high temperature due to energy transfer from excited phonons. At higher kinetic energy (22 < K < 30 eV), for which cage rupture occurs, temperature enhances reactivity without playing a major role in the cage break. These results are in good agreement with ab-initio molecular dynamics simulations. SuMBE is thus a technique able to drive materials growth at low temperature regime.

Primary cortical neurons on PMCS TiO2 films towards bio-hybrid memristive device: A morpho-functional study

We report a comprehensive study of the biocompatibility and neurocompatibility of titanium dioxide films (TiO2) prepared by Pulsed Microplasma Cluster Source (PMCS). This technique uses supersonic pulsed beams seeded by clusters of the metal oxide synthesized in a plasma discharge. The final stoichiometry of the TiO2 thin films is tuned changing the gas mixture, achieving stoichiometric or oxygen overstoichiometric films. All the films showed consistent biocompatibility and a spontaneous absorption of poly-d-lysine (PDL) that favors the adhesion and growth of murine cortical neurons. Moreover, the bioelectrical activity of the neuronal culture grown on the TiO2 film can be modulated by changing the chemistry of the surface. This work paves the way to develop a bio-hybrid neuromorphic device, where viable nerve cells are grown directly over a titanium dioxide film showing a network of memristors.

Structural Characterizations of Palladium Clusters Prepared by Polyol Reduction of [PdCl4]2− Ions

Palladium nanoparticles are of great interest in many industrial fields, ranging from catalysis and hydrogen technology to microelectronics, thanks to their unique physical and chemical properties. In this work, palladium clusters have been prepared by reduction of [PdCl4]2− ions with ethylene glycol, in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) as stabilizer. The stabilizer performs the important role of nucleating agent for the Pd atoms with a fast phase separation, since palladium atoms coordinated to the polymer side-groups are forced at short distances during nucleation. Quasispherical palladium clusters with a diameter of ca. 2.6 nm were obtained by reaction in air at 90°C for 2 hours. An extensive materials characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and other characterizations (TGA, SEM, EDS-SEM, and UV-Vis) has been performed in order to evaluate the structure and oxidation state of nanopalladium.

Synthesis of palladium clusters by reduction of K2PdCl4 with ethylene glycol

Palladium clusters have been prepared by chemical reduction of [PdCl4]2- ions with ethylene glycol in presence of polyvinylpyrrolidone as protective agent. The palladium clusters obtained by reduction at 90°C for 2 hours had a diameter of ca. 2.8 nm and were quite monodispersed. Nano-sized palladium can have important technological applications in different industrial areas (e.g., hydrogen storage, catalysis, hydrogen sensors, etc.).

Emission Enhancement of SiC/SiO2 Core/Shell Nanowires Induced by the Oxide Shell

In this work we report the enhancement of the 3C-SiC band edge luminescence induced by the SiO2 shell in SiC/SiO2 core/shell nanowires (NWs) system. We demonstrate that the shell enhances the SiC near band edge luminescence and we argue the formation of a type-I quantum well between the SiC core and the SiO2 shell, with the consequent injection of carriers from the larger band-gap shell to the narrower band-gap core.