Molecular Doping of CVD-Graphene Surfaces by Perfluoroalkyl-Substituted Perylene Diimides Derivatives.

Non-covalent π-π and dipolar interactions with small aromatic molecules have been widely demonstrated to be a valid option to tune graphene work functions without adding extrinsic scattering centers for charge carriers. In this work, we investigated the interaction between a CVD-graphene monolayer and a thermally evaporated sub-monolayer and the following few-layer thin films of similar perylene diimide derivatives: PDI8-CN2 and PDIF-CN2. The molecular influence on the graphene work function was estimated by XPS and UPS analysis and by investigating the surface potentials via scanning Kelvin probe force microscopy. The perfluorinated decoration and the steric interaction in the early stages of the film growth determined a positive work function shift as high as 0.7 eV in the case of PDIF-CN2, with respect to the value of 4.41 eV for the intrinsic graphene. Our results unambiguously highlight the absence of valence band shifts in the UPS analysis, indicating the prevalence of dipolar interactions between the graphene surface and the organic species enhanced by the presence of the fluorine-enriched moieties.

Detection of Nitroaromatic Explosives in Air by Amino-Functionalized Carbon Nanotubes.

Nitroaromatic explosives are the most common explosives, and their detection is important to public security, human health, and environmental protection. In particular, the detection of solid explosives through directly revealing the presence of their vapors in air would be desirable for compact and portable devices. In this study, amino-functionalized carbon nanotubes were used to produce resistive sensors to detect nitroaromatic explosives by interaction with their vapors. Devices formed by carbon nanotube networks working at room temperature revealed trinitrotoluene, one of the most common nitroaromatic explosives, and di-nitrotoluene-saturated vapors, with reaction and recovery times of a few and tens of seconds, respectively. This type of resistive device is particularly simple and may be easily combined with low-power electronics for preparing portable devices.

Interfacing aptamers, nanoparticles and graphene in a hierarchical structure for highly selective detection of biomolecules in OECT devices.

In several biomedical applications, the detection of biomarkers demands high sensitivity, selectivity and easy-to-use devices. Organic electrochemical transistors (OECTs) represent a promising class of devices combining a minimal invasiveness and good signal transduction. However, OECTs lack of intrinsic selectivity that should be implemented by specific approaches to make them well suitable for biomedical applications. Here, we report on a biosensor in which selectivity and a high sensitivity are achieved by interfacing, in an OECT architecture, a novel gate electrode based on aptamers, Au nanoparticles and graphene hierarchically organized to optimize the final response. The fabricated biosensor performs state of the art limit of detection monitoring biomolecules, such as thrombin-with a limit of detection in the picomolar range (≤ 5 pM) and a very good selectivity even in presence of supraphysiological concentrations of Bovine Serum Albumin (BSA-1mM). These accomplishments are the final result of the gate hierarchic structure that reduces sterich indrance that could contrast the recognition events and minimizes false positive, because of the low affinity of graphene towards the physiological environment. Since our approach can be easily applied to a large variety of different biomarkers, we envisage a relevant potential for a large series of different biomedical applications.

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 [PdCl 4 ] (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.

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.

Electronic properties of CuPc and H2Pc: an experimental and theoretical study.

Phthalocyanine (H2Pc) and its open-shell copper complex (CuPc) deposited on amorphous gold films have been studied by combining the outcomes of several synchrotron based spectroscopic tools (X-ray photoelectron spectroscopy, UV photoelectron spectroscopy and near-edge X-ray absorption fine structure, NEXAFS, spectroscopy) with those of density functional theory (DFT) calculations. The assignment of experimental evidence has been guided by the results of DFT numerical experiments carried out on isolated molecules. With specific reference to CuPc NEXAFS data collected at the N K-edge, they have been assigned by using the open-shell time-dependent DFT (TDDFT) in the framework of the zeroth order regular approximation (ZORA) scalar relativistic approach. The agreement between theory and experiment has been found to be satisfactory, thus indicating that the open-shell TDDFT (F. Wang and T. Ziegler, Mol. Phys., 2004, 102, 2585) may be used with some confidence to look into the X-ray absorption spectroscopy results pertinent to transition metal complexes. As far as the metal-ligand interaction is concerned, the combined use of NEXAFS spectroscopy and DFT outcomes ultimately testified the significant ionic contribution characterizing the bonding between the metal centre and the nitrogen atoms of the phthalocyanine coordinative pocket.

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.

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.

Excitonic recombination in superstoichiometric nanocrystalline TiO2 grown by cluster precursors at room temperature.

Unprecedented room temperature excitonic emissions are achieved from TiO(2) nanocrystals synthesized at 300 K by supersonic cluster beams. Transmission electron microscopy studies show the crystalline nature of the nanoparticles (NPs) with a diameter ranging from 5 to 30 nm. All the samples show mixed rutile and anatase phases as confirmed by Raman spectroscopy. XPS core level analyses evidence an O/Ti ratio of the as-grown nanoparticles of 2.30 ± 0.04. Two room temperature cathodoluminescence excitonic peaks observed at 3.16 and 3.25 eV are ascribed to the coexistence of rutile and anatase crystallographic phases respectively. Subsequent thermal treatments at 450 °C cause the complete quenching of the UV excitonic emissions and result in a more conventional broad visible band centered at 2.5 eV. HRTEM and XPS studies reveal that, after annealing, the NPs remain single crystals in nature with an O/Ti ratio of 2.20 ± 0.04. These results suggest a correlation between the emission properties and the oxygen concentration of our NPs. The achieved ability to tune the optical properties of TiO(2) nanoparticles is very promising for sensing and energy applications.

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.