A. Battiato

Synthesis and properties of monolayer graphene oxyfluoride

Covalent bond-forming reactions can be used to tailor the properties of graphene, aiming at electronic band structure engineering and surface functionalization. We present a novel and easy method for the production of chemically modified monolayer graphene based on the electrochemical intercalation of graphite, that could be used for adding various functional groups to the graphene lattice. Oxy-fluorinated graphene layers have been produced and fully characterized in terms of their chemical composition and functionalization. Moreover, Raman spectroscopy allows ready discrimination between monolayers and few-layers, and field-effect devices have been fabricated in order to study the transport properties of monolayer graphene oxyfluoride. Interesting conduction mechanisms such as two dimensional Mott variable range hopping and colossal negative magneto-resistance are observed, making this novel material suitable for both fundamental research and graphene-based applications.

Spectroscopic measurement of the refractive index of ion-implanted diamond

We present the results of variable-angle spectroscopic ellipsometry and transmittance measurements to determine the variation of the complex refractive index of ion-implanted single-crystal diamond. An increase is found in both real and imaginary parts at increasing damage densities. The index depth variation is determined in the whole wavelength range between 250 and 1690 nm. The dependence from the vacancy density is evaluated, highlighting a deviation from linearity in the high-damage-density regime. A considerable increase (up to 5%) in the real part of the index is observed, attributed to an increase in polarizability, thus offering new microfabrication possibilities for waveguides and other photonic structures in diamond.

Silver Nanocluster/Silica Composite Coatings Obtained by Sputtering for Antibacterial Applications

Silver nanocluster silica composite coatings were deposited by radio frequency co-sputtering technique on several substrates. This versatile method allows tailoring of silver content and antibacterial behaviour of coatings deposited on glasses, ceramics, metals and polymers for several applications. Coating morphology and composition as well as nanocluster size were analyzed by means of UV-Visible absorption, X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), electron dispersive spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM). The antibacterial effect was verified through the inhibition halo test against standard bacterial strain, Staphylococcus aureus, before and after sterilization process. Tape test demonstrated a good adhesion of the coatings to the substrates.

Development and Characterization of a Diamond-Insulated Graphitic Multi Electrode Array Realized with Ion Beam Lithography

The detection of quantal exocytic events from neurons and neuroendocrine cells is a challenging task in neuroscience. One of the most promising platforms for the development of a new generation of biosensors is diamond, due to its biocompatibility, transparency and chemical inertness. Moreover, the electrical properties of diamond can be turned from a perfect insulator into a conductive material (resistivity ∼mΩ·cm) by exploiting the metastable nature of this allotropic form of carbon. A 16-channels MEA (Multi Electrode Array) suitable for cell culture growing has been fabricated by means of ion implantation. A focused 1.2 MeV He+ beam was scanned on a IIa single-crystal diamond sample (4.5 × 4.5 × 0.5 mm3) to cause highly damaged sub-superficial structures that were defined with micrometric spatial resolution. After implantation, the sample was annealed. This process provides the conversion of the sub-superficial highly damaged regions to a graphitic phase embedded in a highly insulating diamond matrix. Thanks to a three-dimensional masking technique, the endpoints of the sub-superficial channels emerge in contact with the sample surface, therefore being available as sensing electrodes. Cyclic voltammetry and amperometry measurements of solutions with increasing concentrations of adrenaline were performed to characterize the biosensor sensitivity. The reported results demonstrate that this new type of biosensor is suitable for in vitro detection of catecholamine release.

Graphene strain tuning by control of the substrate surface chemistry

We show that the Raman spectrum of graphene is sensitive to the surface chemistry of the substrate where the atomic plane is deposited. Two types of functionalized SiO2 surface are experimentally compared: OH-terminated and NH2-terminated. In the case of NH2-terminated surface, the graphene Raman bands are significantly redshifted with respect to the peaks observed on the hydroxylated surface. The observed phonon softening can be ascribed to a biaxial strain induced into graphene by its interaction with the substrate. Therefore, the control of the substrate surface chemistry may be envisaged as a route to graphene strain engineering.

All-carbon multi-electrode array for real-time in vitro measurements of oxidizable neurotransmitters

We report on the ion beam fabrication of all-carbon multi electrode arrays (MEAs) based on 16 graphitic micro-channels embedded in single-crystal diamond (SCD) substrates. The fabricated SCD-MEAs are systematically employed for the in vitro simultaneous amperometric detection of the secretory activity from populations of chromaffin cells, demonstrating a new sensing approach with respect to standard techniques. The biochemical stability and biocompatibility of the SCD-based device combined with the parallel recording of multi-electrodes array allow: i) a significant time saving in data collection during drug screening and/or pharmacological tests over a large number of cells, ii) the possibility of comparing altered cell functionality among cell populations, and iii) the repeatition of acquisition runs over many cycles with a fully non-toxic and chemically robust bio-sensitive substrate.

Planar Diamond-Based Multiarrays to Monitor Neurotransmitter Release and Action Potential Firing: New Perspectives in Cellular Neuroscience

High biocompatibility, outstanding electrochemical responsiveness, inertness, and transparency make diamond-based multiarrays (DBMs) first-rate biosensors for in vitro detection of electrochemical and electrical signals from excitable cells together, with potential for in vivo applications as neural interfaces and prostheses. Here, we will review the electrochemical and physical properties of various DBMs and how these devices have been employed for recording released neurotransmitter molecules and all-or-none action potentials from living cells. Specifically, we will overview how DBMs can resolve localized exocytotic events from subcellular compartments using high-density microelectrode arrays (MEAs), or monitoring oxidizable neurotransmitter release from populations of cells in culture and tissue slices using low-density MEAs. Interfacing DBMs with excitable cells is currently leading to the promising opportunity of recording electrical signals as well as creating neuronal interfaces through the same device. Given the recent increasingly growing development of newly available DBMs of various geometries to monitor electrical activity and neurotransmitter release in a variety of excitable and neuronal tissues, the discussion will be limited to planar DBMs.

Effects of high-power laser irradiation on sub-superficial graphitic layers in single-crystal diamond

We report on the structural modifications induced by a λ = 532 nm ns-pulsed high-power laser on sub-superficial graphitic layers in single-crystal diamond realized by means of MeV ion implantation. A systematic characterization of the structures obtained under different laser irradiation conditions (power density, number of pulses) and subsequent thermal annealing was performed by different electron microscopy techniques. The main feature observed after laser irradiation is the thickening of the pre-existing graphitic layer. Cross-sectional SEM imaging was performed to directly measure the thickness of the modified layers, and subsequent selective etching of the buried layers was employed to both assess their graphitic nature and enhance the SEM imaging contrast. In particular, it was found that for optimal irradiation parameters the laser processing induces a six-fold increase the thickness of sub-superficial graphitic layers without inducing mechanical failures in the surrounding crystal. TEM microscopy and EELS spectroscopy allowed a detailed analysis of the internal structure of the laser-irradiated layers, highlighting the presence of different nano-graphitic and amorphous layers. The obtained results demonstrate the effectiveness and versatility of high-power laser irradiation for an accurate tuning of the geometrical and structural features of graphitic structures embedded in single-crystal diamond, and open new opportunities in diamond fabrication.

Nanodiamonds-induced effects on neuronal firing of mouse hippocampal microcircuits

Fluorescent nanodiamonds (FND) are carbon-based nanomaterials that can efficiently incorporate optically active photoluminescent centers such as the nitrogen-vacancy complex, thus making them promising candidates as optical biolabels and drug-delivery agents. FNDs exhibit bright fluorescence without photobleaching combined with high uptake rate and low cytotoxicity. Focusing on FNDs interference with neuronal function, here we examined their effect on cultured hippocampal neurons, monitoring the whole network development as well as the electrophysiological properties of single neurons. We observed that FNDs drastically decreased the frequency of inhibitory (from 1.81 Hz to 0.86 Hz) and excitatory (from 1.61 to 0.68 Hz) miniature postsynaptic currents, and consistently reduced action potential (AP) firing frequency (by 36%), as measured by microelectrode arrays. On the contrary, bursts synchronization was preserved, as well as the amplitude of spontaneous inhibitory and excitatory events. Current-clamp recordings revealed that the ratio of neurons responding with AP trains of high-frequency (fast-spiking) versus neurons responding with trains of low-frequency (slow-spiking) was unaltered, suggesting that FNDs exerted a comparable action on neuronal subpopulations. At the single cell level, rapid onset of the somatic AP (“kink”) was drastically reduced in FND-treated neurons, suggesting a reduced contribution of axonal and dendritic components while preserving neuronal excitability.

Characterization of the recovery of mechanical properties of ion-implanted diamond after thermal annealing

Abstract Due to their outstanding mechanical properties, diamond and diamond-like materials find significant technological applications ranging from well-established industrial fields (cutting tools, coatings, etc.) to more advanced mechanical devices as micro- and nano-electromechanical systems. The use of energetic ions is a powerful and versatile tool to fabricate three-dimensional micro-mechanical structures. In this context, it is of paramount importance to have an accurate knowledge of the effects of ion-induced structural damage on the mechanical properties of this material, primarily to predict potential undesired side-effects of the ion implantation process, and possibly to tailor the desired mechanical properties of the fabricated devices. We present an Atomic Force Microscopy (AFM) characterization of free-standing cantilevers in single-crystal diamond obtained by a FIB-assisted lift-off technique, which allows the determination of the Youngs modulus of the diamond crystal after the MeV ion irradiation process concurrent to the fabrication of the microstructures, and subsequent thermal annealing. The AFM measurements were performed with the beam-bending technique and show that the thermal annealing process allows for an effective recovery of the mechanical properties of the pristine crystal.