We have measured the radiation tolerance of poly-crystalline and single-crystalline diamonds grown by the chemical vapor deposition (CVD) process by measuring the charge collected before and after irradiation in a 50 m pitch strip detector fabricated on each diamond sample. We irradiated one group of sensors with 800 MeV protons, and a second group of sensors with 24 GeV protons, in steps, to protons cm−2 and protons cm−2 respectively. We observe the sum of mean drift paths for electrons and holes for both poly-crystalline CVD diamond and single-crystalline CVD diamond decreases with irradiation fluence from its initial value according to a simple damage curve characterized by a damage constant for each irradiation energy and the irradiation fluence. We find for each irradiation energy the damage constant, for poly-crystalline CVD diamond to be the same within statistical errors as the damage constant for single-crystalline CVD diamond. We find the damage constant for diamond irradiated with 24 GeV protons to be and the damage constant for diamond irradiated with 800 MeV protons to be . Moreover, we observe the pulse height decreases with fluence for poly-crystalline CVD material and within statistical errors does not change with fluence for single-crystalline CVD material for both 24 GeV proton irradiation and 800 MeV proton irradiation. Finally, we have measured the uniformity of each sample as a function of fluence and observed that for poly-crystalline CVD diamond the samples become more uniform with fluence while for single-crystalline CVD diamond the uniformity does not change with fluence.

We report on the systematic characterization of conductive micro-channels fabricated in single-crystal diamond with direct ion microbeam writing. Focused high-energy (∼MeV) helium ions are employed to selectively convert diamond with micrometric spatial accuracy to a stable graphitic phase upon thermal annealing, due to the induced structural damage occurring at the end-of-range. A variable-thickness mask allows the accurate modulation of the depth at which the microchannels are formed, from several µm deep up to the very surface of the sample. By means of cross-sectional transmission electron microscopy (TEM), we demonstrate that the technique allows the direct writing of amorphous (and graphitic, upon suitable thermal annealing) microstructures extending within the insulating diamond matrix in the three spatial directions, and in particular, that buried channels embedded in a highly insulating matrix emerge and electrically connect to the sample surface at specific locations. Moreover, by means of electrical characterization at both 2 room temperature and variable temperature, we investigate the conductivity and the charge-transport mechanisms of microchannels obtained by implantation at different ion fluences and after subsequent thermal processes, demonstrating that upon high-temperature annealing, the channels implanted above a critical damage density convert into a stable graphitic phase. These structures have significant impact for different applications, such as compact ionizing radiation detectors, dosimeters, bio-sensors and more generally diamond-based devices with buried three-dimensional all-carbon electrodes.

Micro-Graphitic Single Crystal Diamond Multi Electrode Arrays (μG-SCD-MEAs) have so far been used as amperometric sensors to detect catecholamines from chromaffin cells and adrenal gland slices. Besides having time resolution and sensitivity that are comparable with carbon fiber electrodes, that represent the gold standard for amperometry, μG-SCD-MEAs also have the advantages of simultaneous multisite detection, high biocompatibility and implementation of amperometric/potentiometric protocols, aimed at monitoring exocytotic events and neuronal excitability. In order to adapt diamond technology to record neuronal activity, the μG-SCD-MEAs in this work have been interfaced with cultured midbrain neurons to detect electrical activity as well as quantal release of dopamine (DA). μG-SCD-MEAs are based on graphitic sensing electrodes that are embedded into the diamond matrix and are fabricated using MeV ion beam lithography. Two geometries have been adopted, with 4 × 4 and 8 × 8 microelectrodes (20 μm × 3.5 μm exposed area, 200 μm spacing). In the amperometric configuration, the 4 × 4 μG-SCD-MEAs resolved quantal exocytosis from midbrain dopaminergic neurons. KCl-stimulated DA release occurred as amperometric spikes of 15 pA amplitude and 0.5 ms half-width, at a mean frequency of 0.4 Hz. When used as potentiometric multiarrays, the 8 × 8 μG-SCD-MEAs detected the spontaneous firing activity of midbrain neurons. Extracellularly recorded action potentials (APs) had mean amplitude of ∼-50 μV and occurred at a mean firing frequency of 0.7 Hz in 67% of neurons, while the remaining fired at 6.8 Hz. Comparable findings were observed using conventional MEAs (0.9 and 6.4 Hz, respectively). To test the reliability of potentiometric recordings with μG-SCD-MEAs, the D 2 -autoreceptor modulation of firing was investigated by applying levodopa ( L -DOPA, 20 μM), and comparing μG-SCD-MEAs, conventional MEAs and current-clamp recordings. In all cases, L -DOPA reduced the spontaneous spiking activity in most neurons by 70%, while the D 2 -antagonist sulpiride reversed this effect. Cell firing inhibition was generally associated with increased APs amplitude. A minority of neurons was either insensitive to, or potentiated by L -DOPA, suggesting that AP recordings originate from different midbrain neuronal subpopulations and reveal different modulatory pathways. Our data demonstrate, for the first time, that μG-SCD-MEAs are multi-functional biosensors suitable to resolve real-time DA release and AP firing in in vitro neuronal networks.

We present experimental results and numerical Finite Element analysis to describe surface swelling due to the creation of buried graphite-like inclusions in diamond substrates subjected to MeV ion implantation. Numerical predictions are compared to experimental data for MeV proton and helium implantations, performed with scanning ion microbeams. Swelling values are measured with white light interferometric profilometry in both cases. Simulations are based on a model which accounts for the through-the-thickness variation of mechanical parameters in the material, as a function of ion type, fluence and energy. Surface deformation profiles and internal stress distributions are analyzed and numerical results are seen to adequately fit experimental data. Results allow us to draw conclusions on structural damage mechanisms in diamond for different MeV ion implantations.Comment: 15 pages, 4 figure

The quantal release of catecholamines from neuroendocrine cells is a key mechanism which has been investigated with a broad range of materials and devices, among which carbon-based materials such as carbon fibers, diamond-like carbon, carbon nanotubes and nanocrystalline diamond. In the present work we demonstrate that a MeV-ion-microbeam lithographic technique can be successfully employed for the fabrication of an all-carbon miniaturized cellular bio-sensor based on graphitic micro-channels embedded in a single-crystal diamond matrix. The device was functionally characterized for the in vitro recording of quantal exocytic events from single chromaffin cells, with high sensitivity and signal-to-noise ratio, opening promising perspectives for the realization of monolithic all-carbon cellular biosensors.Submitted to 2

This paper reports on the fabrication and characterization of a high purity monocrystalline diamond detector with buried electrodes realized by the selective damage induced by a focused 6 MeV carbon ion beam scanned over a pattern defined at the micrometric scale. A suitable variable-thickness mask was deposited on the diamond surface in order to modulate the penetration depth of the ions and to shallow the damage profile toward the surface. After the irradiation, the sample was annealed at high temperature in order to promote the conversion to the graphitic phase of the end-of range regions which experienced an ioninduced damage exceeding the damage threshold, while recovering the sub-threshold damaged regions to the highly resistive diamond phase. This process provided conductive graphitic electrodes embedded in the insulating diamond matrix; the presence of the variablethickness mask made the terminations of the channels emerging at the diamond surface and available to be connected to an external electronic circuit. In order to evaluate the quality of this novel microfabrication procedure based on direct ion writing, we performed frontal Ion Beam Induced Charge (IBIC) measurements by raster scanning focused MeV ion beams onto Corresponding author: ettore.vittone@unito.it 2 the diamond surface. Charge collection efficiency (CCE) maps were measured at different bias voltages. The interpretation of such maps was based on the Shockley-Ramo-Gunn formalism.

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.

We present a phenomenological model and Finite Element simulations to describe the depth variation of mass density and strain of ion-implanted single-crystal diamond.Several experiments are employed to validate the approach: firstly, samples implanted with 180 keV B ions at relatively low fluences are characterized using high-resolution Xray diffraction (HR-XRD); secondly, the mass density variation of a sample implanted with 500 keV He ions well above its amorphization threshold is characterized with Electron Energy Loss Spectroscopy (EELS). At high damage densities, the experimental depth profiles of strain and density display a saturation effect with increasing damage and