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In the present work, we report on the monolithic fabrication by means of ion beam lithography of hollow micro-channels within a diamond substrate, to be employed for microfluidic applications. The fabrication strategy takes advantage of ion beam induced damage to convert diamond into graphite, which is characterized by a higher reactivity to oxidative etching with respect to the chemically inert pristine structure. This phase transition occurs in sub-superficial layers thanks to the peculiar damage profile of MeV ions, which mostly damage the target material at their end of range. The structures were obtained by irradiating commercial CVD diamond samples with a micrometric collimated C + ion beam at three different energies (4 MeV, 3.5 MeV and 3 MeV) at a total fluence of 2 × 10 16 cm −2 . The chosen multiple-energy implantation strategy allows to obtain a thick box-like highly damaged region ranging from 1.6 μm to 2.1 μm below the sample surface. High-temperature annealing was performed to both promote the graphitization of the ion-induced amorphous layer and to recover the pristine crystalline structure in the cap layer. Finally, the graphite was removed by ozone etching, obtaining monolithic microfluidic structures. These prototypal microfluidic devices were tested injecting aqueous solutions and the evidence of the passage of fluids through the channels was confirmed by confocal fluorescent microscopy. [ABSTRACT FROM AUTHOR]

The Deep Ion Beam Lithography technique has been extensively adopted in recent years for the fabrication of graphitic electrodes in bulk diamond with a wide range of technological applications. Particularly, it has been recently shown that a high current can be driven in devices consisting of micrometer-spaced sub-superficial graphitic electrodes. This effect has been exploited to stimulate electroluminescence from color centers placed in the active region of the device. A deep understanding of the conduction mechanisms governing charge transport in micro-regions of defective diamond comprised between graphitic electrodes is necessary in order to fully exploit the functionality of these opto-electronic devices, as well as to assess the ion-beam-micromachining of diamond as a convenient technique for the fabrication of solid-state micro-devices. In this work, a temperature-dependent characterization of the electrical properties of a sub-superficial graphite-diamond-graphite junction is presented and discussed. The ohmic behavior observed at low bias voltages is ascribed to a donor level with an activation energy of (0.217 ± 0.002) eV, a value compatible with previous reports on nitrogen-related defects. A transition to a high-current regime above a critical voltage V C was also observed, and interpreted in terms of the Space-Charge-Limited Current model. The temperature-dependent measurements allowed to investigate the role of charge trapping in the charge injection mechanism of the junction. By fitting the temperature dependence in the high-current regime it was possible to determine the relevant trap level of the associated Poole-Frenkel mechanism, leading to a value of (0.278 ± 0.001) eV from the conduction band. The Poole-Frenkel conduction model in high-current regime enabled also a preliminary investigation in the effects of ion implantation on the modification of the dc dielectric constant of diamond. [ABSTRACT FROM AUTHOR]

The control of the charge state of nitrogen-vacancy (NV) centers in diamond is of primary importance for the stabilization of their quantum-optical properties, in applications ranging from quantum sensing to quantum computing. In this work buried current-injecting graphitic micro-electrodes were fabricated in bulk diamond by means of a 6 MeV C 3+ scanning micro-beam. The electrodes were exploited to control the variation in the relative population of the negative (NV − ) and neutral (NV 0 ) charge states of a sub-superficial NV centers ensemble located in the inter-electrode gap region. Photoluminescence spectra exhibited an electrically-induced increase up to 40% in the NV − population at the expense of the NV 0 charge state, with a linear dependence from the injected current at applied biases smaller than 350 V, and was interpreted as the result of electron trapping at NV sites. An abrupt current increase at ∼350 V bias resulted in a strong electroluminescence from the NV 0 centers, in addition to two spectrally sharp emission lines at 563.5 nm and 580 nm, not visible under optical excitation and attributed to self-interstitial defects. These results disclose new possibilities in the electrical control of the charge state of NV centers located in the diamond bulk, which are characterized by longer spin coherence times. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Focused MeV ion microbeams are suitable tools for the direct writing of conductive graphitic channels buried in an insulating diamond bulk, as demonstrated in previous works with the fabrication of multi-electrode ionizing radiation detectors and cellular biosensors. In this work we investigate the suitability of the fabrication method for the electrical excitation of color centers in diamond. Differently from photoluminescence, electroluminescence requires an electrical current flowing through the diamond sub-gap states for the excitation of the color centers. With this purpose, buried graphitic electrodes with a spacing of 10 μm were fabricated in the bulk of a detector-grade CVD single-crystal diamond sample using a scanning 1.8 MeV He + micro-beam. The current flowing in the gap region between the electrodes upon the application of a 450 V bias voltage was exploited as the excitation pump for the electroluminescence of different types of color centers localized in the above-mentioned gap. The bright light emission was spatially mapped using a confocal optical microscopy setup. The spectral analysis of electroluminescence revealed the emission from neutrally-charged nitrogen-vacancy centers (NV 0 , λ ZPL = 575 nm), as well as from cluster crystal dislocations (A-band, λ = 400–500 nm). Moreover, an electroluminescence signal with appealing spectral features (sharp emission at room temperature, low phonon sidebands) from He-related defects was detected ( λ ZPL = 536.3 nm, λ ZPL = 560.5 nm); a low and broad peak around λ = 740 nm was also observed and tentatively ascribed to Si-V or GR1 centers. These results pose interesting future perspectives for the fabrication of electrically-stimulated single-photon emitters in diamond for applications in quantum optics and quantum cryptography. [ABSTRACT FROM AUTHOR]