Oliver Aneurin Williams

Nanocrystalline Diamond Nanoelectrode Arrays and Ensembles

In this report, the fabrication of all-nanocrystalline diamond (NCD) nanoelectrode arrays (NEAs) by e-beam lithography as well as of all-diamond nanoelectrode ensembles (NEEs) using nanosphere lithography is presented. In this way, nanostructuring techniques are combined with the excellent properties of diamond that are desirable for electrochemical sensor devices. Arrays and ensembles of recessed disk electrodes with radii ranging from 150 to 250 nm and a spacing of 10 μm have been fabricated. Electrochemical impedance spectroscopy as well as cyclic voltammetry was conducted to characterize arrays and ensembles with respect to different diffusion regimes. One outstanding advantage of diamond as an electrode material is the stability of specific surface terminations influencing the electron transfer kinetics. On changing the termination from hydrogen- to oxygen-terminated diamond electrode surface, we observe a dependence of the electron transfer rate constant on the charge of the analyte molecule. Ru(NH(3))(6)(+2/+3) shows faster electron transfer on oxygen than on hydrogen-terminated surfaces, while the anion IrCl(6)(-2/-3) exhibits faster electron transfer on hydrogen-terminated surfaces correlating with the surface dipole layer. This effect cannot be observed on macroscopic planar diamond electrodes and emphasizes the sensitivity of the all-diamond NEAs and NEEs. Thus, the NEAs and NEEs in combination with the efficiency and suitability of the selective electrochemical surface termination offer a new versatile system for electrochemical sensing.

Chemical mechanical polishing of thin film diamond

The demonstration that Nanocrystalline Diamond (NCD) can retain the superior Young’s modulus (1100 GPa) of single crystal diamond twinned with its ability to be grown at low temperatures (<450 °C) has driven a revival into the growth and applications of NCD thin films. However, owing to the competitive growth of crystals the resulting film has a roughness that evolves with film thickness, preventing NCD films from reaching their full potential in devices where a smooth film is required. To reduce this roughness, films have been polished using Chemical Mechanical Polishing (CMP). A Logitech Tribo CMP tool equipped with a polyurethane/polyester polishing cloth and an alkaline colloidal silica polishing fluid has been used to polish NCD films. The resulting films have been characterised with Atomic Force Microscopy, Scanning Electron Microscopy and X-ray Photoelectron Spectroscopy. Root mean square roughness values have been reduced from 18.3 nm to 1.7 nm over 25 μm2, with roughness values as low as 0.42 nm over ∼0.25 μm2. A polishing mechanism of wet oxidation of the surface, attachment of silica particles and subsequent shearing away of carbon has also been proposed.

Diamond-Modified AFM Probes: From Diamond Nanowires to Atomic Force Microscopy-Integrated Boron-Doped Diamond Electrodes

In atomic force microscopy (AFM), sharp and wear-resistant tips are a critical issue. Regarding scanning electrochemical microscopy (SECM), electrodes are required to be mechanically and chemically stable. Diamond is the perfect candidate for both AFM probes as well as for electrode materials if doped, due to diamonds unrivaled mechanical, chemical, and electrochemical properties. In this study, standard AFM tips were overgrown with typically 300 nm thick nanocrystalline diamond (NCD) layers and modified to obtain ultra sharp diamond nanowire-based AFM probes and probes that were used for combined AFM-SECM measurements based on integrated boron-doped conductive diamond electrodes. Analysis of the resonance properties of the diamond overgrown AFM cantilevers showed increasing resonance frequencies with increasing diamond coating thicknesses (i.e., from 160 to 260 kHz). The measured data were compared to performed simulations and show excellent correlation. A strong enhancement of the quality factor upon overgrowth was also observed (120 to 710). AFM tips with integrated diamond nanowires are shown to have apex radii as small as 5 nm and where fabricated by selectively etching diamond in a plasma etching process using self-organized metal nanomasks. These scanning tips showed superior imaging performance as compared to standard Si-tips or commercially available diamond-coated tips. The high imaging resolution and low tip wear are demonstrated using tapping and contact mode AFM measurements by imaging ultra hard substrates and DNA. Furthermore, AFM probes were coated with conductive boron-doped and insulating diamond layers to achieve bifunctional AFM-SECM probes. For this, focused ion beam (FIB) technology was used to expose the boron-doped diamond as a recessed electrode near the apex of the scanning tip. Such a modified probe was used to perform proof-of-concept AFM-SECM measurements. The results show that high-quality diamond probes can be fabricated, which are suitable for probing, manipulating, sculpting, and sensing at single digit nanoscale.

Anisotropic etching of diamond by molten Ni particles

Nanopores in insulating solid state membranes have recently attracted much interest in the field of probing, characterizing, and manipulating single linear polymers such as DNA/RNA and proteins in their native environment. Here a low cost, fast, and effective way to produce nanostructures such as pyramidal shaped nanopores and nanochannels with dimensions down to about 15 nm in diamond membranes without any need for electron-beam lithography is demonstrated. By use of a catalytic process, anisotropic etching of diamond with self-organized Ni nanoparticles in hydrogen atmosphere at 900 °C is achieved and possible etching mechanisms are discussed. It is shown that diamond planes with the crystallographic orientation of [111] are etched slowest with this method.

Structural and optical properties of DNA layers covalently attached to diamond surfaces

Label-free detection of DNA molecules on chemically vapor-deposited diamond surfaces is achieved with spectroscopic ellipsometry in the infrared and vacuum ultraviolet range. This nondestructive method has the potential to yield information on the average orientation of single as well as double-stranded DNA molecules, without restricting the strand length to the persistence length. The orientational analysis based on electronic excitations in combination with information from layer thicknesses provides a deeper understanding of biological layers on diamond. The pi-pi* transition dipole moments, corresponding to a transition at 4.74 eV, originate from the individual bases. They are in a plane perpendicular to the DNA backbone with an associated n-pi* transition at 4.47 eV. For 8-36 bases of single- and double-stranded DNA covalently attached to ultra-nanocrystalline diamond, the ratio between in- and out-of-plane components in the best fit simulations to the ellipsometric spectra yields an average tilt angle of the DNA backbone with respect to the surface plane ranging from 45 degrees to 52 degrees . We comment on the physical meaning of the calculated tilt angles. Additional information is gathered from atomic force microscopy, fluorescence imaging, and wetting experiments. The results reported here are of value in understanding and optimizing the performance of the electronic readout of a diamond-based label-free DNA hybridization sensor.

Microwave properties of nanodiamond particles

The dielectric properties of nanodiamond powders were characterised at microwave frequencies using a cavity perturbation technique, and results were compared with UV Raman spectroscopy. Surface sp2 hybridisation in the nanodiamond samples was varied by subsequent oxygenation and hydrogenation. Dielectric polarisation and loss increased as the sp2 hybridisation was increased. The sensitivity to surface bound sp2 carbon obtained by the microwave cavity technique far exceeds that of comparable techniques (such as Raman spectroscopy) and is much more convenient in practice, lending itself to studies of real-time modification of such powders by external influences (such as temperature and chemical functionalisation).

Tuneable optical lenses from diamond thin films

Nanocrystalline diamond (NCD) membranes of 150 nm thickness and diameters in the millimeter range grown by microwave-assisted chemical-vapor deposition were bulged to investigate their mechanical properties and their use as tuneable optical lenses. The NCD films were grown at different CH4/H2 gas mixtures to vary the sp2/sp3 ratio and thereby to tune their mechanical, optical, and surface morphology properties. By applying gas over pressure the membrane forms a lens shaped geometry. From deflection data we calculated Young’s moduli which decrease with increasing CH4/H2 ratio from 1160 GPa at 0.5% to 900 GPa at 7%. Optical lens applications show a variation in the focal point from infinity to 3.5 mm. The data indicate that NCD is a promising material for tuneable optical lenses applications.

Topographical and Functional Characterization of the ssDNA Probe Layer Generated Through EDC-Mediated Covalent Attachment to Nanocrystalline Diamond Using Fluorescence Microscopy

The covalent attachment method for DNA on nanocrystalline diamond (NCD), involving the introduction of COOH functionalities on the surface by photoattachment of 10-undecenoic acid (10-UDA), followed by the 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC)-mediated coupling to NH 2-labeled ssDNA, is evaluated in terms of stability, density, and functionality of the resulting biological interface. This is of crucial importance in DNA biosensor development. The covalent nature of DNA attachment will infer the necessary stability and favorable orientation to the ssDNA probe molecules. Using confocal fluorescence microscopy, the influence of buffer type for the removal of excess 10-UDA and ssDNA, the probe ssDNA length, the probe ssDNA concentration, and the presence of the COOH-linker on the density and functionality of the ssDNA probe layer were investigated. It was determined that the most homogeneously dense and functional DNA layer was obtained when 300 pmol of short ssDNA was applied to COOH-modified NCD samples, while H-terminated NCD was resistant for DNA attachment. Exploiting this surface functionality dependence of the DNA attachment efficiency, a shadow mask was applied during the photochemical introduction of the COOH-functionalities, leaving certain regions on the NCD H-terminated. The subsequent DNA attachment resulted in a fluorescence pattern corresponding to the negative of the shadow mask. Finally, NCD surfaces covered with mixtures of the 10-UDA linker molecule and a similar molecule lacking the COOH functionality, functioning as a lateral spacer, were examined for their suitability in preventing nonspecific adsorption to the surface and in decreasing steric hindrance. However, purely COOH-modified NCD samples, patterned with H-terminated regions and treated with a controlled amount of probe DNA, proved the most efficient in fulfilling these tasks.

Coherent anti-Stokes Raman scattering microscopy of single nanodiamonds

Nanoparticles have attracted enormous attention for biomedical applications as optical labels, drug delivery vehicles, and contrast agents in vivo. In the quest for superior photostability and bio-compatibility, nanodiamonds (NDs) are considered one of the best choices due to their unique structural, chemical, mechanical, and optical properties. So far, mainly fluorescent NDs have been utilized for cell imaging. However, their use is limited by the efficiency and costs in reliably producing fluorescent defect centers with stable optical properties. Here, we show that single non-fluorescing NDs exhibit strong coherent anti-Stokes Raman scattering (CARS) at the sp3 vibrational resonance of diamond. Using correlative light and electron microscopy, the relationship between CARS signal strength and ND size is quantified. The calibrated CARS signal in turn enables the analysis of the number and size of NDs internalized in living cells in situ, which opens the exciting prospect of following complex cellular trafficking pathways quantitatively.

The Diamond Superconducting Quantum Interference Device

Diamond is an electrical insulator in its natural form. However, when doped with boron above a critical level (∼0.25 atom %) it can be rendered superconducting at low temperatures with high critical fields. Here we present the realization of a micrometer-scale superconducting quantum interference device (μ-SQUID) made from nanocrystalline boron-doped diamond (BDD) films. Our results demonstrate that μ-SQUIDs made from superconducting diamond can be operated in magnetic fields as large as 4 T independent of the field direction. This is a decisive step toward the detection of quantum motion in a diamond-based nanomechanical oscillator.Soumen Mandal ∗ , Tobias Bautze, Oliver A. Williams, Cécile Naud, Étienne Bustarret, Franck Omnès, Pierre Rodière, Tristan Meunier, Christopher Bäuerle ∗ , and Laurent Saminadayar Institut Néel, CNRS et Université Joseph Fourier, F-38042 Grenoble, France Fraunhofer-Institut für Angewandte Festkörperphysik, Tullastraße 72, 79108 Freiburg, Germany and Institut Universitaire de France, 103 boulevard Saint-Michel, 75005 Paris, France