Laser Engineering Nanocarbon Phases within Diamond for Science and Electronics.

Diamond, as the densest allotrope of carbon, displays a range of exemplary material properties that are attractive from a device perspective. Despite diamond displaying high carbon-carbon bond strength, ultrashort (femtosecond) pulse laser radiation can provide sufficient energy for highly localized internal breakdown of the diamond lattice. The less-dense carbon structures generated on lattice breakdown are subject to significant pressure from the surrounding diamond matrix, leading to highly unusual formation conditions. By tailoring the laser dose delivered to the diamond, it is shown that it is possible to create continuously modified internal tracks with varying electrical conduction properties. In addition to the widely reported conducting tracks, conditions leading to semiconducting and insulating written tracks have been identified. High-resolution transmission electron microscopy (HRTEM) is used to visualize the structural transformations taking place and provide insight into the different conduction regimes. The HRTEM reveals a highly diverse range of nanocarbon structures are generated by the laser irradiation, including many signatures for different so-called diaphite complexes, which have been seen in meteorite samples and seem to mediate the laser-induced breakdown of the diamond. This work offers insight into possible formation methods for the diamond and related nanocarbon phases found in meteorites.

A detailed EIS study of boron doped diamond electrodes decorated with gold nanoparticles for high sensitivity mercury detection.

This work compares the electrochemical impedance response of polished and unpolished boron doped diamond (BDD) electrodes, during mercury detection measurements. For each substrate type both bare electrodes and electrodes decorated with average diameter 30 nm AuNPs were used, to investigate the role of AuNPs during mercury sensing with diamond electrodes. In square wave anodic stripping voltammetry (SWASV) measurements for mercury detection, the mercury ions in the electrolyte are deposited onto, then stripped from the diamond electrode surface. To investigate the different electrode performances during these steps, the EIS measurements were made at the deposition and stripping potentials, alongside scans at open circuit potential for comparison. The performance of the electrodes is assessed in terms of their electron transfer rate (k0). The electrodes decorated with AuNPs are shown to have lower capacitance and higher reactivity than the bare pBDD and BDD electrodes, until the mercury concentration in the electrolyte is < 500 µM, when the sp2/sp3 carbon ratio at the surface of the electrodes has a greater influence on the sensitivity for mercury detection than the presence of AuNPs.

Influence of temperature on the electrochemical window of boron doped diamond: a comparison of commercially available electrodes.

This work compares the electrochemical windows of polished and unpolished boron doped diamond (BDD) electrodes with hydrogen and oxygen terminations at a series of temperatures up to 125 °C. The experiment was run at 5 bar pressure to avoid complications due to bubble formation. An alternative method for determining the electrochemical window is compared to the most commonly used method, which defines the window at an arbitrary current density cut-off (Jcut-off) value. This arbitrary method is heavily influenced by the mass transport of the electrolyte and cannot be used to compare electrodes across literature where different Jcut-off values have been used. A linear fit method is described which is less affected by the experimental conditions in a given measurement system. This enables a more accurate comparison of the relative electrochemical window from various diamond electrode types from reported results. Through comparison of polished and unpolished BDD electrodes, with hydrogen and oxygen surface terminations, it is determined that the electrochemical window of BDD electrodes narrows as temperature increases; activation energies are reported.

Diamond Etching Beyond 10 µm with Near-Zero Micromasking.

To exploit the exceptional properties of diamond, new high quality fabrication techniques are needed to produce high performing devices. Etching and patterning diamond to depths beyond one micron has proven challenging due to the hardness and chemical resistance of diamond. A new cyclic Ar/O2 - Ar/Cl2 ICP RIE process has been developed to address micromasking issues from the aluminium mask by optimising the proportion of O2 in the plasma and introducing a preferential "cleaning" step. High quality smooth features up to, but not limited to, 10.6 µm were produced with an average etched surface roughness of 0.47 nm at a diamond etch rate of 45 nm/min and 16.9:1 selectivity.

Spontaneous Differentiation of Human Neural Stem Cells on Nanodiamonds.

The potential use of stem cells in regenerative medicine requires the ability to be able to control stem cell fate as cellular networks are developed. Here, nanodiamonds (≈10 nm) are supported on glass and shown to be an excellent host for the attachment and proliferation of human neural stem cells. Moreover, it is shown that spontaneous differentiation into neurons occurs on nanodiamonds. The use of variously oxygen terminated and hydrogen terminated nanodiamonds has been explored. It is shown that O-ND monolayers promote the differentiation of human neural stem cells into neurons with increased total neurite length, degree of branching, and density of neurites when compared with H-NDs or the glass control. The total number of neurites and total neurite length expressing MAP2, a protein enriched in dendrites, is over five times higher for spontaneously differentiated neurones on the O-NDs compared to the control. The fact that inexpensive nanodiamonds can be attached through simple sonication from water on 2D and 3D shapes indicates significant promise for their potential as biomaterials in which neuro-regenerative diseases can be studied.

Nanodiamonds for device applications: An investigation of the properties of boron-doped detonation nanodiamonds.

The inclusion of boron within nanodiamonds to create semiconducting properties would create a new class of applications in the field of nanodiamond electronics. Theoretical studies have differed in their conclusions as to whether nm-scale NDs would support a stable substitutional boron state, or whether such a state would be unstable, with boron instead aggregating or attaching to edge structures. In the present study detonation-derived NDs with purposefully added boron during the detonation process have been studied with a wide range of experimental techniques. The DNDs are of ~4 nm in size, and have been studied with CL, PL, Raman and IR spectroscopies, AFM and HR-TEM and electrically measured with impedance spectroscopy; it is apparent that the B-DNDs studied here do indeed support substitutional boron species and hence will be acting as semiconducting diamond nanoparticles. Evidence for moderate doping levels in some particles (~1017 B cm-3), is found alongside the observation that some particles are heavily doped (~1020 B cm-3) and likely to be quasi-metallic in character. The current study has therefore shown that substitutional boron doping in nm NDs is in fact possible, opening-up the path to a whole host of new applications for this interesting class of nano-particles.

Surface functionalisation of nanodiamonds for human neural stem cell adhesion and proliferation.

Biological systems interact with nanostructured materials on a sub-cellular level. These interactions may govern cell behaviour and the precise control of a nanomaterial's structure and surface chemistry allow for a high degree of tunability to be achieved. Cells are surrounded by an extra-cellular matrix with nano-topographical properties. Diamond based materials, and specifically nanostructured diamond has attracted much attention due to its extreme electrical and mechanical properties, chemical inertness and biocompatibility. Here the interaction of nanodiamond monolayers with human Neural Stem Cells (hNSCs) has been investigated. The effect of altering surface functionalisation of nanodiamonds on hNSC adhesion and proliferation has shown that confluent cellular attachment occurs on oxygen terminated nanodiamonds (O-NDs), but not on hydrogen terminated nanodiamonds (H-NDs). Analysis of H and O-NDs by Atomic Force Microscopy, contact angle measurements and protein adsorption suggests that differences in topography, wettability, surface charge and protein adsorption of these surfaces may underlie the difference in cellular adhesion of hNSCs reported here.

Nanoscale, conformal films of graphitic carbon nitride deposited at room temperature: a method for construction of heterojunction devices.

Graphitic carbon nitrides (GCNs) represent a family of 2D materials composed of carbon and nitrogen with variable amounts of hydrogen, used in a wide variety of applications. We report a method of room temperature thin film deposition which allows ordered GCN layers to be deposited on a very wide variety of substrates, including conductive glass, flexible plastics, nanoparticles and nano-structured surfaces, where they form a highly conformal coating on the nanoscale. Film thicknesses of below 20 nm are achievable. In this way we construct functional nanoscale heterojunctions between TiO2 nanoparticles and GCN, capable of producing H2 photocatalytically under visible light irradiation. The films are hydrogen rich, have a band gap around 1.7 eV, display transmission electron microscopy lattice fringes as well as X-ray diffraction peaks despite being deposited at room temperature, and show characteristic Raman and IR bands. We use cluster etching to reveal the chemical environments of C and N in GCN using X-ray photoelectron spectroscopy. We elucidate the mechanism of this deposition, which operates via sequential surface adsorption and reaction analogous to atomic layer deposition. The mechanism may have implications for current models of carbon nitride formation.

Patterning of nanodiamond tracks and nanocrystalline diamond films using a micropipette for additive direct-write processing.

The ability to pattern the seeding of nanodiamonds (NDs), and thus selectively control areas of diamond growth, is a useful capability for many applications, including photonics, microelectromechanical systems (MEMS) prototyping, and biomaterial design. A microprinting technique using a computer-driven micropipette has been developed to deposit patterns of ND monolayers from an unreactive water/glycerol ND ink to 5-µm resolution. The concentration and composition of the ND solution were optimized to realize high-density monolayers of NDs and consistent ND printing. Subsequent nanocrystalline diamond (NCD) patterns grown using chemical vapor deposition showed a high level of compliance with the printed ND pattern. This "direct-write", bottom-up, and additive process offers a versatile and simple alternative to pattern diamond. The process has the particular advantage that it does not require lithography or destructive processing such as reactive-ion etching (RIE) and, pertinently, does not involve reactive chemicals that could alter the surface chemistry of NDs. Furthermore, given that this process obviates the use of conventional lithography, substrates that are not suitable for lithographic processing (e.g., excessively small or three-dimensional structured substrates) can be inscribed with ND patterns. The technique also allows for the growth of discrete, localized, single-crystal nanodiamonds with applications in quantum technology.

Graphene-Nanodiamond Heterostructures and their application to High Current Devices.

Graphene on hydrogen terminated monolayer nanodiamond heterostructures provides a new way to improve carrier transport characteristics of the graphene, offering up to 60% improvement when compared with similar graphene on SiO2/Si substrates. These heterostructures offers excellent current-carrying abilities whilst offering the prospect of a fast, low cost and easy methodology for device applications. The use of ND monolayers is also a compatible technology for the support of large area graphene films. The nature of the C-H bonds between graphene and H-terminated NDs strongly influences the electronic character of the heterostructure, creating effective charge redistribution within the system. Field effect transistors (FETs) have been fabricated based on this novel herterostructure to demonstrate device characteristics and the potential of this approach.

Biocompatibility of nanostructured boron doped diamond for the attachment and proliferation of human neural stem cells.

OBJECTIVE: We quantitatively investigate the biocompatibility of chemical vapour deposited (CVD) nanocrystalline diamond (NCD) after the inclusion of boron, with and without nanostructuring. The nanostructuring method involves a novel approach of growing NCD over carbon nanotubes (CNTs) that act as a 3D scaffold. This nanostructuring of BNCD leads to a material with increased capacitance, and this along with wide electrochemical window makes BNCD an ideal material for neural interface applications, and thus it is essential that their biocompatibility is investigated. APPROACH: Biocompatibility was assessed by observing the interaction of human neural stem cells (hNSCs) with a variety of NCD substrates including un-doped ones, and NCD doped with boron, which are both planar, and nanostructured. hNSCs were chosen due to their sensitivity, and various methods including cell population and confluency were used to quantify biocompatibility. MAIN RESULTS: Boron inclusion into NCD film was shown to have no observable effect on hNSC attachment, proliferation and viability. Furthermore, the biocompatibility of nanostructured boron-doped NCD is increased upon nanostructuring, potentially due to the increased surface area. SIGNIFICANCE: Diamond is an attractive material for supporting the attachment and development of cells as it can show exceptional biocompatibility. When boron is used as a dopant within diamond it becomes a p-type semiconductor, and at high concentrations the diamond becomes quasi-metallic, offering the prospect of a direct electrical device-cell interfacing system.

Ordered growth of neurons on diamond.

Diamond has a number of unique properties that make it an attractive electronic and bio-electronic material. Here we show the ordered growth of mammalian neurons, the principal electrogenic cells of the nervous system, on diamond. Proteins were specifically patterned on diamond surfaces by micro-contact printing. Mouse cortical neurons were then cultured on these substrates. Neuron adhesion and outgrowth was specific for those areas of the diamond that had been stamped with laminin, resulting in ordered growth of high resolution. Neurons survived in culture for the duration of the experiment, and laminin patterns were stable for at least 1 week in culture. The relative biocompatibility of diamond and the suitability of neuron interfacing with the hydrogen surface conductivity layer make this an interesting model for the formation of defined neuronal networks and for implants.

Surface acoustic wave properties of freestanding diamond films.

"Ideal" diamond has the highest acoustic velocity of any material known, and is of great interest as a substrate material for high frequency surface acoustic wave (SAW) device structures. However, little is known of the acoustic wave propagation properties of polycrystalline diamond grown by chemical vapour deposition (CVD) techniques, the commercially accessible form of this material. We report on propagation of laser-generated SAW on three forms of freestanding CVD diamond samples, "white" polycrystalline, "black" polycrystalline, and "highly oriented" diamond. Despite differing sample nature, SAW waves propagating along the smooth (nucleation) side of the diamond showed similar velocities in the range 10600-11900 ms(-1). These results are discussed in terms of the potential of each form of CVD diamond for SAW device fabrication.

Boron-doped nanocrystalline diamond microelectrode arrays monitor cardiac action potentials.

The expansion of diamond-based electronics in the area of biological interfacing has not been as thoroughly explored as applications in electrochemical sensing. However, the biocompatibility of diamond, large safe electrochemical window, stability, and tunable electronic properties provide opportunities to develop new devices for interfacing with electrogenic cells. Here, the fabrication of microelectrode arrays (MEAs) with boron-doped nanocrystalline diamond (BNCD) electrodes and their interfacing with cardiomyocyte-like HL-1 cells to detect cardiac action potentials are presented. A nonreductive means of structuring doped and undoped diamond on the same substrate is shown. The resulting BNCD electrodes show high stability under mechanical stress generated by the cells. It is shown that by fabricating the entire surface of the MEA with NCD, in patterns of conductive doped, and isolating undoped regions, signal detection may be improved up to four-fold over BNCD electrodes passivated with traditional isolators.

Boron δ-doped (111) diamond solution gate field effect transistors.

A solution gate field effect transistor (SGFET) using an oxidised boron δ-doped channel on (111) diamond is presented for the first time. Employing an optimised plasma chemical vapour deposition (PECVD) recipe to deposit δ-layers, SGFETs show improved current-voltage (I-V) characteristics in comparison to previous similar devices fabricated on (100) and polycrystalline diamond, where the device is shown to operate in the enhancement mode of operation, achieving channel pinch-off and drain-source current saturation within the electrochemical window of diamond. A maximum gain and transconductance of 3 and 200µS/mm are extracted, showing comparable figures of merit to hydrogen-based SGFET. The oxidised device shows a site-binding model pH sensitivity of 36 mV/pH, displaying fast temporal responses. Considering the biocompatibility of diamond towards cells, the device's highly mutable transistor characteristics, pH sensitivity and stability against anodic oxidation common to hydrogen terminated diamond SGFET, oxidised boron δ-doped diamond SGFETs show promise for the recording of action potentials from electrogenic cells.

Next generation brain implant coatings and nerve regeneration via novel conductive nanocomposite development.

Composite materials based on the coupling of conductive organic polymers and carbon nanotubes have shown that they possess properties of the individual components with a synergistic effect. Multi-wall carbon nanotube (MWCNT)/ polymer composites are hybrid materials that combine numerous mechanical, electrical and chemical properties and thus, constitute ideal biomaterials for a wide range of regenerative medicine applications. Although, complete dispersion of CNT in a polymer matrix has rarely been achieved, in this study we have succeeded high dispersibility of CNT in POSS-PCU and POSS-PCL, novel polymers based on polyprolactone and polycarbonate polyurethane (PCU) and poly(caprolactoneurea)urethane both having incorporated polyhedral oligomeric silsesquioxane (POSS). We report the synthesis and characterization of a novel biomaterial that possesses unique properties of being electrically conducting and thus being capable of electronic interfacing with tissue. To this end, POSS-PCU/MWCNT composite can be used as a biomaterial for the development of nerve guidance channels to promote nerve regeneration and POSS-PCL/MWCNT as a substrate to increase electronic interfacing between neurons and micro-machined electrodes for potential applications in neural probes, prosthetic devices and brain implants.

The use of nanodiamond monolayer coatings to promote the formation of functional neuronal networks.

Nanostructured materials provide a new dimension of interaction with biological systems that takes place on a sub-cellular level with a high degree of specificity. In the field of neuroscience the nanoscale corresponds to the size of synapses; the specific connections between brain cells. In this context, diamond-based materials have attracted much attention due to their extreme mechanical and electrical properties and their chemical inertness. Here the suitability of nanodiamond (ND) monolayers to act as a platform for neuronal growth is investigated. Neurons cultured on various ND-coated substrates perform remarkably well, and similar to those grown on standard protein-coated materials with respect to their initial cell attachment, sustained neurite outgrowth, cell-autonomous neuronal excitability and functionality of the resulting electrical networks. ND layering provides an excellent growth substrate on various materials for functional neuronal networks and bypasses the necessity of protein coating, which promises great potential for chronic medical implants.