Highly Occupied Surface States at Deuterium-Grown Boron-Doped Diamond Interfaces for Efficient Photoelectrochemistry.

Polycrystalline boron-doped diamond is a promising material for high-power aqueous electrochemical applications in bioanalytics, catalysis, and energy storage. The chemical vapor deposition (CVD) process of diamond formation and doping is totally diversified by using high kinetic energies of deuterium substituting habitually applied hydrogen. The high concentration of deuterium in plasma induces atomic arrangements and steric hindrance during synthesis reactions, which in consequence leads to a preferential (111) texture and more effective boron incorporation into the lattice, reaching a one order of magnitude higher density of charge carriers. This provides the surface reconstruction impacting surficial populations of CC dimers, CH, CO groups, and COOH termination along with enhanced kinetics of their abstraction, as revealed by high-resolution core-level spectroscopies. A series of local densities of states were computed, showing a rich set of highly occupied and localized surface states for samples deposited in deuterium, negating the connotations of band bending. The introduction of enhanced incorporation of boron into (111) facet of diamond leads to the manifestation of surface electronic states below the Fermi level and above the bulk valence band edge. This unique electronic band structure affects the charge transfer kinetics, electron affinity, and diffusion field geometry critical for efficient electrolysis, electrocatalysis, and photoelectrochemistry.

Enhancing electroanalytical performance of porous boron-doped diamond electrodes by increasing thickness for dopamine detection.

Novel porous boron-doped diamond (BDDporous)-based materials have attracted lots of research interest due to their enhanced detection ability and biocompatibility, favouring them for use in neuroscience. This study reports on morphological, spectral, and electrochemical characterisation of three BDDporous electrodes of different thickness given by a number of deposited layers (2, 3 and 5). These were prepared using microwave plasma-enhanced chemical vapour deposition on SiO2 nanofiber-based scaffolds. Further, the effect of number of layers and poly-l-lysine coating, commonly employed in neuron cultivation experiments, on sensing properties of the neurotransmitter dopamine in a pH 7.4 phosphate buffer media was investigated. The boron doping level of ∼2 × 1021 atoms cm-3 and increased content of non-diamond (sp2) carbon in electrodes with more layers was evaluated by Raman spectroscopy. Cyclic voltammetric experiments revealed reduced working potential windows (from 2.4 V to 2.2 V), higher double-layer capacitance values (from 405 µF cm-2 to 1060 µF cm-2), enhanced rates of electron transfer kinetics and larger effective surface areas (from 5.04 mm2 to 7.72 mm2), when the number of porous layers increases. For dopamine, a significant boost in analytical performance was recognized with increasing number of layers using square-wave voltammetry: the highest sensitivity of 574.1 µA µmol-1 L was achieved on a BDDporous electrode with five layers and dropped to 35.9 µA µmol-1 L when the number of layers decreased to two. Consequently, the lowest detection limit of 0.20 µmol L-1 was obtained on a BDDporous electrode with five layers. Moreover, on porous electrodes, enhanced selectivity for dopamine detection in the presence of ascorbic acid and uric acid was demonstrated. The application of poly-l-lysine coating on porous electrode surface resulted in a decrease in dopamine peak currents by 17% and 60% for modification times of 1 h and 15 h, respectively. Hence, both examined parameters, the number of deposited porous layers and the presence of poly-l-lysine coating, were proved to considerably affect the characteristics and performance of BDDporous electrodes.

A Label-Free Diamond Microfluidic DNA Sensor Based on Active Nitrogen-Vacancy Center Charge State Control.

We propose a label-free biosensor concept based on the charge state manipulation of nitrogen-vacancy (NV) quantum color centers in diamond, combined with an electrochemical microfluidic flow cell sensor, constructed on boron-doped diamond. This device can be set at a defined electrochemical potential, locking onto the particular chemical reaction, whilst the NV center provides the sensing function. The NV charge state occupation is initially prepared by applying a bias voltage on a gate electrode and then subsequently altered by exposure to detected charged molecules. We demonstrate the functionality of the device by performing label-free optical detection of DNA molecules. In this experiment, a monolayer of strongly cationic charged polymer polyethylenimine is used to shift the charge state of near surface NV centers from negatively charged NV- to neutral NV0 or dark positively charged NV+. Immobilization of negatively charged DNA molecules on the surface of the sensor restores the NV centers charge state back to the negatively charged NV-, which is detected using confocal photoluminescence microscopy. Biochemical reactions in the microfluidic channel are characterized by electrochemical impedance spectroscopy. The use of the developed electrochemical device can also be extended to nuclear magnetic resonance spin sensing.

Comparison of electrochemical performance of various boron-doped diamond electrodes: Dopamine sensing in biomimicking media used for cell cultivation.

Chemically inert and biocompatible boron-doped diamond (BDD) has been successfully used in neuroscience for sensitive neurochemicals sensing and/or as a growth substrate for neurons. In this study, several types of BDD differing in (i) fabrication route, i.e. conventional microwave plasma enhanced chemical vapour deposition (MW-PECVD) reactor vs. MW-PECVD with linear antenna delivery system, (ii) morphology, i.e. planar vs. porous BDD, and (iii) surface treatment, i.e. H-terminated (H-BDDs) vs. O-terminated (O-BDDs), were characterized from a morphological, structural, and electrochemical point of view. Further, planar and porous BDD-based electrodes were tested for sensing of dopamine in common biomimicking environments of pH 7.4, namely phosphate buffer (PB) and HEPES buffered saline (HBS). In HBS, potential windows are narrowed due to electrooxidation of its buffering component (i.e. HEPES), however, dopamine sensing in HBS is possible. H-BDDs (both planar and porous) outperformed O-BDDs as they provided clearer dopamine signals with higher peak currents. As expected, due to its enlarged surface area and increased sp2 content, the highest sensitivity and lowest detection limits of 8 × 10-8 mol L-1 and 6 × 10-8 mol L-1 in PB and HBS media, respectively, were achieved by square-wave voltammetry on porous H-BDD.

Optical Contrast and Raman Spectroscopy Techniques Applied to Few-Layer 2D Hexagonal Boron Nitride.

The successful integration of few-layer thick hexagonal boron nitride (hBN) into devices based on two-dimensional materials requires fast and non-destructive techniques to quantify their thickness. Optical contrast methods and Raman spectroscopy have been widely used to estimate the thickness of two-dimensional semiconductors and semi-metals. However, they have so far not been applied to two-dimensional insulators. In this work, we demonstrate the ability of optical contrast techniques to estimate the thickness of few-layer hBN on SiO2/Si substrates, which was also measured by atomic force microscopy. Optical contrast of hBN on SiO2/Si substrates exhibits a linear trend with the number of hBN monolayers in the few-layer thickness range. We also used bandpass filters (500-650 nm) to improve the effectiveness of the optical contrast methods for thickness estimations. We also investigated the thickness dependence of the high frequency in-plane E2g phonon mode of atomically thin hBN on SiO2/Si substrates by micro-Raman spectroscopy, which exhibits a weak thickness-dependence attributable to the in-plane vibration character of this mode. Ab initio calculations of the Raman active phonon modes of atomically thin free-standing crystals support these results, even if the substrate can reduce the frequency shift of the E2g phonon mode by reducing the hBN thickness. Therefore, the optical contrast method arises as the most suitable and fast technique to estimate the thickness of hBN nanosheets.

Nanocrystalline Boron-Doped Diamond as a Corrosion-Resistant Anode for Water Oxidation via Si Photoelectrodes.

Due to its high sensitivity to corrosion, the use of Si in direct photoelectrochemical (PEC) water-splitting systems that convert solar energy into chemical fuels has been greatly limited. Therefore, the development of low-cost materials resistant to corrosion under oxidizing conditions is an important goal toward a suitable protection of otherwise unstable semiconductors used in PEC cells. Here, we report on the development of a protective coating based on thin and electrically conductive nanocrystalline boron-doped diamond (BDD) layers. We found that  BDD layers protect the underlying Si photoelectrodes over a wide pH range (1-14) in aqueous electrolyte solutions. A BDD layer maintains an efficient charge carrier transfer from the underlying silicon to the electrolyte solution. Si|BDD photoelectrodes show no sign of performance degradation after a continuous PEC treatment in neutral, acidic, and basic electrolytes. The deposition of a cobalt phosphate (CoPi) oxygen evolution catalyst onto the BDD layer significantly reduces the overpotential for water oxidation, demonstrating the ability of  BDD layers to substitute the transparent conductive oxide coatings, such as indium tin oxide (ITO) and fluorine-doped tin oxide (FTO), frequently used as protective layers in Si photoelectrodes.

The diamond nano-balance.

Detecting nano-gram quantities of analyte in the liquid or gas phase is crucial for pathogen detection, antigen/DNA detection, water monitoring, electrochemical analysis, and many other bio-electrochemical applications. The quartz crystal microbalance (QCM) has become a significant sensor for both liquid and gas phase graviometry due to its high sensitivity, robustness, ease of use and simultaneous electrochemistry capabilities. One key factor plaguing the QCM in most sensor applications is the stability of the surface functionalisation. Diamond offers the most stable surface for functionalisation, the widest electrochemical window and the lowest noise floor. Unfortunately the growth of diamond on QCMs is problematic due to the low curie point of quartz, resulting in the loss of the piezoelectric properties of the QCM. In this work the replacement of the quartz with a high temperature stable piezoelectric material is proposed, and a nanocrystalline diamond coated sensor demonstrated.

P-doped diamond grown on (110)-textured microcrystalline diamond: growth, characterization and devices.

The formation and properties of (110)-textured P-doped microcrystalline CVD diamond were studied. Based on several microscopy techniques, with a special emphasis on electron backscattered diffraction, a detailed determination of the grain orientations with respect to the exact [110] axis is given. The different orientations present in the film, in combination with low phosphine concentrations in the gas phase, lead to a variation in P incorporation that can vary over three orders of magnitude, as determined with cathodoluminescence mapping. The role of the surface morphology in the observation of these large incorporation differences is explained. Hall measurements confirm that the films are n-type conductive with a thermal activation energy of 0.56 eV. Based on B-doped substrates, pn junctions were created, showing a rectification ratio of nearly 10(4) at ± 25 V.

Combination of e-beam lithography and of high velocity AIN/diamond-layered structure for SAW filters in X band.

In this work, we report on the fabrication results of surface acoustic wave (SAW) devices operating at frequencies up to 8 GHz. In previous work, we have shown that high acoustic velocities (9 to 12 km/s) are obtained from the layered AIN/diamond structure. The interdigital transducers (IDTs) made of aluminium with resolutions up to 250 nm were successfully patterned on AIN/diamond-layered structures with an adapted technological process. The uniformity and periodicity of IDTs were confirmed by field emission scanning electron microscopy and atomic force microscopy analyses. A highly oriented (002) piezoelectric aluminum nitride thin film was deposited on the nucleation side of the CVD diamond by magnetron sputtering technique. The X-ray diffraction effectuated on the AIN/diamond-layered structure exhibits high intensity peaks related to the (002) AIN and (111) diamond orientations. According to the calculated dispersion curves of velocity and the electromechanical coupling coefficient (K2), the AIN layer thickness was chosen in order to combine high velocity and high K2. Experimental data extracted from the fabricated SAW devices match with theoretical values quite well.

Effect of diamond nucleation process on propagation losses of AlN/diamond SAW filter.

In this work, the effect of a diamond nucleation process on freestanding aluminium nitride (AlN)/diamond surface acoustic wave (SAW) device performances was studied. Before diamond deposition, silicon (Si) substrates have been mechanically nucleated, using an ultrasonic vibration table with submicron diamond slurry, and bias-enhanced nucleated (BEN). Freestanding diamond layers obtained on mechanically scratched Si substrates exhibit a surface roughness of R(MS) = 13 nm, whereas very low surface roughness (as low as R(MS) < or = 1 nm) can be achieved on a freestanding BEN diamond layer. Propagation losses have been measured as a function of the operating frequency for the two nucleation techniques. Dispersion curves of phase velocities and electromechanical coupling coefficient (K2) were determined experimentally and by calculation as a function of normalized thickness AlN film (kh(AlN) = 2pi h(AlN)/lambda). Experimental results show that the propagation losses strongly depend on the nucleation technique, and that these losses are weakly increased with frequency when the BEN technique is used.

High velocity SAW using aluminum nitride film on unpolished nucleation side of free-standing CVD diamond.

High performances surface acoustic wave (SAW) filters based on aluminium nitride (AlN)/diamond layered structure have been fabricated. The C-axis oriented aluminum nitride films with various thicknesses were sputtered on unpolished nucleation side of free-standing polycrystalline chemical vapor deposition (CVD) diamond obtained by silicon substrate etching. Experimental results show that high order modes as well as Rayleigh waves are excited. Experimental results are in good agreement with the theoretical dispersion curves determined by software simulation with Green's function formalism. We demonstrate that high phase velocity first mode wave (so-called Sezawa wave) with high electromechanical coupling coefficient are obtained on AlN/diamond structure. This structure also has a low temperature coefficient of frequency (TCF), and preliminary results suggest that a zero TCF could be expected.