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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., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Novel porous boron-doped diamond (BDD porous )-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 BDD porous 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 SiO 2 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 × 10 21 atoms cm -3 and increased content of non-diamond (sp 2 ) 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 mm 2 to 7.72 mm 2 ), 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 BDD porous 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 BDD porous 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 BDD porous electrodes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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 NV 0 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.

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 sp 2 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., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 SiO 2 /Si substrates, which was also measured by atomic force microscopy. Optical contrast of hBN on SiO 2 /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 E 2g phonon mode of atomically thin hBN on SiO 2 /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 E 2g 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.

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.