RESUMEN
Robust devices for chronic neural stimulation demand electrode materials which exhibit high charge injection (Q inj) capacity and long-term stability. Boron-doped diamond (BDD) electrodes have shown promise for neural stimulation applications, but their practical applications remain limited due to the poor charge transfer capability of diamond. In this work, we present an attractive approach to produce BDD electrodes with exceptionally high surface area using porous titanium nitride (TiN) as interlayer template. The TiN deposition parameters were systematically varied to fabricate a range of porous electrodes, which were subsequently coated by a BDD thin-film. The electrodes were investigated by surface analysis methods and electrochemical techniques before and after BDD deposition. Cyclic voltammetry (CV) measurements showed a wide potential window in saline solution (between -1.3 and 1.2 V vs. Ag/AgCl). Electrodes with the highest thickness and porosity exhibited the lowest impedance magnitude and a charge storage capacity (CSC) of 253 mC/cm2, which largely exceeds the values previously reported for porous BDD electrodes. Electrodes with relatively thinner and less porous coatings displayed the highest pulsing capacitances (C pulse), which would be more favorable for stimulation applications. Although BDD/TiN electrodes displayed a higher impedance magnitude and a lower C pulse as compared to the bare TiN electrodes, the wider potential window likely allows for higher Q inj without reaching unsafe potentials. The remarkable reduction in the impedance and improvement in the charge transfer capacity, together with the known properties of BDD films, makes this type of coating as an ideal candidate for development of reliable devices for chronic neural interfacing.
RESUMEN
Nucleation is a core scientific concept that describes the formation of new phases and materials. While classical nucleation theory is applied across wide-ranging fields, nucleation energy landscapes have never been directly measured at the atomic level, and experiments suggest that nucleation rates often greatly exceed the predictions of classical nucleation theory. Multistep nucleation via metastable states could explain unexpectedly rapid nucleation in many contexts, yet experimental energy landscapes supporting such mechanisms are scarce, particularly at nanoscale dimensions. In this work, we measured the nucleation energy landscape of diamond during chemical vapor deposition, using a series of diamondoid molecules as atomically defined protonuclei. We find that 26-carbon atom clusters, which do not contain a single bulk atom, are postcritical nuclei and measure the nucleation barrier to be more than four orders of magnitude smaller than prior bulk estimations. These data support both classical and nonclassical concepts for multistep nucleation and growth during the gas-phase synthesis of diamond and other semiconductors. More broadly, these measurements provide experimental evidence that agrees with recent conceptual proposals of multistep nucleation pathways with metastable molecular precursors in diverse processes, ranging from cloud formation to protein crystallization, and nanoparticle synthesis.
RESUMEN
A novel procedure is developed for chemical modification of H-terminated B-doped diamond surfaces with a donor-π-bridge-acceptor molecule (P1). A cathodic photocurrent near 1 µA cm(-2) flows under 1 Sun (AM 1.5) illumination at the interface between the diamond electrode and aqueous electrolyte solution containing dimethylviologen (electron mediator). The efficiency of this new electrode outperforms that of the non-covalently modified diamond with the same dye. The found external quantum efficiency of the P1-sensitized diamond is not far from that of the flat titania electrode sensitized by a standard organometallic dye used in solar cells. However, the P1 dye, both pure and diamond-anchored, shows significant instability during illumination by solar light. The degradation is a two-stage process in which the initially photo-generated products further decompose in complicated dark reactions. These findings need to be taken into account for optimization of organic chromophores for solar cells in general.
RESUMEN
A novel simple and versatile synthetic strategy is developed for the surface modification of boron-doped diamond. In a two-step procedure, polyethyleneimine is adsorbed on the hydrogenated diamond surface and subsequently modified with a model light-harvesting donor-π-bridge-acceptor molecule (coded P1). The sensitized diamond exhibits stable cathodic photocurrents under visible-light illumination in aqueous electrolyte solution with dimethylviologen serving as an electron mediator. In spite of the simplicity of the surface sensitization protocol, the photoelectrochemical performance is similar to or better than that of other sensitized diamond electrodes which were reported in previous studies (2008-2014).
RESUMEN
A novel approach for preparation of ultra-bright fluorescent nanodiamonds (fNDs) was developed and the thermal and kinetic optimum of NV center formation was identified. Combined with a new oxidation method, this approach enabled preparation of particles that were roughly one order of magnitude brighter than particles prepared with commonly used procedures.
