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.