Preparation of etched tantalum semimicro capacitor stimulation electrodes

The ideal electrode for stimulation of the nervous system is one that will inject charge by purely capacitive processes. One approach is to exploit the type of metal-oxide combination used in electrolytic capacitors, e.g., Ta/Ta2O5. For this purpose, fine tantalum wire (0.25 mm diam) was etched electrolytically at constant current in a methanol solution of NH4Br containing 1.5 wt % H2O. Electrolytic etching produced a conical tip with a length of ca. 0.5 mm and shaft diameters ranging from 0.10 to 0.16 mm. The etched electrodes were anodized to 10 V (vs. SCE) in 0.1 vol % H3PO4. The capacitance values normalized to geometric area of etched electrodes ranged from 0.13 to 0.33 micro F mm-2. Comparison of these values to the capacitance of "smooth" tantalum anodized to 10 V (0.011 micro F mm-2) indicated that the degree of surface enhancement, or etch ratio, was 12-30. The surface roughness was confirmed by scanning electron microscopy studies which revealed an intricate array of irregularly shaped surface projections about 1-2 micrometers wide. The etched electrodes were capable of delivering 0.06-0.1 micro C of charge with 0.1 ms pulses at a pulse repetition rate of 400 Hz when operated at 50% of the anodization voltage. This quantity of charge corresponded to volumetric charge densities of 20-30 micro C mm-3 and area charge densities of 0.55-0.88 micro C mm-2. Charge storage was proportionately higher at higher fractional values of the formation voltage. Leakage currents at 5 V were ca. 2 nA. Neither long-term passive storage (1500 h) nor extended pulsing time (18 h) had a deleterious effect on electrode performance. The trend in electrical stimulation work is toward smaller electrodes. The procedures developed in this study should be particularly well-suited to the fabrication of even smaller electrodes because of the favorable electrical and geometric characteristics of the etched surface.