The photoelectrical properties and stability of individual p-silicon (Si) microwire/polyethylenedioxythiophene/polystyrene sulfonate:Nafion/n-Si microwire structures, designed for use as arrays for solar fuel production, were investigated for both H-terminated and CH3-terminated Si microwires. Using a tungsten probe method, the resistances of individual wires, as well as between individual wires and the conducting polymer, were measured vs. time. For the H-terminated samples, the n-Si/polymer contacts were initially rectifying, whereas p-Si microwire/polymer contacts were initially ohmic, but the resistance of both the n-Si and p-Si microwire/polymer contacts increased over time. In contrast, relatively stable, ohmic behavior was observed at the junctions between CH3-terminated p-Si microwires and conducting polymers. CH3-terminated n-Si microwire/polymer junctions demonstrated strongly rectifying behavior, attributable to the work function mismatch between the Si and polymer. Hence, a balance must be found between the improved stability of the junction electrical properties achieved by passivation, and the detrimental impact on the effective resistance associated with the additional rectification at CH3-terminated n-Si microwire/polymer junctions. Nevertheless, the current system under study would produce a resistance drop of ∼20 mV during operation under 100 mW cm−2 of Air Mass 1.5 illumination with high quantum yields for photocurrent production in a water-splitting device.
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