Abstract

The operation of lightly doped Si microwire arrays under high-level injection conditions was investigated by measurement of the current-potential behavior and carrier-collection efficiency of the wires in contact with non-aqueous electrolytes, and through complementary device physics simulations. The current-potential behavior of the lightly doped Si wire array photoelectrodes was dictated by both the radial contact and the carrier-selective back contact. For example, the Si microwire arrays exhibited n-type behavior when grown on a n+-doped substrate and placed in contact with the 1,1′-dimethylferrocene+/0–CH3OH redox system. The microwire arrays exhibited p-type behavior when grown on a p+-doped substrate and measured in contact with a redox system with a sufficiently negative Nernstian potential. The wire array photoelectrodes exhibited internal quantum yields of ∼0.8, deviating from unity for these radial devices. Device physics simulations of lightly doped n-Si wires in radial contact with the 1,1′-dimethylferrocene+/0–CH3OH redox system showed that the carrier-collection efficiency should be a strong function of the wire diameter and the carrier lifetime within the wire. Small diameter (d 400 nm) exhibited higher carrier collection efficiencies that were strongly dependent on the carrier lifetime in the wire, and wires with carrier lifetimes exceeding 5 μs were predicted to have near-unity quantum yields. The simulations and experimental measurements collectively indicated that the Si microwires possessed carrier lifetimes greater than 1 μs, and showed that radial structures with micron dimensions and high material quality can result in excellent device performance with lightly doped, structured semiconductors.

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