Abstract
The photoelectrochemical stability and surface-alteration characteristics of both doped and undoped n-type ZnO single-crystal photoanode electrodes have been investigated. The single-crystal ZnO photoanode properties were analyzed using current-voltage measurements plus spectral and time-dependent quantum-yield methods. These measurements revealed the presence of a distinct anodic peak and an accompanying cathodic surface degradation process at negative potentials. The features of this peak were found to depend on time as well as the NaOH concentration in the electrolyte, but they were independent of the presence of electrode illumination. Current measurements performed at the peak indicate that charging and discharging effects are apparently taking place at the semiconductor/electrolyte interface. This result is consistent with the significant reactive degradation that takes place on the ZnO single crystal photoanode surface and that ultimately leads to the reduction of the ZnO surface to Zn metal. The resulting Zn-metal reaction products create unusual, dendrite-like, surface alteration structural features that were analyzed using x-ray diffraction, energy-dispersive analysis, and scanning electron microscopy. The ZnO doping methods employed here are also shown to be an effective way of increasing the n-type character of the crystals. Higher doping levels result in smaller depletion widths and lower quantum yields, since the minority carrier diffusion lengths are very short in these materials.
