Proceedings of nanoGe Fall Meeting 2018 (NFM18)
DOI: https://doi.org/10.29363/nanoge.nfm.2018.029
Publication date: 6th July 2018
Understanding water splitting at nanostructured electrodes presents some formidable challenges. Here, regular nanostructured photoelectrodes are considered using hematite nanorod arrays as an example. Since Mott Schottky plots are often reported for nanostructured electrodes, we revisit the effects of the cylindrical nanorod geometry on the capacitance-voltage behaviour. The limiting case of complete depletion is discussed in terms of the residual geometric capacity at the base of the nanorods. Since nanorod arrays generally leave areas of the substrate exposed, it is also necessary to consider the parallel capacitance associated with the fraction of uncovered surface. We then turn to the enhancement of external quantum efficiency (EQE) achieved by nanostructuring, again using hematite nanorod arrays as experimental examples. We show that, although very substantial EQE enhancement should be achieved by simple geometric effects, the performance of nanostructured hematite electrodes in the visible region of the spectrum is considerably lower than predicted if all charge carriers generated in the space charge region (SCR) were collected. Further analysis reveals that the internal quantum efficiency increases with photon energy, suggesting that the probability of generating free, rather than bound, electron-hole pairs in hematite depends on the excess energy hν - Egap.
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