Heterojunction Photoelectrodes: III . Cyclic Voltammetry at Indium Tin Oxide‐Coated Silicon/Aqueous Redox Electrolyte Interfaces

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Abstract
Cyclic voltammetry (CV) is shown to be a useful technique for the evaluation of the performance of heterojunction photoelectrodes in photoelectrochemical systems. The Si/Sn‐doped indium oxide (ITO) heterojunction was used as a model system. Photoelectrochemical interfaces were constructed and analyzed, using this heterojunction in series with an aqueous redox electrolyte, comprising or redox couples. Both p‐type as well as n‐type Si substrates were utilized for this purpose. The photovoltage generated at the Si/ITO heterojunction is shown to be modified by overpotential losses at the ITO/redox electrolyte interface. Such losses are minimal for the redox couple (a fast redox system) and appreciable for the system, which is kinetically sluggish even in the presence of Cl− catalyst. The photoresponses of the Si/ITO/redox electrolyte interfaces were analyzed by CV as a function of three variables; namely, redox concentration, light flux, and applied potential. A simple equivalent‐circuit representation is finally presented for a heterojunction photoelectrode.

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