Hydrogen Evolution Efficiency at Illuminated Silicon

The change of kinetic characteristics of photoelectrochemical hydrogen evolution at p-type silicon in acid aqueous electrolyte solutions under prolonged continuous illumination is studied. It is shown that, during the transfer of full charge Q _t < 150 C/cm² through the silicon/electrolyte interface, the interrelation between the reciprocal time of the charge transfer into electrolyte and the steady-state current remains linear. In this case, a Tafel-like relation links the interfacial charge to the steady-state electrode current. Passing current through the electrode even further results, at Q _t > 350 C/cm², in breaking-down the direct relation between the current and the charge transfer time, despite the electrode's retaining high photosensitivity. The effect is probably caused by significant energy and structure distortions in the surface layer of silicon.