Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy.

We present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO, TiO, and AlO) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiO- and AlO-coated Si electrodes are negative relative to samples with native SiO, indicating that SiO is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO or AlO. Adding a Pt catalyst to SiO/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO/Si.