Investigating the Consistency of Models for Water Splitting Systems by Light and Voltage Modulated Techniques.

The optimization of solar energy conversion devices relies on their accurate and nondestructive characterization. The small voltage perturbation techniques of impedance spectroscopy (IS) have proven to be very powerful to identify the main charge storage modes and charge transfer processes that control device operation. Here we establish the general connection between IS and light modulated techniques such as intensity modulated photocurrent (IMPS) and photovoltage spectroscopies (IMVS) for a general system that converts light to energy. We subsequently show how these techniques are related to the steady-state photocurrent and photovoltage and the external quantum efficiency. Finally, we express the IMPS and IMVS transfer functions in terms of the capacitive and resistive features of a general equivalent circuit of IS for the case of a photoanode used for solar fuel production. We critically discuss how much knowledge can be extracted from the combined use of those three techniques.