Determination of Electron Extraction in Semiconductor Photoanodes: Steady‐State and Small‐Perturbation Response

This work develops an analytical model to consistently interpret the steady‐state and small‐perturbation response (both in the time and frequency domain) of photoanodes for solar water‐splitting. In addition to accounting for the fundamental mechanisms of charge‐carrier generation, recombination, and slow hole transfer at the photoanode/electrolyte interface, the model overcomes the key shortcomings of existing models in the literature. These include consistency across measurement/bias conditions and the non‐consideration of imperfect electron extraction at the collecting contact and its corresponding effect on the recombination rate in the bulk. The model is applied to analyze the time constants obtained from intensity‐modulated photocurrent spectroscopy (IMPS) and intensity‐modulated photovoltage spectroscopy (IMVS) measurements of a hematite photoanode, obtaining an electron extraction velocity of 100 cm s −1 close to the 1 sun open‐circuit potential, that corresponds to an electron mobility of 0.022 cm 2 V −1 s −1 . The model further predicts a linear dependence of the photocurrent versus anodic voltage, an observation whose origin is strongly debated in the literature in the case of hematite photoanodes. The generality of the model allows its extension to other photoanodes and photovoltaic systems, by the addition or removal of specific physical mechanisms.