Surface State Mediated Electron Transfer Across the N-Type SiC/Electrolyte Interface

Understanding the mechanisms of charge transfer across the semiconductor/electrolyte interface is a basic prerequisite for a variety of practical applications. In particular, electrically active surface states located in the semiconductor band gap are expected to play an important role, but direct experimental evidence of surface states has proven to be challenging, and further experimental studies are required to verify their influence on the exchange of charge carriers between semiconductor and electrolyte. Due to its wide band gap, chemical stability, and controllable surface termination, silicon carbide (SiC) provides an excellent model system for this purpose. In this report, we provide a fundamental electrochemical study of n-type 6H-SiC and 4H-SiC electrodes in aqueous electrolytes containing the ferricyanide/ferrocyanide redox couple. Cyclic voltammetry and impedance spectroscopy measurements are performed over a wide range of potentials to determine the energetic positions of the SiC band edges and to investigate the electron-transfer kinetics between SiC and the ferricyanide molecules. For both polytypes, a broad distribution of surface states with energy levels close to the conduction band is found to mediate electron transfer, resulting in deviations of the observed charge transport characteristics from the predictions of well-established models. Moreover, a detailed evaluation of the impedance data allows for explicit correlation of the charge-transfer resistance associated with the ferricyanide reduction reaction with the potential-dependent distribution of surface states. In addition to the relevance of our studies for advancing the implementation of SiC in biosensing, electrocatalytic, and photocatalytic applications, the presented methodology can also be adopted for fundamental electrochemical investigations of other semiconductor electrodes. (Figure Presented).