Field‐effect modulated water‐splitting by photoinduced charge carriers on BiFeO3 film

Abstract In this study, the field‐effect generated by illuminated p‐type ferroelectric bismuth ferrite (BiFeO 3 or BFO) semiconductor film is utilized to modulate the water‐splitting performance of a system with a macroscopic spatial separation between the anode and cathode. When the BFO film in contact with an electrolyte is illuminated with a light of sufficiently high frequency, an electrolytic conducting channel is formed due to the field effect induced by photoexcited charge carriers in the BFO film, which in turn alters the water‐splitting pathway and the reaction mechanism. The field effect can be modulated by changing the orientation of the ferroelectric polarization in the BFO film. With a BFO film of 4.5 mm channel length and an overall upward ferroelectric polarization direction, a ∼30% increase in water‐splitting performance in a neutral‐pH electrolyte is achieved in the presence of field‐effect induced by a 20 mW 405 nm light source. The mechanism behind the field‐effect modulation is also further verified by monitoring the pH of the electrolyte during the water‐splitting process and conducting thresholding analysis on the recorded data. The field‐effect modulation described in this study can potentially be used to enhance the performance of a photoelectrochemical water‐splitting system by taking advantage of the presence of light illumination in the system or be utilized in electrochemical sensing applications.