Epitaxial Bi2FeCrO6 Multiferroic Thin Film as a New Visible Light Absorbing Photocathode Material

Ferroelectric materials have been studied increasingly for solar energy conversion technologies due to the efficient charge separation driven by the polarization induced internal electric field. However, their insufficient conversion efficiency is still a major challenge. Here, a photocathode material of epitaxial double perovskite Bi2FeCrO6 multiferroic thin film is reported with a suitable conduction band position and small bandgap (1.9-2.1 eV), for visible-light-driven reduction of water to hydrogen. Photoelectrochemical measurements show that the highest photocurrent density up to -1.02 mA cm-2 at a potential of -0.97V versus reversible hydrogen electrode is obtained in p-type Bi2FeCrO6 thin film photocathode grown on SrTiO3 substrate under AM 1.5G simulated sunlight. In addition, a twofold enhancement of photocurrent density is obtained after negatively poling the Bi2FeCrO6 thin film, as a result of modulation of the band structure by suitable control of the internal electric field gradient originating from the ferroelectric polarization in the Bi2FeCrO6 films. The findings validate the use of multiferroic Bi2FeCrO6 thin films as photocathode materials, and also prove that the manipulation of internal fields through polarization in ferroelectric materials is a promising strategy for the design of improved photoelectrodes and smart devices for solar energy conversion. A new photocathode material Bi2FeCrO6 with a small bandgap (1.9-2.1 eV) and a suitable conduction band position to photoreduce water to H2 is reported. The highest photocurrent density (ca. -1.0 mA cm-2) is obtained at ca. -1.0 V versus a reversible hydrogen electrode. The photocurrent could be further tuned through modulating the ferroelectric polarization.