Tailoring of Interfacial Band Offsets by an Atomically Thin Polar Insulating Layer To Enhance the Water-Splitting Performance of Oxide Heterojunction Photoanodes

An important factor in the performance of photoelectrochemical water splitting is the band edge alignment of the photoelectrodes for efficient transport and transfer of photogenerated carriers. Many studies for improving charge transfer ability between the electrode and the electrolyte have been reported, while research to improve charge transfer at the interface of the photoactive semiconductor and the conducting substrate is largely lacking. Here, we demonstrate that the water-splitting performance of an oxide heterostructured photoelectrode can be increased 6-fold by inserting an atomically thin polar LaAlO₃ interlayer compared with that of an oxide heterostructure without an insertion to modify interfacial band offsets. The electrically lowered Schottky barrier is driven by the atomically thin layer, and the charge transfer resistance between the oxides is reduced by up to 2 orders of magnitude upon insertion of LaAlO₃, a wide-gap (5.6 eV) insulator. We show that the critical thickness of the polar layer for enhancing the charge transfer is 3 unit cells. The dipole moment from the polar sheets of LaAlO₃ introduces an internal electric field, which modifies the effective band offsets in the device. This work serves as a proof of concept that photoelectrochemical performance can be improved by manipulating the band offsets of the heterostructure interface, suggesting a new design strategy for heterostructured water-splitting photoelectrodes.