De-Pinning Fermi Level and Accelerating Surface Kinetics with an ALD Finish Boost the Fill Factor of BiVO₄ Photoanodes to 44

With the rapid development of performance and long-term stability, bismuth vanadate (BiVO₄ ) has emerged as the preferred photoanode in photoelectrochemical tandem devices. Although state-of-the-art BiVO₄ photoanodes realize a saturated photocurrent density approaching the theoretical maximum, the fill factor (FF) is still inferior, pulling down the half-cell applied bias photon-to-current efficiency (HC-ABPE). Among the major fundamental limitations are the Fermi level pinning and sluggish surface kinetics at the low applied potentials. This work demonstrates that the plasma-assisted atomic layer deposition technique is capable of addressing these issues by seamlessly installing an angstrom-scale FeNi-layer between BiVO₄ and electrolyte. Not only this ultrathin FeNi layer serves as an efficient OER cocatalyst, more importantly, it also effectively passivates the surface states of BiVO₄ , de-pins the surface Fermi level, and enlarges the built-in voltage, allowing the photoanode to make optimal use of the photogenerated holes for achieving high FF up to 44% and HC-ABPE to 2.2%. This study offers a new approach for enhancing the FF of photoanodes and provides guidelines for designing efficient unassisted solar fuel devices.