Retarded Charge-Carrier Recombination in Photoelectrochemical Cells from Plasmon-Induced Resonance Energy Transfer

Abstract

N-type metal oxides such as hematite (alpha-Fe2O3) and bismuth vanadate (BiVO4) are promising candidate materials for efficient photoelectrochemical water splitting; however, their short minority carrier diffusion length and restricted carrier lifetime result in undesired rapid charge recombination. Herein, a 2D arranged globular Au nanosphere (NS) monolayer array with a highly ordered hexagonal hole pattern (hereafter, Au array) is introduced onto the surface of photoanodes comprised of metal oxide films via a facile drying and transfer-printing process. Through plasmon-induced resonance energy transfer, the Au array provides a strong electromagnetic field in the near-surface area of the metal oxide film. The near-field coupling interaction and amplification of the electromagnetic field suppress the charge recombination with long-lived photogenerated holes and simultaneously enhance the light harvesting and charge transfer efficiencies. Consequently, an over 3.3-fold higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) is achieved for the Au array/alpha-Fe2O3. Furthermore, the high versatility of this transfer printing of Au arrays is demonstrated by introducing it on the molybdenum-doped BiVO4 film, resulting in 1.5-fold higher photocurrent density at 1.23 V versus RHE. The tailored metal film design can provide a potential strategy for the versatile application in various light-mediated energy conversion and optoelectronic devices.