Elucidating the sole contribution from electromagnetic near-fields in plasmon-enhanced Cu 2 O photocathodes
Despite many promising reports of plasmon-enhanced photocatalysis, the inability to identify the individual contributions from multiple enhancement mechanisms has delayed the development of general design rules for engineering efficient plasmonic photocatalysts. Herein, we construct a plasmonic photocathode comprised of Au@SiO 2 (core@shell) nanoparticles embedded within a Cu 2 O nanowire network to exclusively examine the contribution from one such mechanism: electromagnetic near-field enhancement. The influence of the local electromagnetic field intensity is correlated with the overall light-harvesting efficiency of the device through variation of the SiO 2 shell thickness (5—22 nm) to systematically tailor the distance between the plasmonic Au nanoparticles and the Cu 2 O nanowires. A three-fold increase in device photocurrent is achieved upon integrating the Au@SiO 2 nanoparticles into the Cu 2 O nanowire network, further enabling a ~40% reduction in semiconductor film thickness while maintaining photocathode performance. Photoelectrochemical results are further correlated with photoluminescence studies and optical simulations to confirm that the near-field enhancement is the sole mechanism responsible for increased light absorption in the plasmonic photocathode.