Engineering plasmonic charge kinetics and broadband photoelectrochemical spectral responses using a multi-resonant Au–TiO2 plasmonic particle grating-based optical resonator†

The plasmonic integrated semiconductor has widened the operational spectral region of semiconductors for light–matter interaction-driven solar energy harvesting applications. However, a specific plasmonic resonance has moderate light absorption and is only active in a specific width of the visible spectrum. We present a tailored plasmonic particle grating-based Au–TiO₂ Schottky photoelectrode-based broadband absorber that operates in the extended spectral region of 400–800 nm due to the synergistic interaction of multi-resonant photonic and plasmonic modes of the plasmonic particle grating structure. In the visible spectrum, the proposed photoelectrode increased the incoming photon to electron conversion efficiency (IPCE%) by seven and five times more than TiO₂ for TM (along the grating vector) and TE (perpendicular to the grating vector) incidence, respectively. The plasmonic response of the gold nanoparticle and the grating-coupled surface plasmon polariton (SPP)–guided mode resonance (GMR) are responsible for such increments. Ultrafast pump–probe spectroscopy verifies that the plasmon–GMR interaction causes extended plasmonic charge generation and lifetime. The kinetics of plasmonic-generated charges in grating-coupled SPP and LSPR was investigated through TM and TE polarized pump and probe excitation. Such findings are consistent with the observed PEC spectral responses under their respective polarization illumination. Therefore, our research provides a simple method for integrating photonic and plasmonic materials for innovative broadband spectrum responses in photovoltaic and energy harvesting applications.