Exploring the Near-Field of Strongly Coupled Waveguide-Plasmon Modes by Plasmon-Induced Photocurrent Generation Using a Gold Nanograting-Loaded Titanium Dioxide Photoelectrode

Near-field spectrum measurement techniques, including near-field scanning optical microscopy, electron energy loss spectroscopy, and multiphoton photoemission electron microscopy, are powerful means to investigate near-field interactions directly on closely spaced metallic nanoparticles or a metallic nanostructure coupled with optical modes, such as whispering gallery mode and waveguide mode, which are called coupled plasmonic systems. In the present study, we have successfully measured the near-field spectra of coupled plasmonic systems using a simple photoelectrochemical measurement based on plasmon-induced water oxidation. Coupling was explored between the localized surface plasmon resonance (LSPR.) mode and waveguide mode of periodic gold nanogratings patterned on a thin titanium dioxide waveguide film. It is known that the far-field reflection spectrum of this waveguide-LSPR coupling system shows a complicated shape with multiple peaks, and the coupling has been explored by numerical electromagnetic simulations so far. However, in this study, it was clearly elucidated that an internal quantum efficiency (IQE) spectrum observed in the plasmon-induced photocurrent generation has successfully reproduced the near-field spectrum predicted by electromagnetic simulations under the coupling conditions. The photocurrent generation based on the plasmon-induced charge separation is due to the near-field effect, and it can be considered that the IQE spectrum corresponds to the near-field spectrum. This study paves a new way to indirectly measure the near-field spectrum of plasmonic systems.JSPS KAKENHI [JP17H01041, JP17H05245, JP17H05459, JP15K04589]; Nanotechnology Platform (Hokkaido University); Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials (Five Star Alliance) of MEXTSCI(E)ARTICLE3921627-2163312