Plasmon-Assisted Polarity Switching of a Photoelectric Conversion Device by UV and Visible Light Irradiation

The plasmon-induced charge separation between metallic nanoparticles and a semiconductor following an electron transfer process has been extensively studied as one of the mechanisms in plasmonic light energy conversion devices. In this study, we propose that the switching of photocurrent polarity can be realized by changing the rectification properties of plasmonic photoelectric conversion devices and utilizing the difference in carrier mobility between electrons and holes. We fabricated plasmonic photoelectric conversion devices using gold nanoparticles (Au-NPs), nickel oxide (NiO), and mobility-limited TiO₂ (ML-TiO₂) to control the photocurrent polarity according to irradiation wavelengths of visible and UV light. A pulsed laser deposition technique was employed to deposit the ML-TiO₂ and NiO layers. The photoelectric properties were measured, and in situ spectroelectrochemical measurements were performed to investigate the relationship between the rectification properties of the plasmonic photoelectric conversion devices and the change in the Fermi level of the Au-NPs under UV light irradiation condition. Additionally, UV and visible light irradiation selectively induced the current of opposite polarity with the small applied voltage. The electron transfer phenomena from ML-TiO₂ to Au-NPs and from Au-NPs to ML-TiO₂ give us important information to understand plasmon-related charge separation.