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Enhanced water splitting under modal strong coupling conditions


Strong coupling between plasmons and optical modes, such as waveguide or resonator modes, gives rise to a splitting in the plasmon absorption band. As a result, two new hybrid modes are formed that exhibit near-field enhancement effects. These hybrid modes have been exploited to improve light absorption in a number of systems. Here we show that this modal strong coupling between a Fabry–Pérot nanocavity mode and a localized surface plasmon resonance (LSPR) facilitates water splitting reactions. We use a gold nanoparticle (Au-NP)/TiO2/Au-film structure as a photoanode. This structure exhibits modal strong coupling between the Fabry–Pérot nanocavity modes of the TiO2 thin film/Au film and LSPR of the Au NPs. Electronic excitation of the Au NPs is promoted by the optical hybrid modes across a broad range of wavelengths, followed by a hot electron transfer to TiO2. A key feature of our structure is that the Au NPs are partially inlaid in the TiO2 layer, which results in an enhancement of the coupling strength and water-oxidation efficiency. We observe an 11-fold increase in the incident photon-to-current conversion efficiency with respect to a photoanode structure with no Au film. Also, the internal quantum efficiency is enhanced 1.5 times under a strong coupling over that under uncoupled conditions.

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We are grateful to T. W. Ebbesen for fruitful discussions about the strong coupling between the nanocavity and LSPR. We also acknowledge financial support from JSPS KAKENHI (grant no. JP18H05205, JP17H01041, JP17H05245, JP17H05459, JP16H06506 and JP15K04589), the Nanotechnology Platform (Hokkaido University), and the Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials (Five-Star Alliance) of MEXT.

Author information

H.M. supervised the project. X.S. performed all the experiments. X.S. and K.U. wrote the manuscript. T.O. provided technical support. Q.S. performed the TR-PEEM measurement. K.S. participated in discussions to the theoretical understanding of the mechanism of the nanocavity and the strong coupling between the nanocavity and LSPR. All the authors contributed to the scientific discussions and manuscript revisions.

Competing interests

The authors declare no competing interests.

Correspondence to Hiroaki Misawa.

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    Supplementary Figures 1–12 and Supplementary Notes 1–6

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Fig. 1: Au-NP/TiO2/Au-film with an ultrathin TiO2 film.
Fig. 2: Au-NP inlaid depth dependence of the absorption and IPCE action spectra.
Fig. 3: Au-NP/TiO2/Au-film with a thick TiO2 film.
Fig. 4: IQE calculations.
Fig. 5: Water splitting using a two-electrode system.