Plasmon-induced electron injection into the large negative potential conduction band of Ga2O3 for coupling with water oxidation†
In this study, an interfacial modification layer was applied to improve the plasmon-induced light energy conversion of a gallium(III) oxide (Ga2O3) photoelectrode, which possesses a much more negative conduction band potential compared with the reduction potential of photons to hydrogen. The plasmon-induced photocurrent generation under visible light irradiation was observed with Au nanoparticle-loaded Ga2O3 (Au-NPs/Ga2O3). An interfacial modification was carried out by depositing a titanium dioxide (TiO2) thin-film layer on Au-NPs/Ga2O3via atomic layer deposition. Since the surface states of TiO2 possess excellent hole-trapping ability, this interfacial modification remarkably improved the generation of plasmon-induced photocurrent in the visible region. The photoelectric conversion efficiency of interfacially modified Au-NPs/Ga2O3 showed a TiO2 thin-film thickness dependence because the migration of hot carriers was suppressed with increasing TiO2 thickness. The Au-NPs/Ga2O3 photoelectrode modified with 2 nm-thick TiO2 showed the best photoelectric conversion performance, and the thermodynamic energy conversion efficiency under irradiation with 600 nm light was approximately two times larger than that of the Au-NPs/TiO2-thin film due to the extremely negative onset potential of Au-NPs/Ga2O3 with TiO2. Therefore, the plasmonic Ga2O3 photoanode with the interfacial TiO2 modification could provide both a high reduction ability for H2 evolution and an oxidation ability for water oxidation, because of the negative conduction band of Ga2O3 and the hole-trapping property from TiO2, respectively.