Progress in the development of plasmon-enabled light-harvesting technologies requires a better understanding of their fundamental operating principles and current limitations. Here, we employ picosecond time-resolved X-ray photoemission spectroscopy to investigate photoinduced electron transfer in a plasmonic model system composed of 20 nm sized gold nanoparticles (NPs) attached to a nanoporous film of TiO₂. The measurement provides direct, quantitative access to transient local charge distributions from the perspectives of the electron donor (AuNP) and the electron acceptor (TiO₂). On average, approximately two electrons are injected per NP, corresponding to an electron injection yield per absorbed photon of 0.1%. Back electron transfer from the perspective of the electron donor is dominated by a fast recombination channel proceeding on a time scale of 60 ± 10 ps and a minor contribution that is completed after ∼1 ns. The findings provide a detailed picture of photoinduced charge carrier generation in this NP-semiconductor junction, with important implications for understanding achievable overall photon-to-charge conversion efficiencies.

Cuprous oxide (Cu₂O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu₂O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu₂O surface as well as the interface between Cu₂O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu₂O and provide guidance for future material development.