Confined Hot Electron Relaxation at the Molecular Heterointerface of the Size-Selected Plasmonic Noble Metal Nanocluster and Layered C₆₀

The plasmonic response of metallic nanostructures plays a key role in amplifying photocatalytic and photoelectric conversion. Since the plasmonic behavior of noble metal nanoparticles is known to generate energetic charge carriers such as hot electrons, it is expected that the hot electrons can enhance conversion efficiency if they are transferred into a neighboring molecule or semiconductor. However, the method of transferring the energized charge carriers from the plasmonically generated hot electrons to the neighboring species remains controversial. Herein, we fabricated a molecularly well-defined heterointerface between the size-selected plasmonic noble-metal nanoclusters (NCs) of Ag_n (n = 3-55)/Au_n (n = 21) and the organic C₆₀ film to investigate hot electron generation and relaxation dynamics using time-resolved two-photon photoemission (2PPE) spectroscopy. By tuning the NC size and the polarization of the femtosecond excitation photons, the plasmonic behavior is characterized by 2PPE intensity enhancement by 10-100 times magnitude, which emerge at n ≥ 9 for Ag_n NCs. The 2PPE spectra exhibit contributions from low-energy electrons forming coherent plasmonic currents and hot electrons with an excitation energy up to photon energy owing to two-photon excitation of an occupied state of the Ag_n NC below the Fermi level. The time-resolved pump-probe measurements demonstrate that plasmon dephasing generates hot electrons which undergo electron-electron scattering. However, no photoemission occurs via the charge transfer state forming Ag_n⁺C₆₀^- located in the vicinity of the Fermi level. Thus, this study reveals the mechanism of ultrafast confined hot electron relaxation within plasmonic Ag_n NCs at the molecular heterointerface.