Electron dynamics in supported metal nanoparticles: relaxation and charge transfer studied by time-resolved photoemission

Resonant excitation of the plasmon polariton in supported nanoparticles leads to a strong enhancement of the multiphoton photoemission yield and consequently, the total yield is dominated by the emission from the nanoparticles although they cover only a minor fraction of the surface. This allows investigation of the electron dynamics in supported nanoparticles, directly in the time domain. Here, Ag nanoparticles grown on graphite are used to demonstrate that the transient shape of the photoemission spectrum in time-resolved two-color multiphoton photoemission spectroscopy, reveals the electron relaxation within the nanoparticle, and the dynamic charge transfer between substrate and nanoparticle. The photoemission spectra map the transient electron energy distribution and exhibit a transient shift that is attributed to a dynamic charging of the nanoparticle. The comparison with model calculations comprising the full relaxation cascade in the nanoparticle and substrate, shows that the dynamic charge transfer accounts for almost half of the total deposited energy in the nanoparticle.