Chemical Interface Damping Depends on Electrons Reaching the Surface

Metallic nanoparticles show extraordinary strong light absorption near their plasmon resonance, orders of magnitude larger compared to nonmetallic nanoparticles. This “antenna” effect has recently been exploited to transfer electrons into empty states of an attached material, for example to create electric currents in photovoltaic devices or to induce chemical reactions. It is generally assumed that plasmons decay into hot electrons, which then transfer to the attached material. Ultrafast electron–electron scattering reduces the lifetime of hot electrons drastically in metals and therefore strongly limits the efficiency of plasmon induced hot electron transfer. However, recent work has revived the concept of plasmons decaying directly into an interfacial charge transfer state, thus avoiding the intermediate creation of hot electrons. This direct decay mechanism has mostly been neglected, and has been termed chemical interface damping (CID). CID manifests itself as an additional damping contribution to the homogeneous plasmon line width. In this study, we investigate the size dependence of CID by following the plasmon line width of gold nanorods during the adsorption process of thiols on the gold surface with single particle spectroscopy. We show that CID scales inversely with the effective path length of electrons, i.e., the average distance of electrons to the surface. Moreover, we compare the contribution of CID to other competing plasmon decay channels and predict that CID becomes the dominating plasmon energy decay mechanism for very small gold nanorods

Momentum Distribution of Electrons Emitted from Resonantly Excited Individual Gold Nanorods

Electron emission by femtosecond laser pulses from individual Au nanorods is studied with a time-of-flight momentum resolving photoemission electron microscope (ToF k-PEEM). The Au nanorods adhere to a transparent indium–tin oxide substrate, allowing for illumination from the rear side at normal incidence. Localized plasmon polaritons are resonantly excited at 800 nm with 100 fs long pulses. The momentum distribution of emitted electrons reveals two distinct emission mechanisms: a coherent multiphoton photoemission process from the optically heated electron gas leads to an isotropic emission distribution. In contrast, an additional emission process resulting from the optical field enhancement at both ends of the nanorod leads to a strongly directional emission parallel to the nanorod’s long axis. The relative intensity of both contributions can be controlled by the peak intensity of the incident light