Visualizing hot carrier dynamics by nonlinear optical spectroscopy at the atomic length scale.

Probing and manipulating the spatiotemporal dynamics of hot carriers in nanoscale metals is crucial to a plethora of applications ranging from nonlinear nanophotonics to single-molecule photochemistry. The direct investigation of these highly non-equilibrium carriers requires the experimental capability of high energy-resolution (~ meV) broadband femtosecond spectroscopy. When considering the ultimate limits of atomic-scale structures, this capability has remained out of reach until date. Using a two-color femtosecond pump-probe spectroscopy, we present here the real-time tracking of hot carrier dynamics in a well-defined plasmonic picocavity, formed in the tunnel junction of a scanning tunneling microscope (STM). The excitation of hot carriers in the picocavity enables ultrafast all-optical control over the broadband (~ eV) anti-Stokes electronic resonance Raman scattering (ERRS) and the four-wave mixing (FWM) signals generated at the atomic length scale. By mapping the ERRS and FWM signals from a single graphene nanoribbon (GNR), we demonstrate that both signals are more efficiently generated along the edges of the GNR - a manifestation of atomic-scale nonlinear optical microscopy.