Probing nanoscale spatial distribution of plasmonically excited hot carriers

Surface plasmons (SPs) of metals enable the tight focusing and strong absorption of light to realize an efficient utilization of photons at nanoscale. In particular, the SP-generated hot carriers have emerged as a promising way to efficiently drive photochemical and photoelectric processes under moderate conditions. In situ measuring of the transport process and spatial distribution of hot carriers in real space is crucial to efficiently capture the hot carriers. Here, we use electrochemical tip-enhanced Raman spectroscopy (EC-TERS) to in situ monitor an SP-driven decarboxylation and resolve the spatial distribution of hot carriers with a nanometer spatial resolution. The transport distance of about 20 nm for the reactive hot carriers is obtained from the TERS imaging result. The hot carriers with a higher energy have a shorter transport distance. These conclusions can be guides for the design and arrangement of reactants and devices to efficiently make use of plasmonic hot carriers. Revealing the spatial distribution of hot carriers in real space is crucial to their efficient utilization. Here, the authors show that in-situ electrochemical tip-enhanced Raman spectroscopy is able to resolve the spatial distribution of reactive hot carriers with a nanometer spatial resolution.