“Hot” electrons in metallic nanostructures—non-thermal carriers or heating?

Abstract

Understanding the interplay between illumination and the electron distribution in metallic nanostructures is a crucial step towards developing applications such as plasmonic photocatalysis for green fuels, nanoscale photodetection and more. Elucidating this interplay is challenging, as it requires taking into account all channels of energy flow in the electronic system. Here, we develop such a theory, which is based on a coupled Boltzmann-heat equations and requires only energy conservation and basic thermodynamics, where the electron distribution, and the electron and phonon (lattice) temperatures are determined uniquely. Applying this theory to realistic illuminated nanoparticle systems, we find that the electron and phonon temperatures are similar, thus justifying the (classical) single-temperature models. We show that while the fraction of high-energy “hot” carriers compared to thermalized carriers grows substantially with illumination intensity, it remains extremely small (on the order of 10−8). Importantly, most of the absorbed illumination power goes into heating rather than generating hot carriers, thus rendering plasmonic hot carrier generation extremely inefficient. Our formulation allows for the first time a unique quantitative comparison of theory and measurements of steady-state electron distributions in metallic nanostructures.