Long-lived modulation of plasmonic absorption by ballistic thermal injection

Light–matter interactions that induce charge and energy transfer across interfaces form the foundation for photocatalysis^1,2, energy harvesting³ and photodetection⁴, among other technologies. One of the most common mechanisms associated with these processes relies on carrier injection. However, the exact role of the energy transport associated with this hot-electron injection remains unclear. Plasmon-assisted photocatalytic efficiencies can improve when intermediate insulation layers are used to inhibit the charge transfer^5,6 or when off-resonance excitations are employed⁷, which suggests that additional energy transport and thermal effects could play an explicit role even if the charge transfer is inhibited⁸. This provides an additional interfacial mechanism for the catalytic and plasmonic enhancement at interfaces that moves beyond the traditionally assumed physical charge injection^9–12. In this work, we report on a series of ultrafast plasmonic measurements that provide a direct measure of electronic distributions, both spatially and temporally, after the optical excitation of a metal/semiconductor heterostructure. We explicitly demonstrate that in cases of strong non-equilibrium, a novel energy transduction mechanism arises at the metal/semiconductor interface. We find that hot electrons in the metal contact transfer their energy to pre-existing free electrons in the semiconductor, without an equivalent spatiotemporal transfer of charge. Further, we demonstrate that this ballistic thermal injection mechanism can be utilized as a unique means to modulate plasmonic interactions. These experimental results are well-supported by both rigorous multilayer optical modelling and first-principle ab initio calculations.