Unified theory of plasmon-induced resonance energy transfer and hot electron injection processes for enhanced photocurrent efficiency.

Plasmons in metal nanoparticles (MNPs) promise to enhance solar energy conversion in semiconductors. Two essential mechanisms of enhancement in the near-field regime are hot electron injection (HEI) and plasmon-induced resonance energy transfer (PIRET). Individual studies of both mechanisms indicate that the PIRET efficiency is limited by the short lifetime of the plasmon, whereas the hot electrons result from the plasmon decay. The development of a unified theory of the coupled HEI and PIRET processes is fundamentally interesting and necessary for making reliable predictions but is complicated by the multiple interactions between various components that participate in the enhancement process. In this paper, we use the model-Hamiltonian approach to develop a combined theoretical framework including both PIRET and HEI. The coupled dynamics as well as the time evolution of hot electron energy distribution are studied. The theory further predicts an interference-induced asymmetry in the spectral dependence of PIRET, which can be used to distinguish it from HEI. As the relative contributions of PIRET and HEI strongly depend on the size of the MNPs, this presents itself as a simple route to control the strength of their contributions. The results presented here can further guide future applications of plasmonic solar energy harvesting.