Despite more than a decade of intensive scientific exploration, new plasmonic phenomena continue to be discovered, including quantum interference of plasmons, observation of quantum coupling of plasmons to single particle excitations, and quantum confinement of plasmons in single-nm scale plasmonic particles. Simultaneously, plasmonic structures find widening applications in integrated nanophotonics, biosensing, photovoltaic devices, single photon transistors and single molecule spectroscopy. Decay of surface plasmons to hot carriers is a new direction that has attracted considerable fundamental and application interest, yet a theoretical understanding of ultrafast plasmon decay processes and the underlying microscopic mechanisms remain incomplete.

Recently we analyzed the quantum decay of surface plasmon polaritons and found that the prompt distribution of generated carriers is extremely sensitive to the energy band structure of the plasmonic material. A theoretical understanding of plasmon-driven hot carrier generation and relaxation dynamics at femtosecond timescales is presented here. We report the first ab initio calculations of phonon-assisted optical excitations in metals, which are critical to bridging the frequency range between resistive losses at low frequencies and direct interband transitions at high frequencies. We also present calculations of energy-dependent lifetimes and mean free paths of hot carriers, accounting for electron-electron and electron-phonon scattering, lending insight towards transport of plasmonically-generated carriers at the nanoscale. We will discuss calculations for multiplasmon and nonlinear processes in the ultrafast regime from the mid-IR to visible and in different geometries. Employing a Feynman diagram approach here has been critical to determine the relevant processes.

Based on these theoretical predictions, we designed a solid-state system with wide-bandgap semiconductors and studied the photocurrent generated upon plasmon decay across the extended UV and visible regime for different metals and plasmonic structures. Direct comparison with ab-initio calculations allow us to assess the contribution of direct and indirect transitions and identify guidelines for engineering the generation of plasmonic hot-carriers in the UV-VIS regime.