Ultrafast hot-carrier dynamics in ultrathin monocrystalline gold

Applications in photodetection, photochemistry, and active metamaterials and metasurfaces require fundamental understanding of ultrafast nonthermal and thermal electron processes in metallic nanosystems. Significant progress has been recently achieved in synthesis and investigation of low-loss monocrystalline gold, opening up opportunities for its use in ultrathin nanophotonic architectures. Here, we reveal fundamental differences in hot-electron thermalisation dynamics between monocrystalline and polycrystalline ultrathin (down to 10 nm thickness) gold films. Comparison of weak and strong excitation regimes showcases a counterintuitive unique interplay between thermalised and non-thermalised electron dynamics in mesoscopic gold with the important influence of the X-point interband transitions on the intraband electron relaxation. We also experimentally demonstrate the effect of hot-electron transfer into a substrate and the substrate thermal properties on electron-electron and electron-phonon scattering in ultrathin films. The hot-electron injection efficiency from monocrystalline gold into TiO₂, approaching 9% is measured, close to the theoretical limit. These experimental and modelling results reveal the important role of crystallinity and interfaces on the microscopic electronic processes important in numerous applications.