Continuous angular control over anisotropic photoemission from isotropic gold nanoshells

A variety of applications rely on the efficient generation of hot carriers within metal nanoparticles and charge transfer to surrounding molecules or materials. The optimization of such processes requires a detailed understanding of excited carrier spatial, temporal, and momentum distributions, which also leads to opportunities for active optical control over hot carrier dynamics on nanometer and femtosecond scales. Such capabilities are emerging in nanoplasmonic systems and typically rely on tuning optical polarization and/or frequency to selectively excite one or more discrete hot spots defined by the particle geometry. Here, we introduce a unique case in which hot electron excitation and emission distributions can instead be continuously controlled via linear laser polarization in the azimuthal plane of a gold nanoshell supported on a substrate. In this configuration, it is the laser field that breaks the azimuthal symmetry of the supported nanoshell and determines the plasmonic field distribution. Using angle-resolved photoelectron velocity map imaging, we find that the hot electrons are predominantly emitted orthogonal to the nanoshell dipolar surface plasmon resonance axis defined by the laser polarization. Furthermore, such anisotropic emission is only observed for nanoshells, while solid gold nanospheres are found to be isotropic emitters. We show that all of these effects are recapitulated via simulation of the plasmonic electric field distributions within the nanoparticle volume and ballistic Monte Carlo modeling of the hot electron dynamics. These results demonstrate a highly predictive level of understanding of the underlying physics and possibilities for ultrafast spatiotemporal control over hot carrier dynamics.