Photoelectron emission from plasmonic nanoparticles: Comparison between surface and volume photoelectric effects

Abstract: We study emission of photoelectrons from plasmonic nanoparticles into surrounding matrix. We consider two mechanisms of the photoelectric effect from nanoparticles - surface and volume ones, and use models of these two effects which allow us to obtain analytical results for the photoelectron emission rates from nanoparticle. Calculations have been done for the step potential at surface of spherical nanoparticle, and the simple model for the hot electron cooling have been used. We highlight the effect of the discontinuity of the dielectric permittivity at the nanoparticle boundary in the surface mechanism, which leads to substantial (by 5 times) increase of photoelectron emission rate from nanoparticle compared to the case when such discontinuity is absent. For plasmonic nanoparticle, a comparison of two mechanisms of the photoeffect was done for the first time and showed that surface photoeffect, at least, does not concede the volume one, which agrees with results for the flat metal surface first formulated by Tamm and Schubin in their pioneering development of quantum-mechanical theory of photoeffect in 1931. In accordance with our calculations, this predominance of the surface effect is a result of effective cooling of hot carriers, during their propagation from volume of the nanoparticle to its surface in the scenario of the volume mechanism. Taking into account both mechanisms is essential in development of devices based on the photoelectric effect and in usage of hot electrons from plasmonic nanoantenna.