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We study emission of photoelectrons from plasmonic nanoparticles intosurrounding matrix. We consider two mechanisms of the photoelectric effect fromnanoparticles - surface and volume ones, and use models of these two effectswhich allow us to obtain analytical results for the photoelectron emissionrates from nanoparticle. Calculations have been done for the step potential atsurface of spherical nanoparticle, and the simple model for the hot electroncooling have been used. We highlight the effect of the discontinuity of thedielectric permittivity at the nanoparticle boundary in the surface mechanism,which leads to substantial (by 5 times) increase of photoelectron emission ratefrom nanoparticle compared to the case when such discontinuity is absent. Forplasmonic nanoparticle, a comparison of two mechanisms of the photoeffect wasdone for the first time and showed that surface photoeffect, at least, does notconcede the volume one, which agrees with results for the flat metal surfacefirst formulated by Tamm and Schubin in their pioneering development ofquantum-mechanical theory of photoeffect in 1931. In accordance with ourcalculations, this predominance of the surface effect is a result of effectivecooling of hot carriers, during their propagation from volume of thenanoparticle to its surface in the scenario of the volume mechanism. Takinginto account both mechanisms is essential in development of devices based onthe photoelectric effect and in usage of hot electrons from plasmonicnanoantenna.

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