Hot-Carrier Generation in Plasmonic Nanoparticles: The Importance of Atomic Structure

T. P. Rossi, P. Erhart, and M. Kuisma
ACS Nano 14, 9963 (2020)
doi: 10.1021/acsnano.0c03004
zenodo: 3927527 (associated data)
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Metal nanoparticles are attractive for plasmon-enhanced generation of hot carriers, which may be harnessed in photochemical reactions. In this work, we analyze the coherent femtosecond dynamics of photon absorption, plasmon formation, and subsequent hot-carrier generation through plasmon dephasing using first-principles simulations. We predict the energetic and spatial hot-carrier distributions in small metal nanoparticles and show that the distribution of hot electrons is very sensitive to the local structure. Our results show that surface sites exhibit enhanced hot-electron generation in comparison to the bulk of the nanoparticle. While the details of the distribution depend on particle size and shape, as a general trend lower-coordinated surface sites such as corners, edges, and {100} facets exhibit a higher proportion of hot electrons than higher-coordinated surface sites such as {111} facets or the core sites. The present results thereby demonstrate how hot carriers could be tailored by careful design of atomic-scale structures in nanoscale systems.

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