Probing the role of grain boundaries in single Cu nanoparticle oxidation by in situ plasmonic scattering

Sara Nilsson, Alvaro Posada-Borbón, Mario Zapata-Herrera, Alice Bastos Da Silva Fanta, David Albinsson, Joachim Fritzsche, Vyacheslav M. Silkin, Javier Aizpurua, Henrik Grönbeck, Ruben Esteban*, Christoph Langhammer*

*Corresponding author for this work

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Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and postmortem transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick Cu2O shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the Cu2O shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.

Original languageEnglish
Article number045201
JournalPhysical Review Materials
Issue number4
Number of pages15
Publication statusPublished - 2022


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