Probing the role of grain boundaries in single Cu nanoparticle oxidation by in situ plasmonic scattering
Journal article, 2022

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.

Author

Sara Nilsson

Chalmers, Physics, Chemical Physics

Alvaro Posada Borbon

Chalmers, Physics, Chemical Physics

University of Wisconsin Madison

Mario Zapata-Herrera

Centro de Física de Materiales (CSIC-UPV/EHU)

Alice Bastos da Silva Fanta

Technical University of Denmark (DTU)

David Albinsson

Chalmers, Physics, Chemical Physics

Joachim Fritzsche

Chalmers, Physics, Chemical Physics

Vyacheslav M. Silkin

Donostia International Physics Center

Basque Foundation for Science (Ikerbasque)

University of the Basque Country (UPV/EHU)

Javier Aizpurua

Centro de Física de Materiales (CSIC-UPV/EHU)

Donostia International Physics Center

Henrik Grönbeck

Chalmers, Physics, Chemical Physics

Ruben Esteban

Centro de Física de Materiales (CSIC-UPV/EHU)

Donostia International Physics Center

Christoph Langhammer

Chalmers, Physics, Chemical Physics

Physical Review Materials

24759953 (eISSN)

Vol. 6 4 045201

Areas of Advance

Nanoscience and Nanotechnology

Subject Categories

Ceramics

Materials Chemistry

Condensed Matter Physics

Infrastructure

C3SE (Chalmers Centre for Computational Science and Engineering)

Chalmers Materials Analysis Laboratory

Nanofabrication Laboratory

DOI

10.1103/PhysRevMaterials.6.045201

More information

Latest update

4/12/2023