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
University of Wisconsin Madison
Chalmers, Physics, Chemical Physics
Mario Zapata-Herrera
Spanish National Research Council (CSIC)
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
Basque Foundation for Science (Ikerbasque)
University of the Basque Country (UPV/EHU)
Donostia International Physics Center
Javier Aizpurua
Spanish National Research Council (CSIC)
Donostia International Physics Center
Henrik Grönbeck
Chalmers, Physics, Chemical Physics
Ruben Esteban
Donostia International Physics Center
Spanish National Research Council (CSIC)
Christoph Langhammer
Chalmers, Physics, Chemical Physics
Physical Review Materials
24759953 (eISSN)
Vol. 6 4 045201Areas of Advance
Nanoscience and Nanotechnology
Subject Categories (SSIF 2011)
Ceramics
Materials Chemistry
Condensed Matter Physics
Infrastructure
C3SE (-2020, Chalmers Centre for Computational Science and Engineering)
Chalmers Materials Analysis Laboratory
Myfab (incl. Nanofabrication Laboratory)
DOI
10.1103/PhysRevMaterials.6.045201