Resolving single Cu nanoparticle oxidation and Kirkendall void formation with: In situ plasmonic nanospectroscopy and electrodynamic simulations
Journal article, 2019

Copper nanostructures are ubiquitous in microelectronics and heterogeneous catalysis and their oxidation is a topic of high current interest and broad relevance. It relates to important questions, such as catalyst active phase, activity and selectivity, as well as fatal failure of microelectronic devices. Despite the obvious importance of understanding the mechanism of Cu nanostructure oxidation, numerous open questions remain, including under what conditions homogeneous oxide layer growth occurs and when the nanoscale Kirkendall void forms. Experimentally, this is not trivial to investigate because when a large number of nanoparticles are simultaneously probed, ensemble averaging makes rigorous conclusions difficult. On the other hand, when (in situ) electron-microscopy approaches with single nanoparticle resolution are applied, concerns about beam effects that may both reduce the oxide or prevent oxidation via the deposition and cross-linking of carbonaceous species cannot be neglected. In response we present how single particle plasmonic nanospectroscopy can be used for the in situ real time characterization of multiple individual Cu nanoparticles during oxidation. Our analysis of their optical response combined with post mortem electron microscopy imaging and detailed Finite-Difference Time-Domain electrodynamics simulations enables in situ identification of the oxidation mechanism both in the initial oxide shell growth phase and during Kirkendall void formation, as well as the transition between them. In a wider perspective, this work presents the foundation for the application of single particle plasmonic nanospectroscopy in investigations of the impact of parameters like particle size, shape and grain structure with respect to defects and grain boundaries on the oxidation of metal nanoparticles.

Author

Sara Nilsson

Chalmers, Physics, Chemical Physics

David Albinsson

Chalmers, Physics, Chemical Physics

Tomasz Antosiewicz

University of Warsaw

Joachim Fritzsche

Chalmers, Physics, Chemical Physics

Christoph Langhammer

Chalmers, Physics, Chemical Physics

Nanoscale

2040-3364 (ISSN)

Vol. 11 43 20725-20733

Single Nanoparticle Catalysis, SINCAT

European Commission (Horizon 2020), 2016-01-01 -- 2020-12-31.

Subject Categories

Inorganic Chemistry

Materials Chemistry

Other Chemistry Topics

Infrastructure

Chalmers Materials Analysis Laboratory

Nanofabrication Laboratory

DOI

10.1039/c9nr07681f

PubMed

31650143

More information

Latest update

12/3/2019