Thermally induced alloying processes in a bimetallic system at the nanoscale: AgAu sub-5 nm core–shell particles studied at atomic resolution† †Electronic supplementary information (ESI) available. See DOI: 10.1039/C7NR07286D

Alloying processes in nanometre-sized Ag@Au and Au@Ag core@shell particles with average radii of 2 nm are studied via high resolution Transmission Electron Microscopy (TEM) imaging on in situ heatable carbon substrates. The bimetallic clusters are synthesized in small droplets of superfluid helium under fully inert conditions. After deposition, they are monitored during a heating cycle to 600 K and subsequent cooling. The core-shell structure, a sharply defined feature of the TEM High-Angle Annular Dark-Field images taken at room temperature, begins to blur with increasing temperature and transforms into a fully mixed alloy around 573 K. This transition is studied at atomic resolution, giving insights into the alloying process with unprecedented precision. A new image-processing method is presented, which allows a measurement of the temperature-dependent diffusion constant at the nanoscale. The first quantification of this property for a bimetallic structure <5 nm sheds light on the thermodynamics of finite systems and provides new input for current theoretical models derived from bulk data.