Exploring the formation of gold/silver nanoalloys with gas-phase synthesis and machine-learning assisted simulations

Abstract: While nanoalloys are of paramount scientific and practical interests, the main processes leading to their formation are still poorly understood. Key structural features in the alloy systems, including crystal phase, chemical ordering, and morphology, are challenging to control at the nanoscale, making it difficult to transfer their usage to industrial applications. In this contribution, we focus on the gold/silver system that has two of the most prevalent noble metals, and combine experiments with simulations to uncover the formation mechanisms at the atomic-level. Nanoparticles are produced using state-of-the-art inert-gas aggregation source and analyzed using transmission electron microscopy and energy-dispersive x-ray spectroscopy. Machine-learning-assisted molecular dynamics simulations are employed to model the crystallization process from liquid droplets to nanocrystals. Our study finds a preponderance of nanoparticles with five-fold symmetric morphology, including icosahedron and decahedron which is consistent with previous results on mono-metallic nanoparticles. However, we observe that gold atoms, rather than silver atoms, segregate at the surface of the obtained nanoparticles for all the considered alloy compositions. These segregation tendencies are in contrast to previous studies and have consequences on the crystallization dynamics and the subsequent crystal ordering. We finally show that the underpinnings of this surprising segregation dynamics is due to charge transfer and electrostatic interactions rather than surface energy considerations.