Core atoms escape from the shell: reverse segregation of Pb–Al core–shell nanoclusters via nanoscale melting

Melting is a phase transition that profoundly affects the fabrication and diverse applications of metal nanoclusters. Core–shell clusters offer distinctive properties and thus opportunities compared with other classes of nano-alloys. Molecular dynamics simulations have been employed to investigate the melting behaviour of Pb–Al core–shell clusters containing a fixed Pb₁₄₇ core and varying shell thickness. Our results show that the core and shell melt separately. Surprisingly, core melting always drives the core Pb atoms to break out the shell and coat the nanoclusters in a reversed segregation process at the nanoscale. The melting point of the core increases with the shell thickness to exceed that of the bare core cluster, but the thinnest shell always supresses the core melting point. These results can be a reference for the future fabrication, manipulation, and exploitation of the core–shell nanoalloys chosen. The system chosen is ideally suited for experimental observations.