Stability And Energetics Of Two-Dimensional Surface Crystals In Liquid Ausi Thin Films And Nanoscale Droplets

We employ atomic-scale computational frameworks to study the surface crystallization in AuSi films and droplets as a function of composition, temperature, and size. Above the melting point, the surfaces of both thin films and droplets undergo a first-order transition from a two-dimensional (2D) Au2Si crystalline phase to a laterally disordered yet stratified layer. The thin film surfaces exhibit an effective surface tension that increases with temperature and decreases with Si concentration, while for droplets in the size range 10-30 nm, the bulk Laplace pressure alters the surface segregation as it occurs with respect to a strained bulk. Above the transition, the size effect on the surface tension due to the stratified surface layer is small, while the crystalline surface layer below the transition is strained and composed of 2D crystallites separated by extended grain boundary scars that lead to large fluctuations in its energetics. As a specific application, all-atom simulations of AuSi droplets on Si(111) substrate subject to Si surface flux show that the supersaturation dependent surface tension destabilizes the contact line via formation of a precursor wetting film on the solid-vapor interface and has ramifications for size selection during droplet-catalyzed routes for nanowire growth. Our study sheds light on the interplay between stability and energetics of surfaces in this unique class of binary alloys and offers pathways for exploiting their surface structure for varied applications such as catalytic nanocrystal growth, dealloying, and polymer crystallization.