Segregation at surfaces of metal-covalent binary liquids is often non-classical and in extreme cases such as AuSi, the surface crystallizes above the melting point. In this study, we employ atomic-scale computational frameworks to study the surface crystallization of AuSi films and droplets as a function of composition, temperature and size. For temperatures in the range $T_s^ast=765-780$K above the melting point $(T_s^astapprox1.3,T_m)$, both thin film and droplet surfaces undergo a first order transition, from a 2D Au$_2$Si 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. On the other hand, 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 $T_s^ast$ the size effect on the surface tension is small, while for $T<T_s^ast$ the surface layer 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 VLS-based routes for nanowire growth. Our study sheds light on the interplay between stability and energetics of surfaces in these 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.
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