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Surface and bulk ordering in thin films

Recent experiments that probe the effect of confinement on the dynamical properties of thin liquid films have shown that these films undergo an abrupt transition to a solid below a critical thickness. To model this behavior, we present a mean-field theory for confinement-induced first-order phase transitions based on a Ginzburg-Landau type expression for the free-energy. We show how the equilibrium melting temperature increases as the film thickness is decreased; for thick films, the melting temperature approaches its bulk value. The predicted phase diagram includes three phases: an ordinary liquid (where both the surface layer and the bulk of the film are liquid), a crystalline solid phase (where both the surface layer and the bulk are ordered) and a quasi-liquid phase in which the bulk of the film is liquid-like but the surfaces are ordered. Transitions between the phases are always first order.