Adhesion Properties of Nanometer-Thick Perfluoropolyether Films Confined Between Solid Surfaces: A Coarse-Grained Molecular Dynamics Study

Lubrication with thin liquid films is essential to ensure the tribological reliability of technologically advanced devices, such as micro-electro-mechanical systems and hard disk drives. However, the adhesion and friction properties of thin films and the underlying mechanism remain elusive due to our limited understanding of film structures and motions at the molecular scale. Here, we investigate the adhesion behavior of nanometer-thick perfluoropolyether (PFPE) films confined between two solid surfaces as a function of film thickness using coarse-grained molecular dynamics simulations. Consistent with typical experimental results, our simulations show that the adhesive force exerted by the PFPE films reaches a maximum and then decreases with increasing solid–solid spacing. The maximum adhesive force increases sharply for PFPE films thinner than 4 nm. When exhibiting the maximum adhesive force, PFPE films are slightly stretched within a solid–solid spacing a little larger than the initial film thickness and thereby show lower density than the original equilibrium density. Conventional theories of adhesion, which assume equilibrium density for liquid films, are not applicable in such case. Therefore, we construct a theoretical model that takes decreasing liquid density into account to discuss the underlying mechanism of the adhesive force exerted by nanometer-thick PFPE films on solid surfaces. We infer from the theoretical analyses that the maximum adhesive force originates mainly from solid–liquid interaction for thin films and liquid–liquid interaction for thick films.