Swelling-induced morphology in ultrathin supported films of poly(d,l-lactide)

Abstract

In this study we describe a surface morphology that arises when ultrathin supported films of poly(d,l-lactide) are immersed in water. The films are initially flat with a rms roughness of approximately 2 nm. After immersion the surfaces of the films are covered with craters. The craters have a narrow distribution of sizes and are typically micrometers in diameter. They have depths in the 10-100 nm range. In situ atomic force microscopy shows that the craters occur as a result of a blistering process, which occurs when the films delaminate from the silicon substrate. The films buckle away from the substrate to give a nonzero initial diameter and then the blisters proceed to grow until they reach a maximum size. At any point during the growth process, the blisters can be made to collapse by removing the films from water. This phenomenon is explained in terms of a laterally confined swelling film, which has a buckling instability and releases excess strain energy by wrinkling. An expression for the initial buckling wavelength is extracted using the expressions for a buckling plate. Information about the mechanical properties of the films and the surface interaction between the film and substrate can also be obtained by considering the kinetics of blister growth.