Nanostructured morphology of polymer films prepared by Matrix Assisted Pulsed Laser Evaporation

As recently illustrated, nanostructured glassy polymer films with exceptional thermal and kinetic stability can be formed via Matrix Assisted Pulsed Laser Evaporation (MAPLE) (Guo et al. in Nat. Mater. 11:337, 2012). Relative to the standard poly(methyl methacrylate) glass formed on cooling at standard rates, glasses prepared by MAPLE can be 40 % less dense and have a 40 K higher glass transition temperature (T_g). Furthermore, the kinetic stability in the glassy state can be enhanced by 2 orders-of-magnitude. Here, we examine the stability of the structured morphology. We show that nanostructured glasses may be formed even when the substrate is held at temperatures greater than the polymer T_g during deposition. In addition, we discuss the origin of the enhanced stability and themechanism of nanostructured film formation within the framework of the Zhigileimodel. Finally, we compare the nanostructured morphology to the surface morphology of other MAPLE-deposited films in the literature.