Use of polystyrene brushes to investigate the role of interface between substrates and thin homogeneous films

The viscoelastic properties of thin polystyrene (PS) films depend on confinement, as it can modify the molecular dynamics affecting the glass transition. In the recent past, the authors have investigated the region next to the free interface by means of an atomic force microscope suitably modified to monitor the indentation of a tip into a film during a given lapse of time while applying a constant load. Herein, to explore the interface with the substrate, the authors report on experiments in which PS brushes grafted to native silicon oxide were used. It was found that the film wettability on brushes and H‐terminated silicon can be highly improved when compared with native silicon oxide. In addition, the glass transition temperature of thin films increases up to the bulk value in the case of film/brush combinations with high molecular weight or films with high molecular weight on H‐terminated silicon. Data are discussed according to hypotheses such as residual solvent presence, interface free volume, and molecular mechanical coupling. These observations can be of great interest for nanotechnological applications, especially in those instances where one needs to tailor the temperature dependence of viscoelastic properties of thin films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1149–1156