Glass transitions in nanoscale heated volumes of thin polystyrene films.

Glass transitions in confined polystyrene films on a silicon substrate were studied using atomic force microscopy incorporating a thermal tip. Three-dimensional spatial nanoconfinements were achieved by controlling size and boundary conditions of small heated volumes of polymer nanostrands drawn from the polymer surface with the thermal tip, using appropriate loads and temperatures at the tip-polymer contact. Finite element analysis was performed to model mechanical contact and thermal transport, including the effects of contact radius, film thickness, and load on temperature and pressure distributions in the confined volume at the contact. The glass transition temperature (T(g)) was measured by observing the softening of polymers with increasing temperature. The measured surface T(g) exhibited a strong size dependence, while the subsurface T(g) increased with decreasing the distance to the substrate. A large increase in the surface T(g) was observed when the radius of contact was reduced below about 10 nm. The increase in the glass transition temperature at the surface was attributed to the presence of surface and line tension at the nanometer contact, while the enhanced T(g) near the substrate was attributed to the pinning effects that reduces the mobility of the polymer molecules in the film over several hundreds of nanometers away from the polymer-substrate interface.