Free Space Makes the Polymer "Dead Layer" Alive

The effect of free space on molecular motion inside the polymer "dead layer" or adsorbed nanolayers on solid surfaces is investigated. Free space is introduced into the nanolayer by choosing a polymer with a relatively big side group, poly n-butyl methacrylate (PnBMA), and polarization-resolved single-molecule fluorescence microscopy is adopted as the method. The rotational motion of the doped fluorescent probes is found to be considerably excited at moderate temperatures, attributed to the free space brought by the side group of the PnBMA. The development of the adsorbed nanolayer by the prolonged annealing of the parent film is carefully monitored, together with the evolution of the molecular motion and the glass transition temperature (T_g). The T_g values of the exposed nanolayers are considerably lower than that of the bulk system, while they become higher than those in the bulk situation when the nanolayer is covered with a polymer top layer. The experimental evidence has demonstrated that the free space made available by the side group and the air-polymer interface has considerably promoted the molecular motion inside the adsorbed nanolayers, even under the situation of overwhelming surface attraction.