Dense polystyrene (PS) brushes were synthesized on silica wafers via a
“grafting from” technique using activators regenerated by electron transfer atom transfer
radical polymerization (ARGET ATRP). Spectroscopic ellipsometry and fluorescence
spectroscopy were used to investigate the effect of nanoscale confinement on the glass
transition temperature (Tg) and its distribution in dense PS brushes and bilayer constructs
of brushes and freely deposited PS films. Single-layer PS brushes exhibit an overall
average Tg that is nearly invariant with thickness down to 11 nm, with Tg values of the
dense brushes differing by no more than 2 °C from those of bulk PS of the same
molecular weight as that of the brush. These results differ greatly from those obtained
with freely deposited PS films that show major Tgreductions with confinement.
Distributions of Tgs were also studied by fluorescence in dense, ∼70-nm-thick PS brushes.
Relative to Tg,bulk, chain segments within 10 nm of the substrate exhibit a ∼36 °C increase
inTg while segments within 5 nm of the free surface exhibit a 14 °C decrease in Tg.
Fluorescence was also used to characterize the tunability of Tg within a single layer of
bilayer constructs. As brush thickness increases from 13 to 94 nm, the Tg of a 15-nm-
thick PS overlayer film decreases from 100 °C to 87 °C; in contrast, as the overlayer PS
film thickness increases from 0 to 101 nm, the Tg of an 11-nm-thick underlayer PS brush
increases from 98 °C to 126 °C. These results are compared with the few previous
experimental reports of Tg-confinement effects of densely grafted PS brushes and bilayer
constructs of brushes and films.