Published online by Cambridge University Press: 01 February 2011
The glass transition temperature (Tg) of thin supported films of stereoregular poly(methyl methacrylate) on silicon has been investigated by ellipsometry in temperature. The Tg of the spin coated layers of isotactic PMMA increases for thickness lower than 100 nm whereas a depression of the Tg is observed for the syndiotactic PMMA. This opposite trend in the Tg variation in thin layer between the two isomers evidenced a fascinating effect of the chain organization at an interacting interface. Hydrofluric acid surface etching of the silicon wafer was shown to decrease the threshold thickness at which the change in Tg occurs for both PMMA isomers. The influence of the interfacial interactions along with the tacticity dependent characteristics of the polymer will be discussed.