Novel methods for the fabrication of well-defined and patterned polymer brushes

The surface-initiated polymerization of well-defined and patterned poly(caprolactone) brushes was investigated. Initially, non-reactive self-assembled monolayers formed from CH3(CH2)15SH were microcontact printed unto a gold surface using standard techniques. A second functionalized thiol, HO(CH2CH2O)2(CH2)11SH, was selectively-assembled unto the bare regions of the gold surface by simple immersion into the solution. To overcome the uncontrolled growth of the polymer, a predetermined amount of free' initiator, benzyl alcohol, was added to the reaction. The thickness of the poly(caprolactone) film was a linear function of the degree of polymerization of the polymer found in solution from the free' initiator.