Control of self-assembly of lithographically patternable block copolymer films

Poly(α-methylstyrene)-block-poly(4-hydroxystyrene) acts as both a lithographic deep UV photoresist and a self-assembling material, making it ideal for patterning simultaneously by both top-down and bottom-up fabrication methods. Solvent vapor annealing improves the quality of the self-assembled patterns in this material without compromising its ability to function as a photoresist. The choice of solvent used for annealing allows for control of the self-assembled pattern morphology. Annealing in a nonselective solvent (tetrahydrofuran) results in parallel orientation of cylindrical domains, while a selective solvent (acetone) leads to formation of a trapped spherical morphology. Finally, we have self-assembled both cylindrical and spherical phases within lithographically patterned features, demonstrating the ability to precisely control ordering. Observing the time evolution of switching from cylindrical to spherical morphology within these features provides dues to the mechanism of ordering by selective solvent. © 2008 American Chemical Society.