Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer

Abstract

We report on the thin film self-assembly and post-fabrication functionalization of cylinder-forming poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (PS-b-PVDMA) block copolymers (BCPs). Thermal annealing of an asymmetric BCP composition, to drive microphase separation in thin films, results in high defect densities and poor long-range order. Using FTIR spectroscopy and ellipsometry, we demonstrate that thermal annealing results in reactions between the azlactone groups and the underlying substrate leading to BCP “pinning”. We demonstrate that solvent annealing circumvents these issues and drives high fidelity microphase separation of the BCP in thin films. The solvent annealing approach also enables control over domain orientation; we show that parallel and perpendicularly oriented cylinders with diameters of 11.7 ± 1.2 nm and a center-to-center distance of 25.2 ± 2.6 nm can be obtained using a BCP with Mn = 29.5 kDa and fS = 0.75. The PVDMA segments in these self-assembled thin films remain available f...