Nanostructured Thin Films of Moderately Functionalized PMMA-b-PS.

A library of poly(methyl methacrylate)-block-polystyrene (PMMA-b-PS) block copolymers (BCPs) bearing small amounts (<10 mol%) of functional comonomer in either one or both blocks is investigated for their phase separation behavior in bulk and in thin films. Particularly, functionalities typically involved in modern postpolymerization modifications are considered, e.g., azide, pentafluorophenyl, furfuryl. Small-angle X-ray scattering and atomic force microscopy are employed to determine the characteristic dimensional features of lamellae-forming BCPs, which differ essentially in the functional groups. It is shown that the presence of the reactive moieties does not perturb the ability to phase separate in bulk, yet has an impact on the dimensions of the domains. Using a classic two-step procedure involving surface neutralization with a statistical PMMA-co-PS copolymer, it is observed that some functional copolymers are not able to form homogeneous thin films. Solvent stability and crosslinking ability of the films are then briefly assessed as a first step to establishing the functional films as nanoresolved molecular immobilization platform with feature sizes of 20 nm and below.