Interface Manipulations Using Cross-Linked Underlayers and Surface-Active Diblock Copolymers to Extend Morphological Diversity in High-χ Diblock Copolymer Thin Films

Top and bottom interfaces of high-χ cylinder-forming polystyrene- block -maltoheptaose (PS -b- MH) diblock copolymer (BCP) thin films are manipulated using cross-linked copolymer underlayers and a fluorinated phase-preferential surface-active polymer (SAP) additive to direct the self-assembly (both morphology and orientation) of BCP microdomains into sub-10 nm patterns. A series of four photo-cross-linkable statistical copolymers with various contents of styrene, a 4-vinylbenzyl azide cross-linker, and a carbohydrate-based acrylamide are processed into 15 nm-thick cross-linked passivation layers on silicon substrates. A partially fluorinated analogue of the PS -b- MH phase-preferential SAP additive is designed to tune the surface energy of the top interface. The self-assembly of PS -b- MH thin films on top of different cross-linked underlayers and including 0–20 wt % of SAP additive is investigated by atomic force microscopy and synchrotron grazing incidence small-angle X-ray scattering analysis. The precise manipulation of the interfaces of ca. 30 nm thick PS -b- MH films not only allows the control of the in-plane/out-of-plane orientation of hexagonally packed (HEX) cylinders but also promotes epitaxial order–order transitions from HEX cylinders to either face-centered orthorhombic or body-centered cubic spheres without modifying the volume fraction of both blocks. This general approach paves the way for the controlled self-assembly of other high-χ BCP systems.