Synthesis of semicrystalline/fluorinated side-chain crystalline block copolymers and their bulk and thin film nanoordering

Semicrystalline/fluorinated side-chain crystalline block copolymers, dinonylphenyl end capped poly (ethylene glycol)-block-poly(fluorinated methyl medracrylate) (DNPEPEO-b-PFMAs), were synthesized by ATRP of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate using a surfactant poly(ethylene glycol) dinonylphenyl ether as precursor. Bulk and thin film morphologies in the block copolymers of DNPEPEO-b-PFMAs were investigated by DSC, WAXS, SAXS, TEM, AFM, and GISAXS. The block copolymers show microphase separated and ordered structures. In the bulk, a cylindrical morphology with PEO cylinders 4 confined in PFMA matrix was confirmed by SAXS and TEM. WAXS studied on the copolymers bulk revealed semicrystalline PEO cylinders and PFMA matrix with the fluorinated side chain organized in bilayers. In thin films of DNPEPEO-b-PFMAs on PDMS modified silicon substrates, well ordered hexagonally packed arrays with PEO cylindrical microdomains normal to the substrate were observed This fluorinated block polymer with strong unfavorable interaction between two blocks and subsequently hierarchical self assembly could be a promising material for nanolithography applications.