Block copolymers (BCPs) for self-assembly applications comprise a linear fluorinated linking group L′ joining a pair of adjacent blocks. A film layer comprising a BCP, which is disposed on an underlayer and in contact with an atmosphere, is capable of forming a perpendicularly oriented domain pattern when the underlayer is preferentially wetted by one domain of an otherwise identical self-assembled BCP in which all fluorines of L′ are replaced by hydrogen. The BCP can be a low-chi or high-chi BCP. In a preferred embodiment, the BCP comprises a styrene-based first block, and a second block comprises a carbonate and/or ester repeat unit formed by ring opening polymerization of a cyclic carbonate and/or cyclic ester monomer. The linking group L′ has a lower surface energy than each of the polymer blocks.