A high-chi diblock copolymer (BCP) for self-assembly comprises a first block comprising repeat units of trimethylsilyl styrene (TMSS) and styrene, and a second block comprising an aliphatic carbonate repeat unit. The blocks are linked together by a fluorinated junction group L′ in which none of the fluorines of L′ are covalently bound to an atomic center of the polymer backbone. A top-coat free film layer comprising the BCP, which is disposed on an underlayer and in contact with an atmosphere, is capable of forming a perpendicularly oriented lamellar domain pattern on an underlayer that is preferential or non-preferential to the domains of the block copolymer. The domain pattern can be selectively etched to provide a relief pattern comprising a remaining domain. The relief pattern having good critical dimensional uniformity compared to an otherwise identical polymer lacking the silicon.