Compositions for directed self-assembly (DSA) patterning techniques are provided. Methods for directed self-assembly are also provided in which a DSA composition comprising a block copolymer (BCP) is applied to a substrate and then self-assembled to form the desired pattern. The block copolymer includes at least two blocks and is selected to have a high interaction parameter (χ). The BCPs are able to form perpendicular lamellae by simple thermal annealing on a neutralized substrate, without a top coat. The BCPs are also capable of micro-phase separating into lines and spaces measuring at 10 nm or smaller, with sub-20-nm L0 capability.