A method for forming a self aligned pattern on an existing pattern on a substrate comprising applying a coating of the masking material to the substrate; and allowing at least a portion of the masking material to preferentially attach to portions of the existing pattern. The pattern is comprised of a first set of regions of the substrate having a first atomic composition and a second set of regions of the substrate having a second atomic composition different from the first composition. The first set of regions may include one or more metal elements and the second set of regions may include a dielectric. The masking material may comprise a polymer containing a reactive grafting site that selectively binds to the portions of the pattern. The masking material may include a polymer that binds to the portions of the pattern to provide a layer of functional groups suitable for polymerization initiation, a reactive molecule having functional groups suitable for polymerization propagation, or a reactive molecule, wherein reaction of the reactive molecule with the portion of the pattern generates a layer having reactive groups, which participate in step growth polymerization. Structures in accordance with the method. Compositions for practicing the method.