Semiconductor structures include a patterned interlayer dielectric overlaying a semiconductor substrate. The interlayer dielectric includes a first dielectric layer and at least one additional dielectric layer disposed on the first dielectric layer, wherein the patterned interlayer dielectric comprises at least one opening extending through the interlayer dielectric to the semiconductor substrate. Chemically enriched regions including ions of Si, P, B, N, O and combinations thereof are disposed in surfaces of the first dielectric layer and the at least one dielectric layer defined by the at least one opening. Also described are methods of for forming an interconnect structure in a semiconductor structure.