Protective caps residing at an interface between metal lines and dielectric diffusion barrier (or etch stop) layers are used to improve electromigration performance of interconnects. Protective caps are formed by depositing a source layer of dopant-generating material (e.g., material generating B, Al, Ti, etc.) over an exposed copper line, converting the upper portion of the source layer to a passivated layer (e.g., nitride or oxide) while allowing an unmodified portion of a dopant-generating source layer to remain in contact with copper, and, subsequently, allowing the dopant from the unmodified portion of source layer to controllably diffuse into and/or react with copper, thereby forming a thin protective cap within copper line. The cap may contain a solid solution or an alloy of copper with the dopant.