Processes of forming an insulated wire into an interlayer dielectric layer (ILD) of a back-end metallization includes thermally treating a metallic barrier precursor under conditions to cause at least one alloying element in the barrier precursor to form a dielectric barrier between the wire and the ILD. The dielectric barrier is therefore a self-forming, self-aligned barrier. Thermal processing is done under conditions to cause the at least one alloying element to migrate from a zone of higher concentration thereof to a zone of lower concentration thereof to further form the dielectric barrier. Various apparatus are made by the process.