A nanostructure barrier for copper wire bonding includes metal grains and inter-grain metal between the metal grains. The nanostructure barrier includes a first metal selected from nickel or cobalt, and a second metal selected from tungsten or molybdenum. A concentration of the second metal is higher in the inter-grain metal than in the metal grains. The nanostructure barrier may be on a copper core wire to provide a coated bond wire. The nanostructure barrier may be on a bond pad to form a coated bond pad. A method of plating the nanostructure barrier using reverse pulse plating is disclosed. A wire bonding method using the coated bond wire is disclosed.