A conductive connector for a microelectronic structure may be formed in an opening in a dielectric layer, wherein a ruthenium/aluminum-containing liner is disposed between the dielectric layer and a substantially aluminum-free copper fill material within the opening. The ruthenium/aluminum-containing liner may be formed by depositing a ruthenium-containing liner and migrating aluminum into the ruthenium-containing liner with an annealing process. The aluminum may be presented as a layer formed either before or after the deposition of a copper fill material, or may be presented within a copper/aluminum alloy fill material wherein the annealing process migrates the aluminum out of the copper/aluminum alloy and into the ruthenium-containing liner.