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The performance and reliability of Cu/Low-κ damascene interconnects are investigated from the view point of the material interface structure. We are focusing especially on the heterointerfaces between the Cu and the barrier metal (BM), as well as between the hard mask (HM) and the capping barrier dielectrics (CAP) covered on the Cu interconnects. It is found that the highest via reliabilities of electromigration (EM) and thermal cycle are established by the barrier-metal-free (BMF) structure without the heterointerface between the Cu and the BM due to the strong Cu-to-Cu connection at the via bottom. The interline time-dependant dielectric breakdown lifetime is improved mostly by using a HM with the same materials as the CAP layer, referred to as an unified structure, which diminishes the heterointerface between the HM and the CAP. These ideal structures without the material heterointerfaces derive the highest reliability and performance. Structural control of the material heterointerfaces in the actual Cu/low-κ damascene interconnect is crucial for the high reliability and performance.