Degradation of the Polyimide/Copper Interface

A comparative investigation of polyimide/Cu interface degradation has been carried out for ultrathin photosensitive, non-photosensitive, and preimidized polyimide precursor films cured while in contact with a Cu substrate. The role of curing byproducts and environmental conditions on interface degradation has been elucidated by means of X-ray photoelectron spectroscopy. Immediately after curing, we observed some oxidation of the Cu in contact with non-photosensitive and photosensitive polyimide overlayers. On the other hand, only negligible oxidation was observed for the preimidized polyimide/Cu interface. Experiments in which samples were stored in vacuum, air and a humidity chamber show a dependence of the oxidation kinetics on air/moisture exposure. Preimidized and photosensitive polyimide/Cu interfaces, stored in air, became more extensively oxidized with time relative to identical samples stored in vacuum. Moreover, all three polyimide/Cu interfaces exhibited significantly more oxidation after 3 days in a humidity chamber than after 19 days of storage in air. Taken together, these data clearly demonstrate that absorbed water and its interaction with curing byproducts are key factors in the extent of Cu oxidation at the interface.