The interaction of Cu with Si separated by thin (50 nm) layers of tantalum, Ta2N, and a nitrogen alloy of Ta has been investigated to determine the factors that affect the success of these materials as diffusion barriers to copper. Intermixing in these films was followed as a function of annealing temperature byinsituresistance measurements, Rutherford backscattering spectra, scanning electron microscopy, and cross‐section transmission electron microscopy. Ta prevents Cu‐silicon interaction up to 550 °C for 30 min in flowing purified He. At higher temperatures, copper penetration results in the formation of &eegr;‘‐Cu3Si precipitates at the Ta‐Si interface. Local defect sites appear on the surface of the sample in the early stages of this reaction. The Ta subsequently reacts with the substrate at 650 °C to form a planar hexagonal‐TaSi2layer. Ta silicide formation, which does not occur until 700 °C in a Ta‐Si binary reaction couple, is accelerated by the presence of Cu. Nitrogen‐alloyed Ta is a very similar diffusion barrier to Ta. It was found that Ta2N is a more effective barrier to copper penetration, preventing Cu reaction with the substrate for temperatures up to at least 650 °C for 30 min. In this case, local Cu‐Si reaction occurs along with the formation of a uniform Ta5Si3layer at the Ta2N‐Si interface.