As-deposited and annealed tantalum films, grown by plasma-promoted chemical vapor deposition (PPCVD) using pentabromotantalum and hydrogen as coreactants, were evaluated as diffusion barriers in copper metallization. Stacks consisting of 500-nm-thick sputtered Cu/55-nm-thick untreated PPCVD Ta/Si were annealed in argon in the range 450 to 650 °C, in 50 °C intervals, along with sputtered Cu/preannealed PPCVD Ta/Si and sputtered Cu/sputtered Ta/Si stacks of identical thickness. Pre- and postannealed stacks were characterized by x-ray photoelectron spectroscopy, Auger electron spectroscopy, Rutherford backscattering spectrometry, hydrogen profiling, x-ray diffraction, atomic force microscopy, sheet resistance measurements, and Secco chemical treatment and etch-pit observation by scanning electron microscopy. The sputtered and preannealed PPCVD Ta films acted as viable diffusion barriers up to 550 °C, while the as-deposited PPCVD Ta films failed above 500 °C. In all cases, breakdown occurred through the migration of Cu into Si, rather than an interfacial reaction between Ta and Si, in agreement with previously reported results for sputtered Ta films. The accelerated barrier failure for as-deposited PPCVD Ta might have been caused by the presence of approximately 20 at.% hydrogen in the as-deposited PPCVD Ta, an observation which was supported by the enhanced performance of the same PPCVD Ta films after annealing-induced hydrogen removal.