Ta N x diffusion barriers with good barrier properties at subnanometer thickness were deposited by plasma-enhanced atomic layer deposition (PE-ALD) from pentakis(dimethylamino)Ta. Hydrogen and/or nitrogen plasma was used as reactants to produce TaNx thin films with a different nitrogen content. The film properties including the carbon and oxygen impurity content were affected by the nitrogen flow during the process. The deposited film has nanocrystalline grains with hydrogen-only plasma, while the amorphous structure was obtained for nitrogen plasma. The diffusion barrier properties of deposited TaN films for Cu interconnects have been studied by thermal stress test based on synchrotron x-ray diffraction. The results indicate that the PE-ALD TaN films are good diffusion barriers even at a small thickness as 0.6nm. Better diffusion barrier properties were obtained for higher nitrogen content. Based on a diffusion kinetics analysis, the nanocrystalline microstructure of the films was responsible for the better diffusion barrier properties compared to polycrystalline PE-ALD TaN films deposited from TaCl5.