We have studied reactively sputtered ZrN, the most thermally stable of the refractory metal nitrides, for its diffusion barrier properties in aluminum metallization schemes with Rutherford backscattering spectroscopy and transmission electron microscopy (TEM). We find this compound to be very effective against aluminum diffusion up to 500 °C, independently of subtrate temperature during sputtering. The useful temperature range can be extended by 50 °C with proper pre-annealing prior to aluminum deposition. The TEM study of the ZrN grain size as a function of annealing temperature revealed that the grain size does not change significantly upon annealing and that the grains are relatively small even at the highest annealing temperatures (about 300 Å at 900 °C). In addition, for annealing temperatures of and below 500 °C large portions of ZrN films were found to be of either amorphous or extremely fine-grain material, thus inhibiting the diffusion along grain boundaries. The presence of Zr3Al4Si5 ternary compound in samples annealed at 600 °C, as determined by X-ray analysis, may suggest that the ZrN barrier fails by decomposition of the film by aluminum. © 1983.