Backscattering spectrometry, Auger electron spectroscopy, and x‐ray diffraction have been used to monitor the thin‐film reactions and nitrogen redistribution in the 〈Si〉/Ti/W–N/Al metallization system. It is found that nitrogen in the W–N layer redistributes into Ti after annealing at temperatures above 500 °C. As a consequence of this redistribution of nitrogen, a significant amount of interdiffusion between Al and the underlayers is observed after annealing at 550 °C. This result contrasts markedly with that for the 〈Si〉/W–N/Al system, where no interdiffusion can be detected after the same thermal treatment. We attribute this redistribution of nitrogen to the stronger affinity of Ti for nitrogen than W. If the Ti layer is replaced by a sputtered TiSi_(2.3) film, no redistribution of nitrogen or reactions can be detected after annealing at 550 °C for 30 min