Tungsten-rich W-Ti (or W-Ti-N) alloy films are known for their applicability as diffusion barriers in advanced silicon technology, especially in the case of aluminium-based metallizations. For a wide variety of deposition conditions and post-deposition anneal treatments these refractory-metal barriers show a columnar microstructure. In contact with aluminium the W-Ti films do not form absolute barriers, because of mutual diffusion resulting in compound formation. The reactivity of the W-Ti barriers with the Al99Si1 interconnect has been studied by in-situ resistance measurements in vacuum at temperatures of approximately 450 °C (for W-Ti alloy films) and 475 °C (for W-Ti-N alloy films). In this paper new results dealing with the relationship between deposition conditions, microstructure and barrier properties will be discussed. Furthermore, it will be shown that the actual distribution of the titanium atoms in the tungsten matrix has a substantial influence on the reactivity of the barrier film with the Al99Si1 interconnect.