The effect of heat treatments on the structure and composition of a system consisting of a conductive outer layer made of Al(0.8% Si) thin film, TiW(30:70 at. %) thin film as a diffusion barrier, and a polycrystalline Si substrate was studied. It was established that heat treatments at temperatures ranging between 400 and 500 °C led to the diffusion of Si and Al through the TiW layer, following which Al diffused into the polycrystalline Si, while Si diffused into the Al film. The silicides of TiSi, TiSi2, and intermetallic compounds of Al3Ti and WAl12were formed at the Al/TiW interface as a result of the 30‐min heat treatment at temperatures ranging between 450 and 500 °C.