The influence of some important process parameters on the quality of electrical contacts to a silicon substrate has been studied for a double‐level metallization system consisting of Al–MoSi2–Al(Cu,Si)–cSi. This double‐level metallization scheme is presently used in the production of advanced complementary metal–oxide semiconductor devices. The metal films were produced in two commercially available sputtering systems. A detailed picture of the reactions within the metal films and at the interface to the substrate was obtained by means of Rutherford backscattering spectroscopy, secondary ion mass spectroscopy, x‐ray diffraction (diffractometer and Read camera), differential scanning calorimetry, metallographic sectioning, and scanning electron microscopy, in addition to electrical measurements on contact chains and Kelvin contact structures. The dependence of the stoichiometry of the deposited MoSi2film on the sputtering pressure was determined in the range 1–15 mTorr. The formation of hexagonal MoSi2from the amorphous as‐deposited film was found to occur around 380 °C with an activation energy of 1.9 eV and an enthalpy of crystallization of about 40 kJ/mol. These results are shown to be compatible with theoretical estimates. Depending on the particular conditions during the deposition of the MoSi2film, Si was found to be taken up or rejected during anneals up to 425 °C. This led to spiking and precipitation, respectively. Diffusion of Mo into the Al films is shown to have resulted in the formation of MoAl12. The contacts were found to be stable during at least 70 min for temperatures up to 450 °C. It is shown that by proper tailoring of the sputtering conditions and a judicious choice of time and temperature for the postanneal cycle, it is possible to avoid the problems of spiking and silicon precipitation inherent in a metallization system based on a combination of aluminum with a near‐stoichiometric silicide.