For advanced CMOS, Molybdenum is now attracting attention as the alternative metal to W in source/drain contacts and local interconnect. This work reports that the electron Schottky barrier height was reduced to 0.48 eV at Mo/n-Si junctions by inserting a semimetal MoSi_n (n = 8) film. The SBH modulation effect was kept even after annealing up to at 700 °C. The MoSi_n film was formed with an excellent coverage by using MoF₆ and SiH₄, and then the Mo electrode was successively formed onto MoSi_n in the same deposition system. Thus, the MoSi_n film is promising as a contact material.