The reaction mechanisms and related microstructures in the Cu/Si, Ru/Si, and Cu/Ru/Si metallization system were studied experimentally. With the help of sheet resistance measurements, x-ray diffraction, field-emission scanning electron microscopy, secondary ion mass spectroscopy, and transmission electron microscopy, the metallization structure with Ru barrier layer was observed to fail completely at temperatures around 700 °C, regardless of the Ru thickness because of the formation of polycrystalline Ru2Si3 followed by Cu3Si protrusions.