Although there are substantial studies on chemical mechanical polishing (CMP) processes of ruthenium (Ru) as a barrier layer in periodate-based slurries, little is known about the passivation mechanism of inhibitors and the galvanic corrosion mechanism of Cu. In this study, the synergetic effect of benzotriazole (BTA) and potassium molybdate (K2MoO4) on the polishing performance of Ru and Cu in KIO4-based slurry was investigated. The galvanic corrosion of Cu in a Cu-Ru coupled system was studied from a completely different perspective. X-ray photoelectron spectroscopy combined with other measurements was used to reveal the synergetic passivation mechanism of BTA and K2MoO4. The results show that the galvanic corrosion of Cu is strongly mitigated in the presence of both BTA and K2MoO4. Based on the data, it was regarded that the adsorbed MoO42- not only modified the surface structure of Ru and Cu, but also supported the adsorption of BTA passivation film. Also, it was found that insoluble salts were deposited into the gaps of the passivation film, which improved the compactness of the molybdate-BTA film. The CMP tests showed that the selectivity of the material removal rate of Cu to Ru can be evidently improved in the presence of BTA and K2MoO4. The increase of oxidizer content and the reduction of polishing down force could help to further decrease the MRR selectivity between Cu and Ru. (C) 2014 Elsevier B.V. All rights reserved.