Galvanic corrosion inhibition from aspect of bonding orbital theory in Cu/Ru barrier CMP

Abstract

In this report, the galvanic corrosion inhibition between Cu and Ru metal films is studied, based on bonding orbital theory, using pyridinecarboxylic acid groups which show different affinities depending on the electron configuration of each metal resulting from a π-backbonding. The sp2 carbon atoms adjacent to nitrogen in the pyridine ring provide π-acceptor which forms a complex with filled d-orbital of native oxides on Cu and Ru metal film. The difference in the d-orbital electron density of each metal oxide leads to different π-backbonding strength, resulting in dense or sparse adsorption on native metal oxides. The dense adsorption layer is formed on native Cu oxide film due to the full-filled d-orbital electrons, which effectively suppresses anodic reaction in Cu film. On the other hand, only a sparse adsorption layer is formed on native Ru oxide due to its relatively weak affinity between partially filled d-orbital and pyridine groups. The adsorption behaviour is investigated through interfacial interaction analysis and electrochemical interaction evaluation. Based on this finding, the galvanic corrosion behaviour between Cu and Ru during chemical mechanical planarization (CMP) processing has been controlled.