Interfacial native oxide effects on the corrosion protection of copper coated with ALD alumina.

The effect of the interfacial air-formed native copper oxide layer on the corrosion protection of copper with 20 nm Atomic Layer Deposited (ALD) alumina was investigated in 0.5 M NaCl using electrochemical and surface analysis techniques. The results show that dissolution of the interfacial native oxide by a pre-treatment of the copper substrate with phosphoric acid is beneficial to the sealing property of the coating and to the corrosion resistance of the substrate exposed through channel defects. Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) elemental depth profiling evidenced the modifications of the interfacial copper oxide on a pre-treated substrate including cleaning from organic contaminants. The beneficial effects of the pre-treatment include improved ALD nucleation and growth due to interface cleaning and decreased cathodic electrochemical activity (assigned to oxygen reduction) at the end of the channel defects exposing the substrate to the environment. Electrochemical Impedance Spectroscopy (EIS) analysis revealed a remarkably lower porosity of the bulk of the ALD alumina layers as compared to the coating/substrate interface, suggesting interfacial trenching as a major failure mechanism for the corrosion protection. Interfacial trenching can be reduced with a freshly re-grown interfacial oxide on the pre-treated substrate surface. The necessity for better controlling the interface chemistry for improved corrosion protection by ALD alumina is demonstrated. [ABSTRACT FROM AUTHOR]