Investigation of the Corrosion Behavior of Atomic Layer Deposited Al₂O₃/TiO₂ Nanolaminate Thin Films on Copper in 0.1 M NaCl

Fifty nanometers of Al₂O₃ and TiO₂ nanolaminate thin films deposited by atomic layer deposition (ALD) were investigated for protection of copper in 0.1 M NaCl using electrochemical techniques. Coated samples showed increases in polarization resistance over uncoated copper, up to 12 MΩ-cm²_, as measured by impedance spectroscopy. Over a 72-h immersion period, impedance of the titania-heavy films was found to be the most stable, as the alumina films experienced degradation after less than 24 h, regardless of the presence of dissolved oxygen. A film comprised of alternating Al₂O₃ and TiO₂ layers of 5 nm each (referenced as ATx5), was determined to be the best corrosion barrier of the films tested based on impedance spectroscopy measurements over 72 h and equivalent circuit modeling. Dissolved oxygen had a minimal effect on ALD film stability, and increasing the deposition temperature from 150 °C to 250 °C, although useful for increasing film quality, was found to be counterproductive for long-term corrosion protection. Implications of ALD film aging and copper-based surface film formation during immersion and testing are also discussed briefly. The results presented here demonstrate the potential for ultra-thin corrosion barrier coatings, especially for high aspect ratios and component interiors, for which ALD is uniquely suited.