Hydrogen-argon plasma pre-treatment for improving the anti-corrosion properties of thin Al2O3 films deposited using atomic layer deposition on steel

The effect of H-2-Ar plasma pre-treatment prior to thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) of Al2O3 films on steel for corrosion protection was investigated. Time-of-flight secondary ion mass spectrometry and transmission electron microscopy were used to observe the changes in the interface. The electrochemical properties of the samples were studied with polarization measurements, and the coating porosities were calculated from the polarization results for easier comparison of the coatings. Prior to thermal ALD the plasma pre-treatment was observed to reduce the amount of impurities at the interface and coating porosity by 1-3 orders of magnitude. The anti-corrosion properties of the PEALD coatings could also be improved by the pre-treatment. However, exposure of the pre-treatment plasma activated steel surface to oxygen plasma species in PEALD led to facile oxide layer formation in the interface. The oxide layer formed this way was thicker than the native oxide layer and appeared to be detrimental to the protective properties of the coating. The best performance for PEALD Al2O3 coatings was achievedwhen, after the plasma pre-treatment, the surface was given time to regrow a thin protective interfacial oxide prior to exposure to the oxygen plasma. The different effects that thermal and plasma-enhanced ALD have on the substrate-coating interfacewere compared. The reactivity of the oxygen precursorwas shown to have a significant influence on substrate surface in the early stages of film growth and thereafter also on the overall quality of the protective film. (C) 2013 Elsevier B.V. All rights reserved.