The role of surface preparation in corrosion protection of copper with nanometer-thick ALD alumina coatings

Surface smoothening by substrate annealing was studied as a pre-treatment for improving the corrosion protection provided to copper by 10, 20 and 50 nm thick alumina coatings deposited by atomic layer deposition. The interplay between substrate surface state and deposited film thickness for controlling the corrosion protection provided by ultrathin barrier films is demonstrated. Pre-annealing at 750 degrees C heals out the dispersed surface heterogeneities left by electropolishing and reduces the surface roughness to less than 2 nm independently of the deposited film thickness. For 10 nm coatings, substrate surface smoothening promotes the corrosion resistance. However, for 20 and 50 nm coatings, it is detrimental to the corrosion protection due to local detachment of the deposited films. The weaker adherence of the thicker coatings is assigned to the stresses accumulated in the films with increasing deposited thickness. Healing out the local heterogeneities on the substrate surface diminishes the interfacial strength that is bearing the stresses of the deposited films, thereby increasing adhesion failure for the thicker films. Pitting corrosion occurs at the local sites of adhesion failure. Intergranular corrosion occurs at the initially well coated substrate grain boundaries because of the growth of a more defective and permeable coating at grain boundaries. (C) 2016 Elsevier B.V. All rights reserved.