The Effects of Surface Spin Polarization on Copper Oxidation by Triplet Oxygen

The process of copper oxidation has been thoroughly studied for many years, yielding a significant understanding of its kinetics and chemistry. However, the possible roles of surface spin polarization in important issues such as oxidation rates have not been widely explored despite the triplet nature of molecular oxygen. Here, we investigate the spin-dependent oxidation of copper films by triplet O₂, exploiting engineered ferromagnetic substrates to impose controlled surface spin polarization. Three sample architectures that enable comparison between spin-polarized and nonpolarized surfaces were implemented to enable direct comparison between regions of varying spin polarization on the same sample. Combining various surface-sensitive techniques, including atomic force microscopy, Kelvin probe force microscopy, ellipsometry, and magneto-optical Kerr effect, we followed oxide growth kinetics and electronic property changes over time scales from minutes to weeks. Our results demonstrate that spin-polarized surfaces exhibit a significant acceleration in copper oxide formation compared with less polarized regions. The difference appears to be driven by a preference toward the formation of cupric oxide (CuO), the second oxidation state of copper, over cuprous oxide (Cu₂O), the first oxidation state. We suggest that the results are related to the different magnetic properties of each oxide. Our data also reveal that the CuO oxidation phase propagates from the Cu film edges toward the center of the sample. These findings provide direct evidence of the surface-spin influence on metal oxidation kinetics and support the notion that spin polarization can induce a lower activation energy barrier for electron transfer between metal to triplet O₂. Beyond advancing the fundamental understanding of corrosion chemistry, this spin-dependent control of surface reactivity opens potential avenues for tailored catalyst design, spintronic device stability, and corrosion mitigation strategies.