Durability and Surface Oxidation States of Antiviral Nano-Columnar Copper Thin Films

Antiviral coatings that inactivate a broad spectrum of viruses are important in combating the evolution and emergence of viruses. In this study, nano-columnar Cu thin films have been proposed, inspired by cicada wings (which exhibit mechano-bactericidal activity). Nano-columnar thin films of Cu and its oxides were fabricated by the sputtering method, and their antiviral activities were evaluated against envelope-type bacteriophage Φ6 and non-envelope-type bacteriophage Qβ. Among all of the fabricated films, Cu thin films showed the highest antiviral activity. The infectious activity of the bacteriophages was reduced by 5 orders of magnitude within 30 min by the Cu thin films, by 3 orders of magnitude by the Cu₂O thin films, and by less than 1 order of magnitude by the CuO thin films. After exposure to ambient air for 1 month, the antiviral activity of the Cu₂O thin film decreased by 1 order of magnitude; the Cu thin films consistently maintained a higher antiviral activity than the Cu₂O thin films. Subsequently, the surface oxidation states of the thin films were analyzed by X-ray photoelectron spectroscopy; Cu thin films exhibited slower oxidation to the CuO than Cu₂O thin films. This oxidation resistance could be a characteristic property of nanostructured Cu fabricated by the sputtering method. Finally, the antiviral activity of the nano-columnar Cu thin films against infectious viruses in humans was demonstrated by the binding inhibition of the SARS-CoV-2 spike protein to the angiotensin-converting enzyme 2 receptor within 10 min.