Sub-10 nm Nanolaminated AlO/HfO Coatings for Long-Term Stability of Cu Plasmonic Nanodisks in Physiological Environments.

By supporting localized plasmon modes, metal-based plasmonic nanostructures can confine optical fields at deep-subwavelength scale in various applications, such as biological and chemical sensing, nanoscale light emission, and solar energy harvesting. While Cu is a low-cost complementary metal oxide semiconductor (CMOS) compatible material, its poor chemical stability limits the use of Cu plasmonic nanodevices in corrosive biochemical aqueous environments. In this paper, we demonstrate that sub-10 nm AlO/HfO nanolaminated coatings can significantly extend the lifetime of Cu nanodisk arrays from ∼5 h to ∼180 days in the physiological environment of 1× phosphate-buffered saline (PBS) at 37 °C. Cu nanodisk arrays are fabricated using freestanding Au nanohole array films as the physical vapor deposition masks and sub-10 nm nanolaminated coatings composed of alternating AlO and HfO nanolayers are grown on Cu nanodisk arrays by atomic layer deposition (ALD). Time-dependent optical extinction measurements of Cu nanodisk arrays are conducted in 1× solutions at 37 °C to investigate the anticorrosion performance for different pure and nanolaminated ALD coatings. We observe a linear relationship between the lifetime of Cu nanodisk arrays in 1× PBS at 37 °C and the nanolaminated coating thickness, and ∼1.3 nm nanolaminated coatings of ∼10 ALD cycles can extend the lifetime of Cu plasmonics up to ∼20 days. Furthermore, we find that the anticorrosion performance of AlO/HfO nanolaminated ALD coatings strongly depends on the processing and the geometric parameters, such as the annealing temperature and the nanolaminated backbone unit size.