Nanoscale Study of the Tarnishing Process in Electron Beam Lithography-Fabricated Silver Nanoparticles for Plasmonic Applications

Silver is the ideal material for plasmonics because of its low loss at optical frequencies, though it is often replaced by a lossier metal, gold. This is because of silver’s tendency to tarnish, an effect which is enhanced at the nanoscale due to the large surface-to-volume ratio. Despite chemical tarnishing of Ag nanoparticles (NPs) has been extensively studied for decades, it has not been well understood whether resulted by sulfidation or oxidation processes. This intriguing quest is herein rationalized by studying the atmospheric corrosion of electron beam lithography-fabricated Ag NPs, through nanoscale investigation performed by high-resolution transmission electron microscopy (HRTEM) combined with electron energy loss (EEL) and energy dispersive X-ray (EDX) spectroscopies. We demonstrate that tarnishing of Ag NPs upon exposure to indoor air of an environment located inside a rural site, not particularly influenced by naturally and human-made sulfur sources, is caused by chemisorbed sulfur-based cont...