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 contaminants rather than via an oxidation process. Furthermore, we show that the sulfidation occurs through the formation of crystalline Ag2S bumps onto Ag surface in place of a homogeneous growth of a silver sulfide film. From a single 2D Z-contrast scanning transmission electron microscopy image, a method for 3D reconstruction of silver nanoparticles with extremely high spatial resolution has been derived thus establishing the preferential nucleation of Ag2S bumps in proximity of lattice defects located on the NP surface. Finally, we also provide a straightforward and low-cost solution to achieve stable Ag NPs by passivating them with a self-assembled monolayer of hexanethiols. The sulfidation mechanism inhibition allows to prevent the increased material damping and scattering losses.