Plasmonic Double-Walled Nanoframes with Face-to-Face Nanogaps for Strong SERS Activity

A synthesis method for plasmonic double-walled nanoframes was developed, where single-walled truncated octahedral nanoframes with (111) open facets and (100) solid flat planes are nested in a core-shell manner. By applying multiple chemical toolkits to Au cuboctahedrons as a starting template, Au double-walled nanoframes with controllable face-to-face nanogaps were successfully synthesized in high homogeneity in size and shape. Importantly, when the gap distance between inner and outer flat walled frames became closer, augmentation of electromagnetic near-field focusing was achieved, leading to generation of hot-zones, which was verified by surface-enhanced Raman spectroscopy. The unique optical property of Au double-walled nanoframes with high structural intricacy was carefully investigated and the SERS substrates comprising Au double-walled nanoframes with the narrowest nanogaps exhibited much improved near-field enhancement toward strongly and/or weakly adsorbing analytes, allowing for gas phase detection in chemical warfare agents, which is a huge challenge in early warning systems.