Plasmon Near-Field Coupling in Metal Dimers as a Step toward Single-Molecule Sensing

In this study, we report on ultrasensitive protein detection with lithographically prepared plasmonic nanostructures. We have engineered optical nanosensors by the combined approach of negative resist, electron beam lithography, and reactive ion etching to form highly reproducible arrays of gold dinners in which the near-field coupling in their subwavelength gap enables for scaling the sensing volume down to the single-protein scale. In good agreement with recent theoretical predictions, the dinner geometry offers enhanced sensitivity compared to isolated particles for the detection of both small organic molecules and proteins. Beyond, by exploiting size exclusion, we are capable of monitoring the number of proteins able to bind across the gap region through the precise engineering of the structures coupled to the selective binding of a surface-assembled monolayer and covalent attachment of the protein.