Plasmonics–Nanofluidics Hydrid Metamaterial: An Ultrasensitive Platform for Infrared Absorption Spectroscopy and Quantitative Measurement of Molecules

One of the most attractive potentials of plasmonic metamaterials is the amplification of intrinsically weak signals such as molecular infrared absorption or Raman scattering for detection applications. This effect, however, is only effective when target molecules are located at the enhanced electromagnetic field of the plasmonic structures (i.e., hot-spots). It is thus of significance to control the spatial overlapping of molecules and hot-spots, yet it is a long-standing challenge, since it involves the handling of molecules in nanoscale spaces. Here a metamaterial consisting of a nanofluidic channel with a depth of several tens of nanometers sandwiched between plasmonic resonators and a metal film enables the controllable delivery of small molecules into the most enhanced field arising from the quadrupole mode of the structures, forming a plasmon-molecular coupled system. It offers an ultrasensitive platform for detection of IR absorption and molecular sensing. Notably, the precise handling of molecules in a fixed and ultrasmall (10-100 nm) gap also addressed some critical issues in IR spectroscopy such as quantitative measurement and measurement in aqueous solution. Moreover, a drastic change in the reflectance characteristic resulting from the strong coupling between molecules and plasmonic structures indicates that molecules can also be utilized as triggers for actively switching the optical property of metamaterials.