3D printed metamaterial absorbers for mid-infrared surface-enhanced spectroscopy

The resonant nature and geometric scalability make metamaterials an ideal platform for an enhanced light–matter interaction over a broad frequency range. The mid-infrared (IR) spectral range is of great importance for vibrational spectroscopy of molecules, while IR metamaterials created from lithography-based planar nanostructures have been used to demonstrate enhanced molecular detection. Compared with visible and near-infrared, the relative long wavelengths of IR light make it possible to achieve three-dimensional (3D) IR metamaterials via the state-of-the-art 3D fabrication techniques. Here, we design and fabricate a 3D printed plasmonic metamaterial absorber (MMA), and by performing Fourier-transform IR spectroscopy, we demonstrate that a series of molecular fingerprint vibrations of glycine can be significantly enhanced by the high absorption mode supported by the 3D meta-atoms of the MMA. The observed enhanced IR detection can also be partially attributed to the improved accessibility offered by the 3D architecture of the MMA. In particular, due to capillary forces during the drying process, the microscale 3D printed features lead to selective analyte deposition in high-field regions, which provides another degree of freedom in the design of the 3D printed structures for surface-enhanced IR detection. Our study shows the flexibility of metastructures based on advanced 3D printing technology in tailoring the interaction between IR light and materials on a subwavelength scale.