Here, we report a new nanoantenna for surface-enhanced infrared absorption (SEIRA) detection, consisting of a fan-shaped Au structure positioned at a well-specified distance above a reflective plane with an intervening silica spacer layer. We examine how to optimize both the antenna dimensions and the spacer layer for optimal SEIRA enhancement of the C-H stretching mode. This tunable 3D geometry yields a theoretical SEIRA enhancement factor of 10(5), corresponding to the experimental detection of 20-200 zeptomoles of octadecanethiol, using a standard commercial FTIR spectrometer. Experimental studies illustrate the sensitivity of the observed SEIRA signal to the gap dimensions. The optimized antenna structure exhibits an order of magnitude greater SEIRA sensitivity than previous record-setting designs.

Surface-enhanced infrared absorption (SEIRA) spectroscopy has outstanding potential in chemical detection as a complement to surface-enhanced Raman spectroscopy (SERS), yet it has historically lagged well behind SERS in detection sensitivity. Here we report a new ultrasensitive infrared antenna designed to bring SEIRA spectroscopy into the few-molecule detection range. Our antenna consists of a bowtie-shaped Au structure with a sub-3 nm gap, positioned to create a cavity above a reflective substrate. This three-dimensional geometry tightly confines incident mid-infrared radiation into its ultrasmall junction, yielding a hot spot with a theoretical SEIRA enhancement factor of more than 10, which can be designed to span the range of frequencies useful for SEIRA. We quantitatively evaluated the IR detection limit of this antenna design using mixed monolayers of 4-nitrothiophenol (4-NTP) and 4-methoxythiolphenol (4-MTP). The optimized antenna structure allows the detection of as few as ∼500 molecules of 4-NTP and ∼600 molecules of 4-MTP with a standard commercial FTIR spectrometer. This strategy offers a new platform for analyzing the IR vibrations of minute quantities of molecules and lends insight into the ultimate limit of single-molecule SEIRA detection.

Aluminum is an abundant and high-quality material for plasmonics with potential for large-area, low-cost photonic technologies. Here we examine aluminum nanoclusters with plasmonic Fano resonances that can be tuned from the near-UV into the visible region of the spectrum. These nanoclusters can be designed with specific chromaticities in the blue-green region of the spectrum and exhibit a remarkable spectral sensitivity to changes in the local dielectric environment. We show that such structures can be used quite generally for colorimetric localized surface plasmon resonance (LSPR) sensing, where the presence of analytes is detected by directly observable color changes rather than through photodetectors and spectral analyzers. To quantify our results and provide a metric for optimization of such structures for colorimetric LSPR sensing, we introduce a figure of merit based on the color perception ability of the human eye.

Since its discovery in the 1970s, surface-enhanced Raman scattering (SERS) has been primarily associated with substrates composed of nanostructured noble metals. Here we investigate chemically synthesized nanocrystal aggregates of aluminum, an inexpensive, highly abundant, and sustainable metal, as SERS substrates. Al nanocrystal aggregates are capable of substantial near-infrared SERS enhancements, similar to Au nanoparticles. The intrinsic nanoscale surface oxide of Al nanocrystals supports molecule-substrate interactions that differ dramatically from noble metal substrates. The preferential affinity of the single-stranded DNA (ssDNA) phosphate backbone for the Al oxide surface preserves both the spectral features and nucleic acid cross sections relative to conventional Raman spectroscopy, enabling quantitative ssDNA detection and analysis.

While there has been a tremendous increase of recent interest in noble metal-based antennas as substrates for surface-enhanced infrared absorption spectroscopy, more abundant and manufacturable metals may offer similar or additional opportunities for this mid-infrared sensing modality. Here we examine the feasibility of aluminum antennas for SEIRA, by designing and fabricating asymmetric aluminum cross antennas with nanometer-scale gaps. The asymmetric cross design enables the simultaneous detection of multiple infrared vibrational resonances over a broad region of the mid-infrared spectrum. The presence of the Al2O3 amorphous surface oxide layer not only passivates the metal antenna structures but also enables a very straightforward covalent binding chemistry for analyte molecules to the antenna through multiple approaches, in this case by the use of carboxylic acid functional groups. The aluminum–oxygen stretching mode of the oxide can be used as a self-calibration standard to quantify the number of analyte molecules on the antenna surface.