Nanogapped Au Antennas for Ultrasensitive Surface-Enhanced Infrared Absorption Spectroscopy
Abstract
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 7, 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.
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Squeezing the gap between adjacent plasmonic nanoantennas to the nanometer scale increases electric field intensity but ruins sensing performance by decreasing active area and increasing fabrication cost.
“The other method to improve the sensitivity is to increase the intensity of the electric field by squeezing the gap between adjacent PNA into the nanometer scale29–31. However, the narrow gap ruins the sensing performance by a decrement in the active area and increases fabrication cost.”
From Wavelength-multiplexed hook nanoantennas for machine learning enabled mid-infrared spectroscopy (2022) · cites this paper as [30]
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- Authors
- Dong, L., Yang, X., Zhang, C., Cerjan, B., Zhou, L., Tseng, M. L., Zhang, Y., Alabastri, A., Nordlander, P., & Halas, N. J.
- Affiliations
- Rice University (US)
- Corresponding author
- Halas, Naomi J.
- ORCID
- Venue
- Nano Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-08-16
- Volume
- 17
- Issue
- 9
- Pages
- 5768-5774
- ISSN
- 1530-6984 (ISSN-L)
- 1530-6992
- OpenAlex
- W2744183462
- Cited by
- 274
- References
- 50
- Citations by year
- 2026: 15 · 2025: 38 · 2024: 33 · 2023: 28 · 2022: 32 · 2021: 30 · 2020: 30 · 2019: 36 · 2018: 32
- FWCI
- 12.09
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Nano Letters (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Welch Foundation (C-1220, C-1222)
- Army Research Office (W911NF-12-1-0407)
- Air Force Office of Scientific Research (FA9550-15-1-0022)
- Division of Electrical, Communications and Cyber Systems (ECCS-1610229)
- Defense Threat Reduction Agency (HDTRA1-16-1-0042)
- Topics
- Physical Sciences › Engineering › Biomedical Engineering › Plasmonic and Surface Plasmon Research
- Physical Sciences › Materials Science › Electronic, Optical and Magnetic Materials › Gold and Silver Nanoparticles Synthesis and Applications
- Physical Sciences › Engineering › Biomedical Engineering › Near-Field Optical Microscopy
- Keywords
- surface-enhanced infrared absorption, bowtie nanoantennas, single-molecule detection, 4-nitrothiophenol, detection limit, chemical sensing
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