Surface‐enhanced Raman spectroscopy (SERS) has become a sensitive detection technique for biochemical analysis. Despite significant research efforts, most SERS substrates consisting of single‐resonant plasmonic nanostructures on the planar surface suffer from limitations of narrowband SERS operation and unoptimized nano‐bio interface with living cells. Here, it is reported that nanolaminate plasmonic nanocavities on 3D vertical nanopillar arrays can support a broadband SERS operation with large enhancement factors (>106) under laser excitations at 532, 633, and 785 nm. The multi‐band Raman mapping measurements show that nanolaminate plasmonic nanocavities on vertical nanopillar arrays exhibit broadband uniform SERS performance with diffraction‐limited resolution at a single nanopillar footprint. By selective exposure of embedded plasmonic hotspots in individual metal–insulator–metal (MIM) nanogaps, nanoscale broadband SERS operation at the single MIM nanocavity level with visible and near‐infrared (vis–NIR) excitations is demonstrated. Numerical studies reveal that nanolaminate plasmonic nanocavities on vertical nanopillars can support multiple hybridized plasmonic modes to concentrate optical fields across a broadband wavelength range from 500 to 900 nm at the nanoscale.
Plasmonic nanostructures exhibit intriguing optical properties due to spectrally selective plasmon resonance and thus have broad applications, including biochemical sensing and photoelectric detections. However, excited plasmons are often strongly influenced by the substrates supporting the metallic nanostructures, which not only weakens the intrinsic plasmon coupling effect, but also results in a great reduction of optical near‐field enhancement. Here, a plasmonic nanostructure combining collapsible Au‐nanofingers with selective‐etching that enables Au to be suspended is demonstrated, thus avoiding the undesirable influence of the substrates on the local near‐field distribution and forming symmetric electromagnetic‐field enhancements at both the top and bottom surfaces. The polymer support of the Au‐nanofingers is selectively etched by oxygen plasma, while the Au‐cap retains its original size. After an ultrathin dielectric coating is applied on the Au‐nanofingers, suspended Au‐caps with extremely small dielectric gaps are formed via the collapse of neighboring Au‐nanofingers by exposing them to ethanol. These nanostructures can provide a surface‐enhanced Raman scattering (SERS) enhancement of up to ≈109, which is nearly twice that in the nonsuspended system. As a highly active SERS substrate, the label‐free detection of low‐concentration harmful plastic phthalates in a child's urine without any pretreatment is successfully demonstrated, which suggests that this method is suitable for medical prediagnosis.
more » « less- Award ID(s):
- 1635612
- NSF-PAR ID:
- 10458837
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 8
- Issue:
- 2
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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