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Abstract The process of tip‐enhanced Raman scattering (TERS) depends critically on the morphology near the apex of the tip used in the experiment. Many tip designs have focused on optimization of electromagnetic enhancement in the near‐field, which is controlled to a large extent by subtle details at the nanoscale that remain difficult to reproduce in the tip fabrication process. The use of focused ion beams (FIB) permit modification of larger features on the tip in a reproducible manner, yet this approach cannot produce sub‐20‐nm structures important for optimum near‐field enhancement. Nonetheless, FIB milling offers excellent opportunities for improving the far‐field radiation properties of the tip‐antenna, a feature that has received relatively little attention in the TERS research community. In this work, we use finite‐difference time‐domain (FDTD) simulations to study both the near‐field and far‐field radiation efficiency of several tip‐antenna systems that can be constructed with FIB techniques in a feasible manner. Starting from blunt etched tips, we find that excellent overall enhancement of the TERS signal can be obtained with pillar‐type tips. Furthermore, by applying vertical grooves on the tip's shaft, the overall efficiency can be improved even more, producing TERS signals that are up to 10‐fold stronger than signals obtained from an ideal (unmodified) sharp tip of 10‐nm radius. The proposed designs constitute a feasible route toward a tip fabrication process that not only yields more reproducible tips but also promises much stronger TERS signals.
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Methods to fabricate and recycle plasmonic probes for ultrahigh vacuum scanning tunneling microscopy‐based tip‐enhanced Raman spectroscopy
Abstract Scanning tunneling microscopy‐based tip‐enhanced Raman spectroscopy (TERS) is a powerful analytical technique for surface characterization, providing both topological and chemical information with sub‐nm spatial resolution, well below the diffraction limit of light. In order to take advantage of plasmonic activity, it is necessary to use silver (Ag) probes due to their plasmonic range in the visible region. However, the Ag probe fabrication process remains challenging and is not yet standardized in practice, leading to inconsistent enhancements even for two similar types of tips prepared consecutively. In this work, we demonstrate an alternative way to reuse and recycle a plasmonic tip for distinct molecular systems inside an ultrahigh vacuum (UHV). We provide evidence of the ability to recycle tips without compromising the TERS experimental results. A long‐term preservation (>2 months) of plasmonically active probes inside UHV is demonstrated.
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- Award ID(s):
- 1807465
- PAR ID:
- 10452384
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Raman Spectroscopy
- Volume:
- 52
- Issue:
- 2
- ISSN:
- 0377-0486
- Page Range / eLocation ID:
- p. 573-580
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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