Chemically-synthesized single-crystalline silver nanowire (AgNW) probes can combine the scanning tunneling microscopy (STM) technique with tip-enhanced Raman scattering spectroscopy (TERS) for complementary morphological and chemical information with nanoscale spatial resolution. However, its performance has been limited by the blunt nanowire tip geometry, the insulating surfactant layer coating AgNW surfaces, and the thermal-induced mechanical vibrations. Here, we report a reproducible fabrication method for the preparation of sharp-tip AgNW-based TERS probes. By removing the polyvinylpyrrolidone (PVP) surfactant molecules from the AgNW surfaces for stable electrical conductivity and controlling the protruding length with μm-level accuracy for improved mechanical stability, we demonstrate atomic-resolution STM imaging with the sharp-tip AgNW probe. Furthermore, the sharp-tip AgNW has an excellent TER enhancement (∼1.1 × 10 6 ), which is about 66 folds of that achieved by regular AgNWs. Our experiments demonstrate that AgNWs with clean interfaces and the proper tip geometry can provide reliable and reproducible STM and TER characterizations, which remove the hurdles preventing the implementation of AgNW in STM-based near-field optical applications for a broad community.
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Optimizing the near‐field and far‐field properties of tips in tip‐enhanced Raman scattering
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.
more » « less- Award ID(s):
- 1905582
- PAR ID:
- 10367432
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Raman Spectroscopy
- Volume:
- 52
- Issue:
- 12
- ISSN:
- 0377-0486
- Page Range / eLocation ID:
- p. 2018-2028
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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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null (Ed.)Microsphere Photolithography (MPL) is a nanopatterning technique that utilizes a self-assembled monolayer of microspheres as an optical element to focus incident radiation inside a layer of photoresist. The microspheres produces a sub-diffraction limited photonic-jet on the opposite side of each microsphere from the illumination. When combined with pattern transfer techniques such as etching/lift-off, MPL provides a versatile, low-cost fabrication method for producing hexagonal close-packed metasurfaces. This article investigates the MPL process for creating refractive index (RI) sensors on the cleaved tips of optical fiber. The resonant wavelength of metal elements on the surface is dependent on the local dielectric environment and allows the refractive index of an analyte to be resolved spectrally. A numerical study of hole arrays defined in metal films shows that the waveguide mode provides good sensitivity to the analyte refractive index. This can be readily tuned by adjusting the MPL exposure and the simulation results guide the fabrication of a defect tolerant refractive index sensor on the tip of a fiber tip with a sensitivity of 613 nm/RIU. The conformal nature of the microsphere monolayer simplifies the fabrication process and provides a viable alternative to direct-write techniques such as Focused Ion Beam (FIB) millingmore » « less
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null (Ed.)Abstract Tip-enhanced nano-spectroscopy, such as tip-enhanced photoluminescence (TEPL) and tip-enhanced Raman spectroscopy (TERS), generally suffers from inconsistent signal enhancement and difficulty in polarization-resolved measurement. To address this problem, we present adaptive tip-enhanced nano-spectroscopy optimizing the nano-optical vector-field at the tip apex. Specifically, we demonstrate dynamic wavefront shaping of the excitation field to effectively couple light to the tip and adaptively control for enhanced sensitivity and polarization-controlled TEPL and TERS. Employing a sequence feedback algorithm, we achieve ~4.4 × 10 4 -fold TEPL enhancement of a WSe 2 monolayer which is >2× larger than the normal TEPL intensity without wavefront shaping. In addition, with dynamical near-field polarization control in TERS, we demonstrate the investigation of conformational heterogeneity of brilliant cresyl blue molecules and the controllable observation of IR-active modes due to a large gradient field effect. Adaptive tip-enhanced nano-spectroscopy thus provides for a systematic approach towards computational nanoscopy making optical nano-imaging more robust and widely deployable.more » « less
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Abstract We demonstrate the use of tip-enhanced Raman spectroscopy (TERS) on polymeric microstructures fabricated by two-photon polymerization direct laser writing (TPP-DLW). Compared to the signal intensity obtained in confocal Raman microscopy, a linear enhancement of almost two times is measured when using TERS. Because the probing volume is much smaller in TERS than in confocal Raman microscopy, the effective signal enhancement is estimated to be ca. 104. We obtain chemical maps of TPP microstructures using TERS with relatively short acquisition times and with high spatial resolution as defined by the metallic tip apex radius of curvature. We take advantage of this high resolution to study the homogeneity of the polymer network in TPP microstructures printed in an acrylic-based resin. We find that the polymer degree of conversion varies by about 30% within a distance of only 100 nm. The combination of high resolution topographical and chemical data delivered by TERS provides an effective analytical tool for studying TPP-DLW materials in a non-destructive way.
