In this talk, I will present ultrastable tip-enhanced Raman spectroscopy (TERS) setup that has a home-built feedback system to compensate possible drift in all three dimensions during hyperspectral Raman imaging. The ultrastable optical nanoimaging system enables long-duration and high resolution TERS imaging of large-sized nanostructured samples far beyond conventional TERS imaging systems. I will show applications of ultrastable TERS imaging of 2D material systems, in which nanoscale characterization of unique physical properties of atomic layer of 2D semiconductors and structural properties of self-assembled biomolecular nanoarchitectures on 2D materials is performed.
Field-enhanced biosensing has attracted considerable attention due to its capability of highly sensitive biomolecular detection and analysis. Here, we demonstrate a variety of nanogap-enhanced spectroscopies (fluorescence, Raman, infrared absorption) of biomolecular complexes using plasmonic and dielectric nanostructures. Plasmonic nanogaps between gold nanoparticles and gold nanoholes enabled us to perform plasmonic digital biosensing with the limit of detection (LOD) down to sub-fM level. All-dielectric nanogap antennas also allowed us for highly sensitive fluorescence immunosensing.
Visualization of enhanced optical fields in metallic and dielectric nanostructures resonated with infrared light is fundamentally important to control optical properties of metamaterials. However, conventional optical microscopic techniques, such as Fourier Transform Infrared absorption spectroscopy cannot resolve optically induced light fields of dielectric structures because of their low spatial resolution due to the diffraction limit of the infrared light. We introduced super-resolution far-field infrared spectroscopy to visualize the distribution of optical fields of dielectric-based metamaterials in the infrared region. Our newly developed novel infrared spectroscopic technique called as mid-infrared photothermal microscopy demonstrates to investigate optical field properties of silicon-based metamaterials at the sub-micrometer scale, which is far-beyond the diffraction limit of the infrared light.
Plasmon-enhanced biosensing has attracted considerable attention due to its capability of highly sensitive biomolecular detection and analysis. Here, we demonstrate several types of gap-mode plasmon-enhanced spectroscopies for detection of biomolecular complexes. The first one is demonstrated with a nanometric gap between a silver tip and gold substrate, enabling to detect gap-enhanced Raman scattering from an inorganic-binding peptide and to spectroscopically elucidate the binding dynamics and mechanism. The other demonstration is based on gap-mode SPR sensing of coronavirus (SARS-CoV-2) in which antibody-functionalized gold nanoparticle with relatively large diameter played crucial plasmonic roles in detecting SARS-CoV-2 nucleocapsid proteins at femtomolar lever.
Tip-enhanced Raman scattering (TERS) microscopy has been regarded as a promising application of plasmonics for nano-imaging and nano-analysis with a nanoscale spatial resolution far beyond the diffraction limit of light. However, TERS microscopy has been still limited to passive measurement of intrinsic molecular properties and functions. Here, we demonstrate active TERS microscopy in association with the local external stimuli, enabling to reversibly control chemical reactions in the vicinity of a plasmonic tip. The active function in TERS microscopy opens up a new approach to actively control molecular properties and functions at nanoscale.
The confinement and the enhancement of optical fields in the vicinity of metallic or dielectric nanostructures provide versatile applications in nanoscale devices and spectroscopies. It is therefore of great importance to investigate optical properties of nanostructures, such as the distribution of optical fields on the nanometer scale. In this work, we visualized the nanoscale distribution of optical fields induced by metallic and dielectric nanostructures in visible and infrared region, respectively. We utilized enhanced vibrational spectroscopies, such as a mid-infrared photothermal microscopy technique and a tip-enhanced Raman spectroscopy-based technique to study optical fields of nanostructures at the nanoscale.
We propose all dielectric metasurfaces for highly sensitive infrared absorption spectroscopy. The dielectric metasurfaces consisting of silicon microdisk arrays were designed and fabricated, realizing perfect reflection at certain mid-infrared wavelengths. Furthermore, tunable perfect reflection was achieved over the fingerprint region by changing diameter and height of Si disk, and also periodicity of the array, allowing us for molecular specific detection. Our dielectric perfect reflectors are promising for non-invasive molecular detection owing to ultralow heat generation under infrared irradiation.
Vibrational imaging based on mid-infrared photothermal (MIP) microscopy with the sub-micrometer spatial resolution is an indispensable analytical tool for a wide range of fields, such as polymer and medical science. In this talk, we will report multimodal imaging of polymer blends and biomolecules combining a MIP imaging with other optical microscopic techniques such as Raman or fluorescence imaging. Since Raman scattering exhibits complementary information of molecular vibrations and fluorescence imaging helps to understand biological dynamics by visualizing the distribution of biomarkers, our demonstration of multimodal imaging offers accurate and detailed characterization of molecular structures and functions of various samples.
Tip-enhanced optical microscopy using a metallic probe has been recognized as one of the most promising applications of plasmonics. Here, we present multimodal tip-enhanced vibrational microscopy enabling to perform nanoscale Raman and IR imaging beyond the diffraction limit of light.
Dielectric nanostructures with a high refractive index and a low optical loss have recently attracted considerable attention as an alternative to plasmonic nanostructures. The electromagnetic multipoles excited in the high-index dielectric nanostructures enable the manipulation of light beyond the diffraction limit and offer high electromagnetic field enhancement comparable to that exhibited by the plasmonic nanostructures. Here, we demonstrate all-dielectric field enhanced spectroscopy using high-index dielectric nanoantenna and metasurface, enabling us to perform Raman and Infrared spectroscopies with single molecule detection sensitivity.
Tip-enhanced spectroscopies have attracted considerable attention due to the capability of nanoscale optical characterization. Here, we demonstrated multimodal tip-enhanced vibrational spectroscopy for nanoscale analysis and imaging. A metallic probe tip was utilized to locally enhance not only Raman scattering but also IR absorption of sample molecules. Simultaneous detection of nano-Raman and nano-IR signal enabled us to elucidate nanoscale physicochemical properties of a variety of nanomaterials such as polymer thin films, self-assembled monolayers and biomaterials.
Plasmonically-induced optical heating is a crucial issue for field-enhanced spectroscopy of heat sensitive materials such as biomolecules. Here in this talk, we introduce efficient ways to spectroscopically evaluate the elevated temperature in the vicinity of metallic nanostructures and even to significantly suppress it. As an alternative to plasmonic nanostructures, we also introduce low-loss dielectric nanostructures to achieve complete suppression of the optical heating along with high field enhancement, enabling us to demonstrate field-enhanced spectroscopy of biomolecules without any thermal damages.
Dielectric nanostructures with high refractive index and low optical loss have attracted considerable attention as an alternative to plasmonic nanostructures. We experimentally demonstrated to control the visible electromagnetic resonances of Si-based core-shell nanostructures by thermally varying the core-shell ratio. We also found a Fano resonance which was generated by the interference between the electric and magnetic dipole moments excited in the core-shell nanostructures. The all-dielectric nanostructures realized low energy loss and high electromagnetic field enhancement comparable with that exhibited by plasmonic nanostructures. These unique optical properties would enable us to demonstrate effective field-enhanced spectroscopy and imaging with low heat generation.
Tip-enhanced Raman spectroscopy (TERS) offers one of the best techniques for analysis and imaging of molecule structures at nanoscale spatial resolution. An important issue in TERS is to improve the detection sensitivity of inherently weak Raman scattering so as to observe varieties of materials. For enhancement of the Raman signal, fully metallized tips are utilized in TERS, which enhance signals through plasmon oscillation at the tip apex. However, length of metal along the tip axis is on the order of a few to a few tens of micrometers, which means the plasmon resonant wavelength is much longer than the wavelength of the visible light used in TERS. From that point, if the tip has a metallic nanostructure on the apex, it would give better enhancement in the visible range compared with fully metallized tips. In this research, we employed photoreduction as a new fabrication method to grow a metallic nanostructure at the tip apex. We found a particular property of photoreduction that it occurs selectively at sharp corners, such as the tip apex of silicon cantilevers. Through this property, we succeeded in growing silver nanoparticles selectively at the tip apex. One of the advantages of the photoreduction is that the size of metal nanostructures is well controlled by optimizing various parameters. We controlled the size of silver nanoparticles from 100 to 400 nm by changing the laser exposure time. Furthermore, we obtained an order of magnitude higher enhancement from our fabricated tip compared with fully metalized tips through TERS measurements.
When Raman scattering is excited from the evanescent light field created by illuminating the apex of a sharp metallic
nano-tip, it achieves new aspects with strong enhancement of scattering efficiencies and super resolving capabilities. The
primary mechanism of tip-sample interaction is electromagnetic, which is based on the excitation of localized surface
plasmon polaritons. However, when the tip is close enough to the sample, typically at molecular distances, the chemical
interactions between the tip and the sample become important. Strong temporal fluctuations of Raman scattering,
including fluctuations of peak frequencies and peak intensities, together with extraordinary enhancement of several
peaks, were observed. These temporal fluctuations, which are typical signature of single molecule detection, were
attributed to the changes of molecular orientations of the sample molecules in the upper layer of the nanocluster, which
got chemically adsorbed at the tip molecules.
Near-field Raman scattering has been successfully utilized to study the interaction between a metal-coated nano-tip and
carbon nanostructures, such as carbon-60 molecules and single walled carbon nanotubes. The enhanced and localized
light field in the vicinity of the tip apex provides high resolution imaging as well as the detection of weak vibrational
modes. Apart from the electromagnetic and chemical interactions, a mechanical interaction between tip molecules and
the sample molecules has also been investigated.
A light microscope capable to show images of molecules in nanometer scale has been a dream of scientists, which, however, is difficult due to the strict limitation of spatial resolution due to the wave nature of light. While there have been attempts to overcome the diffraction limit by using nonlinear response of materials, near-field optical microscopy could provide better detecting accuracy. In this paper, we present molecular distribution nano-imaging colored by Raman-scattering spectral shifting, which is probed with a metallic tip. The metallic probe tip has been used to enhance the optical field only in the vicinity of probe tip. The effect is similar to the one seen in the detection of molecules on the metal-island film, known as surface-enhanced Raman spectroscopy (SERS), while in this case a single metallic tip works for the field enhancement in nanometer scale.
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