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.
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.
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.
We propose a new nano-imaging technique for intrinsic absorption properties of materials under a platform of conventional aperture-less near-field scanning optical microscopy (NSOM). In aperture-less NSOM, when a silicon nanotip is utilized and illuminated by the visible light instead of a metallic tip, Raman scattering of silicon from the tip apex can be obtained. Since the wavelength of this Raman scattered light is shifted to 520cm-1 from the one of the excitation light, far-field background signal excited by the diffraction limited focus spot of the incident light, which is one of the major problems in aperture-less NSOM, can be avoided. When the silicon nano-tip is on the sample and illuminated, the Raman signal of silicon can be partially absorbed by the sample while passing through it, so that measuring the intensity of the Raman signal of silicon enables us to observe the absorption behavior of the sample at nano-scale. Because the absorbance of light is dependent on the absorption coefficient of the sample as well as its sample topography, it is needed to eliminate the effect of the sample topography from the absorption measurement to technically evaluate the absorption coefficient of the sample. For this purpose, we simultaneously employed two different incident lasers and utilized absorbance ratio between two wavelengths to monitor the absorption coefficient of the sample. As an example, we demonstrated that two types of carbon nanotubes, which have different absorption properties, could be clearly distinguished with nano-scale resolution by our technique.
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