Solid-state physics, material science, as well as biology, need continuously more and more information from their samples. High spatial resolution information such as optical or electrical properties, chemical species identification as well as topography are important information that optical microscopy or Scanning Probe Microscopy (SPM) can provide. Although electron microscopy (SEM and TEM) certainly assumes a position of absolute importance in the field, its cost and its need to be used by highly specialised personnel still make it an instrument of limited everyday use. On the contrary, probe microscopy has now become of very high diffusion in research labs. To develop my thesis I focused myself on three main and somehow related microscopy techniques: high resolution Raman microscopy, Scanning Near-field Optical Microscopy (SNOM), and Tip Enhanced Raman Spectroscopy (TERS). All of them are state-of-the-art on surface optical analysis techniques but still present relevant limits; among others, respectively: spatial resolution, local power density, complexity and field of applicability. My approach wants to combine some aspects of these techniques to go beyond their limits. Raman spectroscopy is a powerful optical technique, which measures the inelastic scattering of an incoming EM radiation due to the vibrational modes of the molecules present on the surface of a sample. Thanks to its high specificity, it is very powerful in identifying the chemical components of a sample. Several organic and inorganic molecules have their typical Raman spectral peaks, hence, by the Raman spectra, it’s possible to provide a qualitative and quantitative analysis of the elements of a sample. High spatial resolution Raman setups uses the combination of a confocal microscope with a spectrometer assisted by a series of long pass and band pass filters. Despite its extreme versatility, basing Raman spectroscopy on a confocal system also constrains it to acquire its limit in spatial resolution determined by the limit of diffraction. To overcome this limit the most used techniques in SPM are Scanning Near-field Optical Microscopy (SNOM) and Tip Enhanced Raman Spectroscopy (TERS). Both of them exploits evanescent field, which is an electric field that is created by oscillating charges and/or currents and does not propagate in the far field as a classical electromagnetic wave, but is spatially concentrated very near to its source. This confinement allows to obtain field sources definitely smaller than in confocal systems. In SNOM technique, the excitation light is focused through an aperture smaller than the wavelength, creating an evanescent field strongly localized near the aperture itself. Scanning the sample in this near range brings the spatial resolution down to the aperture dimension. The main disadvantage of aperture SNOM is that the overall optical efficiency of probes is very low. The excitation power cannot be too high in order to prevent any damage of the probe, hence the energy that reaches the sample is usually not enough for Raman analysis. TERS instead is more suitable for this purpose. It basically exploits Surface Enhanced Raman Spectroscopy (SERS) principles, using a laser irradiated gold sharp tip to obtain a local enhancement at its apex. Its good efficiency permits to analyze Raman effects with a spatial super-resolution, but, on the other hand, TERS probes usually lack of reprodubility and require very skilled and specialised users. My PhD project has been focused to investigate and optimize an original approach to perform high resolution optical microscopy and Raman spectroscopy, well below the diffraction limit. The concept is to exploit the optical proprieties of a dielectric micro bead lens to achieve a powerful nanoscale near field confinement of light and the Scanning Probe Microscopy (SPM) technique to scan a sample to acquire optical maps. When a dielectric micro bead is hit by an Electromagnetic (EM) wave its effect is to transmit and concentrate the incident EM radiation in a specific area called nanojet, at first glance similar to that created with a standard lens. Some optical proprieties of the nanojets have been already introduced in the literature, but their application in the world of SPM, their employment in Raman microscopy and their combination with nanostructures to improve the spatial resolution are novel features whose investigation is promising. I gave to this technique the name of Beam Mediated Microscopy (BeMM). The combination of super resolution bead mediated SPM with Raman spectroscopy opens interesting perspectives about powerful surface analysis for samples that need a versatile optical probe with a high spatial resolution and soft interaction with the sample, like soft matter substrates or biosamples.

Bead Mediated Microscopy: from high resolution microscopy to nano-Raman

BIAGINI, CLAUDIO
2020-11-24

Abstract

Solid-state physics, material science, as well as biology, need continuously more and more information from their samples. High spatial resolution information such as optical or electrical properties, chemical species identification as well as topography are important information that optical microscopy or Scanning Probe Microscopy (SPM) can provide. Although electron microscopy (SEM and TEM) certainly assumes a position of absolute importance in the field, its cost and its need to be used by highly specialised personnel still make it an instrument of limited everyday use. On the contrary, probe microscopy has now become of very high diffusion in research labs. To develop my thesis I focused myself on three main and somehow related microscopy techniques: high resolution Raman microscopy, Scanning Near-field Optical Microscopy (SNOM), and Tip Enhanced Raman Spectroscopy (TERS). All of them are state-of-the-art on surface optical analysis techniques but still present relevant limits; among others, respectively: spatial resolution, local power density, complexity and field of applicability. My approach wants to combine some aspects of these techniques to go beyond their limits. Raman spectroscopy is a powerful optical technique, which measures the inelastic scattering of an incoming EM radiation due to the vibrational modes of the molecules present on the surface of a sample. Thanks to its high specificity, it is very powerful in identifying the chemical components of a sample. Several organic and inorganic molecules have their typical Raman spectral peaks, hence, by the Raman spectra, it’s possible to provide a qualitative and quantitative analysis of the elements of a sample. High spatial resolution Raman setups uses the combination of a confocal microscope with a spectrometer assisted by a series of long pass and band pass filters. Despite its extreme versatility, basing Raman spectroscopy on a confocal system also constrains it to acquire its limit in spatial resolution determined by the limit of diffraction. To overcome this limit the most used techniques in SPM are Scanning Near-field Optical Microscopy (SNOM) and Tip Enhanced Raman Spectroscopy (TERS). Both of them exploits evanescent field, which is an electric field that is created by oscillating charges and/or currents and does not propagate in the far field as a classical electromagnetic wave, but is spatially concentrated very near to its source. This confinement allows to obtain field sources definitely smaller than in confocal systems. In SNOM technique, the excitation light is focused through an aperture smaller than the wavelength, creating an evanescent field strongly localized near the aperture itself. Scanning the sample in this near range brings the spatial resolution down to the aperture dimension. The main disadvantage of aperture SNOM is that the overall optical efficiency of probes is very low. The excitation power cannot be too high in order to prevent any damage of the probe, hence the energy that reaches the sample is usually not enough for Raman analysis. TERS instead is more suitable for this purpose. It basically exploits Surface Enhanced Raman Spectroscopy (SERS) principles, using a laser irradiated gold sharp tip to obtain a local enhancement at its apex. Its good efficiency permits to analyze Raman effects with a spatial super-resolution, but, on the other hand, TERS probes usually lack of reprodubility and require very skilled and specialised users. My PhD project has been focused to investigate and optimize an original approach to perform high resolution optical microscopy and Raman spectroscopy, well below the diffraction limit. The concept is to exploit the optical proprieties of a dielectric micro bead lens to achieve a powerful nanoscale near field confinement of light and the Scanning Probe Microscopy (SPM) technique to scan a sample to acquire optical maps. When a dielectric micro bead is hit by an Electromagnetic (EM) wave its effect is to transmit and concentrate the incident EM radiation in a specific area called nanojet, at first glance similar to that created with a standard lens. Some optical proprieties of the nanojets have been already introduced in the literature, but their application in the world of SPM, their employment in Raman microscopy and their combination with nanostructures to improve the spatial resolution are novel features whose investigation is promising. I gave to this technique the name of Beam Mediated Microscopy (BeMM). The combination of super resolution bead mediated SPM with Raman spectroscopy opens interesting perspectives about powerful surface analysis for samples that need a versatile optical probe with a high spatial resolution and soft interaction with the sample, like soft matter substrates or biosamples.
24-nov-2020
bead; SNOM; Raman; optical microscopy; bead microscopy; Raman microscopy; Raman spectroscopy; microbead; microsphere
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11567/1030687
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