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For decades, infrared (IR) spectroscopy has advanced on two distinct frontiers: enhancing spatial resolution and broadening spectroscopic information. Although atomic force microscopy (AFM)-based IR microscopy overcomes Abbe’s diffraction limit and reaches sub-10 nm spatial resolutions, time-domain two-dimensional IR spectroscopy (2DIR) provides insights into molecular structures, mode coupling and energy transfers. Here we bridge the boundary between these two techniques and develop AFM-2DIR nanospectroscopy. Our method offers the spatial precision of AFM in combination with the rich spectroscopic information provided by 2DIR. This approach mechanically detects the sample’s photothermal responses to a tip-enhanced femtosecond IR pulse sequence and extracts spatially resolved spectroscopic information via FFTs. In a proof-of-principle experiment, we elucidate the anharmonicity of a carbonyl vibrational mode. Further, leveraging the near-field photons’ high momenta from the tip enhancement for phase matching, we photothermally probe hyperbolic phonon polaritons in isotope-enriched h10BN. Our measurements unveil an energy transfer between phonon polaritons and phonons, as well as among different polariton modes, possibly aided by scattering at interfaces. The AFM-2DIR nanospectroscopy enables the in situ investigations of vibrational anharmonicity, coupling and energy transfers in heterogeneous materials and nanostructures, especially suitable for unravelling the relaxation process in two-dimensional materials at IR frequencies.
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Revealing Phonon Polaritons in Hexagonal Boron Nitride by Multipulse Peak Force Infrared Microscopy
Abstract Probing of polaritons in 2D materials is facilitated by spectroscopic imaging with nanometer spatial resolution. The combination of atomic force microscopy and infrared laser sources provides access for in situ mappings of phonon polaritons. Here, it is demonstrated that the photothermal‐based peak force infrared microscopy is capable of revealing phonon polaritons with high spatial resolution in isotopically pure hexagonal boron nitride microstructures without damaging the sample. To further improve the sensitivity, peak force infrared microscopy is enhanced with a scheme of multiple laser pulse excitation. The resulting method of multipulse peak force infrared microscopy can detect phonon polaritons with high sensitivity, which is particularly useful for probing polaritons in 2D materials with high damping characteristics.
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- PAR ID:
- 10457672
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Optical Materials
- Volume:
- 8
- Issue:
- 5
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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