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Title: Atomic-force-microscopy-based time-domain two-dimensional infrared nanospectroscopy
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.  more » « less
Award ID(s):
1847765
PAR ID:
10568367
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Nature Springer
Date Published:
Journal Name:
Nature Nanotechnology
Volume:
19
Issue:
8
ISSN:
1748-3387
Page Range / eLocation ID:
1108 to 1115
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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