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Atomic-force-microscopy-based time-domain two-dimensional infrared nanospectroscopy

Nature Nanotechnology (2024)Cite this article

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Abstract

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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Fig. 1: Operation flow of the AFM-2DIR method with PFIR detection.
Fig. 2: Representations of 2D-PFIR spectrum of carbonyl vibrational mode.
Fig. 3: Real-space mapping and interpretation of hyperbolic PhP of an h10BN flake.
Fig. 4: 2D-PFIR spectra of h10BN revealing energy transfers.
Fig. 5: PhP propagation characteristics in h10BN and energy transfer pathways.

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Data availability

The data that support the findings of this study are available from the corresponding author upon request. Source data are provided with this paper.

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Acknowledgements

We would like to thank M. T. Zanni, G. C. Walker, J.-H. Jiang and J. T. King for encouragement and consultation on the 2DIR spectroscopy or time-resolved spectroscopy. X.G.X. would like to acknowledge support from the Beckman Young Investigator Award from the Arnold and Mabel Beckman Foundation, the Sloan Research Fellowship from the Alfred P. Sloan Foundation and the Camille Dreyfus Teacher-Scholar Award from the Camille and Henry Dreyfus Foundation. Q.X. and X.G.X. would also like to acknowledge support from the National Science Foundation, award no. CHE 1847765, and Lehigh grant no. COREAWD41. Support for the hBN crystal growth came from the Office of Naval Research, award no. N00014-22-1-2582.

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Authors and Affiliations

  1. Department of Chemistry, Lehigh University, Bethlehem, PA, US

    Qing Xie & Xiaoji G. Xu

  2. Ames National Laboratory, Iowa State University, Ames, IA, US

    Yu Zhang

  3. Tim Taylor Department of Chemical Engineering, Kansas State University, Manhattan, KS, US

    Eli Janzen & James H. Edgar

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Contributions

X.G.X. conceived the design of the AFM-2DIR experiment and instrument. The experimental setup was built by X.G.X. and Q.X. Q.X. carried out the experiment, simulation, data collection and analysis. E.J. and J.H.E. provides the isotope-enriched h10BN for the study. Y.Z. provided assistance on the carbonyl anharmonicity interpretation. The paper was written together by X.G.X. and Q.X. X.G.X. oversaw the research.

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Correspondence to Xiaoji G. Xu.

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Nature Nanotechnology thanks Qing Dai and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–8 and Note 1.

Source data

41565_2024_1670_MOESM2_ESM.xlsx

Source Data Fig. 2. Raw data for the carbonyl measurements shown in Fig. 2a,c. There are four columns in each dataset: time axis of t1, PFIR photothermal signal, scanned t2-stage location and scanned t1-stage location. After sequential FFTs, the time-domain 2D spectrum should be plotted from the raw data here. Source Data Fig. 4. Raw data for the h10BN AFM-2DIR measurements shown in Fig. 4d,e.

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Xie, Q., Zhang, Y., Janzen, E. et al. Atomic-force-microscopy-based time-domain two-dimensional infrared nanospectroscopy. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01670-w

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