Review: Tip-based vibrational spectroscopy for nanoscale analysis of emerging energy materials

Abstract

Vibrational spectroscopy is one of the key instrumentations that provide non-invasive investigation of structural and chemical composition for both organic and inorganic materials. However, diffraction of light fundamentally limits the spatial resolution of far-field vibrational spectroscopy to roughly half the wavelength. In this article, we thoroughly review the integration of atomic force microscopy (AFM) with vibrational spectroscopy to enable the nanoscale characterization of emerging energy materials, which has not been possible with far-field optical techniques. The discussed methods utilize the AFM tip as a nanoscopic tool to extract spatially resolved electronic or molecular vibrational resonance spectra of a sample illuminated by a visible or infrared (IR) light source. The absorption of light by electrons or individual functional groups within molecules leads to changes in the sample’s thermal response, optical scattering, and atomic force interactions, all of which can be readily probed by an AFM tip. For example, photothermal induced resonance (PTIR) spectroscopy methods measure a sample’s local thermal expansion or temperature rise. Therefore, they use the AFM tip as a thermal detector to directly relate absorbed IR light to the thermal response of a sample. Optical scattering methods based on scanning near-field optical microscopy (SNOM) correlate the spectrum of scattered near-field light with molecular vibrational modes. More recently, photo-induced force microscopy (PiFM) has been developed to measure the change of the optical force gradient due to the light absorption by molecular vibrational resonances using AFM’s superb sensitivity in detecting tip-sample force interactions. Such recent efforts successfully breech the diffraction limit of light to provide nanoscale spatial resolution of vibrational spectroscopy, which will become a critical technique for characterizing novel energy materials.

Key words： vibrational spectroscopy; atomic force microscopy; photo-thermal induced resonance; scanning near-field optical microscopy; tip-enhanced Raman spectroscopy; photo-induced force microscopy; molecular resonances; surface phonon polaritons; energy materials

Acknowledgments

This work was supported by the National Science Foundation (CBET-1605584) and the University of Utah Funding Incentive Seed Grant. A.J. also acknowledges financial supports from the University of Utah’s Sid Green Fellowship and the National Science Foundation Graduate Research Fellowship (No. 2016213209). C.S. acknowledges financial support from the University of Utah Undergraduate Research Opportunities Program (UROP).

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