Remote near-field spectroscopy of vibrational strong coupling between organic molecules and phononic nanoresonators

Vibrational strong coupling (VSC) promises ultrasensitive IR spectroscopy and modification of material properties. Here, nanoscale mapping of VSC between organic molecules and individual IR nanoresonators is achieved by remote near-field spectroscopy. Phonon polariton (PhP) nanoresonators can dramatically enhance the coupling of molecular vibrations and infrared light, enabling ultrasensitive spectroscopies and strong coupling with minute amounts of matter. So far, this coupling and the resulting localized hybrid polariton modes have been studied only by far-field spectroscopy, preventing access to modal near-field patterns and dark modes, which could further our fundamental understanding of nanoscale vibrational strong coupling (VSC). Here we use infrared near-field spectroscopy to study the coupling between the localized modes of PhP nanoresonators made of h-BN and molecular vibrations. For a most direct probing of the resonator-molecule coupling, we avoid the direct near-field interaction between tip and molecules by probing the molecule-free part of partially molecule-covered nanoresonators, which we refer to as remote near-field probing. We obtain spatially and spectrally resolved maps of the hybrid polariton modes, as well as the corresponding coupling strengths, demonstrating VSC on a single PhP nanoresonator level. Our work paves the way for near-field spectroscopy of VSC phenomena not accessible by conventional techniques.This work was supported by the MCIN/AEI/10.13039/501100011033 under the María de Maeztu Units of Excellence Program (CEX2020-001038-M) and the Projects RTI2018-094830-B-100, PID2021-123949OB-I00, PID2019-107432GB-I00 and PID2021-122511OB-I00, as well as by the Graphene Flagship (GrapheneCore3, No. 881603). J.L. and J.H.E. are grateful for support from the Office of Naval Research (Award No. N00014-20-1-2474), for the BN crystal growth. S.V. acknowledges financial support by the Comunidad de Madrid through the Atracción de Talento program (grant no. 2020-T1/IND-20041). C.M.-E., R.E., and J.A. received funding from grant no. IT 1526-22 from the Basque Government for consolidated groups of the Basque University