This Perspective highlights recent advances in infrared vibrational chemical nano-imaging. In its implementations of scattering scanning near-field optical microscopy (s-SNOM) and photothermal-induced resonance (PTIR), IR nanospectroscopy provides few-nanometer spatial resolution for the investigation of polymer, biomaterial, and related soft-matter surfaces and nanostructures. Broad-band IR s-SNOM with coherent laser and synchrotron sources allows for chemical recognition with small-ensemble sensitivity and the potential for sensitivity reaching the single-molecule limit. Probing selected vibrational marker resonances, it gives access to nanoscale chemical imaging of composition, domain morphologies, order/disorder, molecular orientation, or crystallographic phases. Local intra- and intermolecular coupling can be measured through frequency shifts of a vibrational marker in heterogeneous environments and associated inhomogeneities in vibrational dephasing. In combination with ultrafast spectroscopy, the vibrational coherent evolution of homogeneous sub-ensembles coupled to their environment can be observed. Outstanding challenges are discussed in terms of extensions to coherent and multidimensional spectroscopies, implementation in liquid and in situ environments, general sample limitations, and engineering s-SNOM scanning probes to better control the nano-localized optical excitation and to increase sensitivity.

Molecular self-assembly, the function of biomembranes and the performance of organic solar cells rely on nanoscale molecular interactions. Understanding and control of such materials have been impeded by difficulties in imaging their properties with the desired nanometre spatial resolution, attomolar sensitivity and intermolecular spectroscopic specificity. Here we implement vibrational scattering-scanning near-field optical microscopy with high spectral precision to investigate the structure–function relationship in nano-phase separated block copolymers. A vibrational resonance is used as a sensitive reporter of the local chemical environment and we image, with few nanometre spatial resolution and 0.2 cm−1 spectral precision, solvatochromic Stark shifts and line broadening correlated with molecular-scale morphologies. We discriminate local variations in electric fields between nano-domains with quantitative agreement with dielectric continuum models. This ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems.

Optical resonators can enhance light–matter interaction, modify intrinsic molecular properties such as radiative emission rates, and create new molecule–photon hybrid quantum states. To date, corresponding implementations are based on electronic transitions in the visible spectral region with large transition dipoles yet hampered by fast femtosecond electronic dephasing. In contrast, coupling molecular vibrations with their weaker dipoles to infrared optical resonators has been less explored, despite long-lived coherences with 2 orders of magnitude longer dephasing times. Here, we achieve excitation of molecular vibrations through configurable optical interactions of a nanotip with an infrared resonant nanowire that supports tunable bright and nonradiative dark modes. The resulting antenna–vibrational coupling up to 47 ± 5 cm –1 exceeds the intrinsic dephasing rate of the molecular vibration, leading to hybridization and mode splitting. We observe nanotip-induced quantum interference of vibrational excitation pathways in spectroscopic nanoimaging, which we model classically as plasmonic electromagnetically induced scattering as the phase-controlled extension of the classical analogue of electromagnetically induced transparency and absorption. Our results present a new regime of IR spectroscopy for applications of vibrational coherence from quantum computing to optical control of chemical reactions.

Nanoscale spectroscopy and imaging of organic materials reveal heterogeneity in molecular orientation in crystalline domains.