3192323.pdf

Principle of Mixer and Tapping Demodulatio

Nano-FTIR Absorption Spectroscopy of Molecular Fingerprints at 20 nm Spatial Resolution

We demonstrate Fourier transform infrared nanospectroscopy (nano-FTIR) based on a scattering-type scanning near-field optical microscope (s-SNOM) equipped with a coherent-continuum infrared light source. We show that the method can straightforwardly determine the infrared absorption spectrum of organic samples with a spatial resolution of 20 nm, corresponding to a probed volume as small as 10 zeptoliter (10^–20 L). Corroborated by theory, the nano-FTIR absorption spectra correlate well with conventional FTIR absorption spectra, as experimentally demonstrated with poly­(methyl methacrylate) (PMMA) samples. Nano-FTIR can thus make use of standard infrared databases of molecular vibrations to identify organic materials in ultrasmall quantities and at ultrahigh spatial resolution. As an application example we demonstrate the identification of a nanoscale PDMS contamination on a PMMA sample

Ultrafast Dynamics of Surface Plasmons in InAs by Time-Resolved Infrared Nanospectroscopy

We report on time-resolved mid-infrared (mid-IR) near-field spectroscopy of the narrow bandgap semiconductor InAs. The dominant effect we observed pertains to the dynamics of photoexcited carriers and associated surface plasmons. A novel combination of pump–probe techniques and near-field nanospectroscopy accesses high momentum plasmons and demonstrates efficient, subpicosecond photomodulation of the surface plasmon dispersion with subsequent tens of picoseconds decay under ambient conditions. The photoinduced change of the probe intensity due to plasmons in InAs is found to exceed that of other mid-IR or near-IR media by 1–2 orders of magnitude. Remarkably, the required control pulse fluence is as low as 60 μJ/cm², much smaller than fluences of ∼1–10 mJ/cm² previously utilized in ultrafast control of near-IR plasmonics. These low excitation densities are easily attained with a standard 1.56 μm fiber laser. Thus, InAsa common semiconductor with favorable plasmonic properties such as a low effective masshas the potential to become an important building block of optically controlled plasmonic devices operating at infrared frequencies

Graphene-Based Platform for Infrared Near-Field Nanospectroscopy of Water and Biological Materials in an Aqueous Environment

Scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful nanoscale spectroscopic tool capable of characterizing individual biomacromolecules and molecular materials. However, applications of scattering-based near-field techniques in the infrared (IR) to native biosystems still await a solution of how to implement the required aqueous environment. In this work, we demonstrate an IR-compatible liquid cell architecture that enables near-field imaging and nanospectroscopy by taking advantage of the unique properties of graphene. Large-area graphene acts as an impermeable monolayer barrier that allows for nano-IR inspection of underlying molecular materials in liquid. Here, we use s-SNOM to investigate the tobacco mosaic virus (TMV) in water underneath graphene. We resolve individual virus particles and register the amide I and II bands of TMV at <i>ca</i>. 1520 and 1660 cm^–1, respectively, using nanoscale Fourier transform infrared spectroscopy (nano-FTIR). We verify the presence of water in the graphene liquid cell by identifying a spectral feature associated with water absorption at 1610 cm^–1

Efficiency of Launching Highly Confined Polaritons by Infrared Light Incident on a Hyperbolic Material

We investigated phonon–polaritons in hexagonal boron nitridea naturally hyperbolic van der Waals materialby means of the scattering-type scanning near-field optical microscopy. Real-space nanoimages we have obtained detail how the polaritons are launched when the light incident on a thin hexagonal boron nitride slab is scattered by various intrinsic and extrinsic inhomogeneities, including sample edges, metallic nanodisks deposited on its top surface, random defects, and surface impurities. The scanned tip of the near-field microscope is itself a polariton launcher whose efficiency proves to be superior to all the other types of polariton launchers we studied. Our work may inform future development of polaritonic nanodevices as well as fundamental studies of collective modes in van der Waals materials

Ultrafast and Nanoscale Plasmonic Phenomena in Exfoliated Graphene Revealed by Infrared Pump–Probe Nanoscopy

Pump–probe spectroscopy is central for exploring ultrafast dynamics of fundamental excitations, collective modes, and energy transfer processes. Typically carried out using conventional diffraction-limited optics, pump–probe experiments inherently average over local chemical, compositional, and electronic inhomogeneities. Here, we circumvent this deficiency and introduce pump–probe infrared spectroscopy with ∼20 nm spatial resolution, far below the diffraction limit, which is accomplished using a scattering scanning near-field optical microscope (s-SNOM). This technique allows us to investigate exfoliated graphene single-layers on SiO₂ at technologically significant mid-infrared (MIR) frequencies where the local optical conductivity becomes experimentally accessible through the excitation of surface plasmons via the s-SNOM tip. Optical pumping at near-infrared (NIR) frequencies prompts distinct changes in the plasmonic behavior on 200 fs time scales. The origin of the pump-induced, enhanced plasmonic response is identified as an increase in the effective electron temperature up to several thousand Kelvin, as deduced directly from the Drude weight associated with the plasmonic resonances