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As a two-dimensional semimetal, graphene offers clear advantages for plasmonic applications over conventional metals, such as stronger optical field confinement, in situ tunability, and relatively low intrinsic losses. However, the operational frequencies at which plasmons can be excited in graphene are limited by the Fermi energy EF, which in practice can be controlled electrostatically only up to a few tenths of an electronvolt. Higher Fermi energies open the door to novel plasmonic devices with unprecedented capabilities, particularly at mid-infrared and shorter-wave infrared frequencies. In addition, this grants us a better understanding of the interaction physics of intrinsic graphene phonons with graphene plasmons. Here, we present FeCl3-intercalated graphene as a new plasmonic material with high stability under environmental conditions and carrier concentrations corresponding to EF > 1 eV. Near-field imaging of this highly doped form of graphene allows us to characterize plasmons, including their corresponding lifetimes, over a broad frequency range. For bilayer graphene, in contrast to the monolayer system, a phonon-induced dipole moment results in increased plasmon damping around the intrinsic phonon frequency. Strong coupling between intrinsic graphene phonons and plasmons is found, supported by ab initio calculations of the coupling strength, which are in good agreement with the experimental data.

The development of a mild, general, and green method for the C-H arylation of pyrazoles with relatively unreactive aryl halides is an ongoing challenge in organic synthesis. We describe herein a novel sonophotoreactor based on an ultrasonic cleaning bath and blue LED light (visible light) that induce copper-catalyzed monoarylation for pharmacologically relevant pyrazoles. The hybrid effect of ultrasonic irradiation and blue LED is discussed to interpret the observed synergistic action. A broad array of pyrazoles coupled with iodobenzene avoids expensive palladium metal or salts, and certain designed substrates were attained. Only comparatively inexpensive copper(I)iodide and 1,10-phenanthroline were used all together as the catalyst. The presented technique is a greener way to create C-H arylation of pyrazoles. It significantly reduces the amount of energy needed. [ABSTRACT FROM AUTHOR]

We establish a solid basis for the interpretation of infrared near-field spectra of thin organic films on highly reflective substrates and provide guidelines for their straightforward comparison to standard far-field Fourier transform infrared (FTIR) spectra. Particularly, we study the spectral behavior of near-field absorption and near-field phase, both quantities signifying the presence of a molecular resonance. We demonstrate that the near-field phase spectra only weakly depend on the film thickness and can be used for an approximate comparison with grazing incidence FTIR (GI-FTIR) spectra. In contrast, the near-field absorption spectra can be compared more precisely with far-field spectra: for ultrathin films they match well GI-FTIR spectra, while for thick films a good agreement with standard transmission FTIR spectra is found. Our results are based on experimental data obtained by nanoscale FTIR (nano-FTIR) spectroscopy and supported by a comprehensive theoretical analysis. [ABSTRACT FROM AUTHOR]

We report the development and characterization of a detection technique for scattering-type scanning near-field optical microscopy (s-SNOM) that enables near-field amplitude and phase imaging at two or more wavelengths simultaneously. To this end, we introduce multispectral pseudoheterodyne (PSH) interferometry, where infrared lasers are combined to form a beam with a discrete spectrum of laser lines and a time-multiplexing scheme is employed to allow for the use of a single infrared detector. We first describe and validate the implementation of multispectral PSH into a commercial s-SNOM instrument. We then demonstrate its application for the real-time correction of the negative phase contrast (NPC), which provides reliable imaging of weak IR absorption at the nanoscale. We anticipate that multispectral PSH could improve data throughput, reduce effects of sample and interferometer drift, and help to establish multicolor s-SNOM imaging as a regular imaging modality, which could be particularly interesting as new infrared light sources become available.

Scattering-type scanning near-field optical microscopy (s-SNOM) and Fourier transform infrared nanospectroscopy (nano-FTIR) are emerging tools for nanoscale chemical material identification. Here, we push s-SNOM and nano-FTIR one important step further by enabling them to quantitatively measure local dielectric constants and infrared absorption. Our technique is based on an analytical model, which allows for a simple inversion of the near-field scattering problem. It yields the dielectric permittivity and absorption of samples with 2 orders of magnitude improved spatial resolution compared to far-field measurements and is applicable to a large class of samples including polymers and biological matter. We verify the capabilities by determining the local dielectric permittivity of a PMMA film from nano-FTIR measurements, which is in excellent agreement with far-field ellipsometric data. We further obtain local infrared absorption spectra with unprecedented accuracy in peak position and shape, which is the key to quantitative chemometrics on the nanometer scale.

We report the development of infrared-resonant antenna probes for tip-enhanced optical microscopy. We employ focused-ion-beam machining to fabricate high-aspect ratio gold cones, which replace the standard tip of a commercial Si-based atomic force microscopy cantilever. Calculations show large field enhancements at the tip apex due to geometrical antenna resonances in the cones, which can be precisely tuned throughout a broad spectral range from visible to terahertz frequencies by adjusting the cone length. Spectroscopic analysis of these probes by electron energy loss spectroscopy, Fourier transform infrared spectroscopy, and Fourier transform infrared near-field spectroscopy corroborates their functionality as resonant antennas and verifies the broad tunability. By employing the novel probes in a scattering-type near-field microscope and imaging a single tobacco mosaic virus (TMV), we experimentally demonstrate high-performance mid-infrared nanoimaging of molecular absorption. Our probes offer excellent perspectives for optical nanoimaging and nanospectroscopy, pushing the detection and resolution limits in many applications, including nanoscale infrared mapping of organic, molecular, and biological materials, nanocomposites, or nanodevices.