Development of Spiropyran Immobilization and Characterization Protocols for Reversible Photopatterning of SiO Surfaces.

Spiropyran is a dynamic organic compound that is distinguished by its reversible conversion between two forms: the colorless closed spiropyran (SP) form and the purple open merocyanine (MC) form. Typically triggered by UV light and reversed by visible light, spiropyran-functionalized surfaces offer reversible conversion in properties including color, polarity, reactivity, and fluorescence, making them applicable to diverse applications in chemical sensors, biosensors, drug delivery, and heavy metal extraction. While spiropyran has been successfully incorporated into various material platforms with SiO surfaces, its application on flat surfaces has been limited due to surface area constraints and a lack of standardized evaluation methods, which largely depend on the integration approach and substrate type used.

High-fidelity nano-FTIR spectroscopy by on-pixel normalization of signal harmonics.

Scattering-type scanning near-field optical microscopy (s-SNOM) and Fourier transform infrared nanospectroscopy (nano-FTIR) are emerging tools for physical and chemical nanocharacterization of organic and inorganic composite materials. Being based on () diffraction-limited illumination of a scanning probe tip for nanofocusing of light and () recording of the tip-scattered radiation, the efficient suppression of background scattering has been critical for their success. Here, we show that indirect tip illumination via far-field reflection and scattering at the sample can produce s-SNOM and nano-FTIR signals of materials that are not present at the tip position - despite full background suppression.

Subsurface chemical nanoidentification by nano-FTIR spectroscopy.

Nano-FTIR spectroscopy based on Fourier transform infrared near-field spectroscopy allows for label-free chemical nanocharacterization of organic and inorganic composite surfaces. The potential capability for subsurface material analysis, however, is largely unexplored terrain. Here, we demonstrate nano-FTIR spectroscopy of subsurface organic layers, revealing that nano-FTIR spectra from thin surface layers differ from that of subsurface layers of the same organic material.

Double Rabi Splitting in a Strongly Coupled System of Core-Shell Au@Ag Nanorods and J-Aggregates of Multiple Fluorophores.

The interaction of several components in the strong coupling regime yielding multiple Rabi splittings opens up remarkable possibilities for studies of multimode hybridization and energy transfer, which is of considerable interest in both fundamental and applied science. Here we demonstrate that three different components, such as core-shell Au@Ag nanorods and J-aggregates of two different dyes, can be integrated into a single hybrid structure, which leads to strong collective exciton-plasmon coupling and double-mode Rabi splitting totaling 338 meV. We demonstrate strong coupling in these multicomponent plexitonic nanostructures by means of magnetic circular dichroism spectroscopy and demonstrate strong magneto-optical activity for the three hybridized states resulting from this coupling.

Probing low-energy hyperbolic polaritons in van der Waals crystals with an electron microscope.

Van der Waals materials exhibit intriguing structural, electronic, and photonic properties. Electron energy loss spectroscopy within scanning transmission electron microscopy allows for nanoscale mapping of such properties. However, its detection is typically limited to energy losses in the eV range-too large for probing low-energy excitations such as phonons or mid-infrared plasmons.

Strong Magneto-Optical Response of Nonmagnetic Organic Materials Coupled to Plasmonic Nanostructures.

Plasmonic nanoparticles (PNPs) can significantly modify the optical properties of nearby organic molecules and thus present an attractive opportunity for sensing applications. However, the utilization of PNPs in conventional absorption, fluorescence, or Raman spectroscopy techniques is often ineffective due to strong absorption background and light scattering, particularly in the case of turbid solutions, cell suspensions, and biological tissues. Here we show that nonmagnetic organic molecules may exhibit magneto-optical response due to binding to a PNP.

Recovery of permittivity and depth from near-field data as a step toward infrared nanotomography.

The increasing complexity of composite materials structured on the nanometer scale requires highly sensitive analytical tools for nanoscale chemical identification, ideally in three dimensions. While infrared near-field microscopy provides high chemical sensitivity and nanoscopic spatial resolution in two dimensions, the quantitative extraction of material properties of three-dimensionally structured samples has not been achieved yet. Here we introduce a method to perform rapid recovery of the thickness and permittivity of simple 3D structures (such as thin films and nanostructures) from near-field measurements, and provide its first experimental demonstration.

Structural analysis and mapping of individual protein complexes by infrared nanospectroscopy.

Mid-infrared spectroscopy is a widely used tool for material identification and secondary structure analysis in chemistry, biology and biochemistry. However, the diffraction limit prevents nanoscale protein studies. Here we introduce mapping of protein structure with 30 nm lateral resolution and sensitivity to individual protein complexes by Fourier transform infrared nanospectroscopy (nano-FTIR).

Quantitative Measurement of Local Infrared Absorption and Dielectric Function with Tip-Enhanced Near-Field Microscopy.

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.

One-dimensional model of inertial pumping.

A one-dimensional model of inertial pumping is introduced and solved. The pump is driven by a high-pressure vapor bubble generated by a microheater positioned asymmetrically in a microchannel. The bubble is approximated as a short-term impulse delivered to the two fluidic columns inside the channel.

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.

Enhanced resolution in subsurface near-field optical microscopy.

We report an experimental analysis of the capabilities of scattering-type scanning near-field optical microscopy for mapping sub-surface features at varying depths. For the first time, we demonstrate experimentally that both the spatial resolution and depth contrast can be improved in subsurface microscopy by demodulating the measured near-field signal at higher harmonics of the probe's tapping frequency and by operating at smaller tapping amplitudes. Our findings are qualitatively supported by a simple dipole model.

Phase in nanooptics.

Quantitative phase measurements in imaging, microscopy, and nanooptics provide information not carried in amplitude measurements alone. In this issue of ACS Nano, Honigstein et al. present a new method in phase measurement.

Phaseless three-dimensional optical nanoimaging.

We propose a method for optical nanoimaging in which the structure of a three-dimensional inhomogeneous medium may be recovered from far-field power measurements. Neither phase control of the illuminating field nor phase measurements of the scattered field are necessary. The method is based on the solution to the inverse scattering problem for a system consisting of a weakly-scattering dielectric sample and a strongly-scattering nanoparticle tip.

Gain-assisted slow to superluminal group velocity manipulation in nanowaveguides.

We study the energy propagation in subwavelength waveguides and demonstrate that the mechanism of material gain, previously suggested for loss compensation, is also a powerful tool to manipulate dispersion and propagation characteristics of electromagnetic pulses at the nanoscale. We show theoretically that the group velocity in lossy nanowaveguides can be controlled from slow to superluminal values by the material gain and waveguide geometry and develop an analytical description of the relevant physics. We utilize the developed formalism to show that gain-assisted dispersion management can be used to control the transition between "photonic-funnel" and "photonic-compressor" regimes in tapered nanowaveguides.