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Register a new userSubstrate matters: Surface-polariton enhanced infrared nanospectroscopy of molecular vibrations
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Infrared nanospectroscopy based on Fourier transform infrared near-field spectroscopy (nano-FTIR) is an emerging nanoanalytical tool with large application potential for label-free mapping and identification of organic and inorganic materials with nanoscale spatial resolution. However, the detection of thin molecular layers and nanostructures on standard substrates is still challenged by weak signals. Here, we demonstrate a significant enhancement of nano-FTIR signals of a thin organic layer by exploiting polariton-resonant tip-substrate coupling and surface polariton illumination of the probing tip. When the molecular vibration matches the tip-substrate resonance, we achieve up to nearly one order of magnitude signal enhancement on a phonon-polaritonic quartz (c-SiO2) substrate, as compared to nano-FTIR spectra obtained on metal (Au) substrates, and up to two orders of magnitude when compared to the standard infrared spectroscopy substrate CaF2. Our results will be of critical importance for boosting nano-FTIR spectroscopy towards the routine detection of monolayers and single molecules.
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Waveguide-integrated plasmonics is a growing field with many innovative concepts and demonstrated devices in the visible and near-infrared. Here, we extend this body of work to the mid-infrared for the application of surface-enhanced infrared absorption (SEIRA), a spectroscopic method to probe molecular vibrations in small volumes and thin films. Built atop a silicon-on-insulator (SOI) waveguide platform, two key plasmonic structures useful for SEIRA are examined using computational modeling: gold nanorods and coaxial nanoapertures. We find resonance dips of 80% in near diffraction-limited areas due to arrays of our structures and up to 40% from a single resonator. Each of the structures are evaluated using the simulated SEIRA signal from poly(methyl methacrylate) and an octadecanethiol self-assembled monolayer. The platforms we present allow for a compact, on-chip SEIRA sensing system with highly efficient waveguide coupling in the mid-IR.
Polar van der Waals (vdW) crystals that support phonon polaritons have recently attracted much attention because they can confine infrared and terahertz (THz) light to deeply subwavelength dimensions, allowing for the guiding and manipulation of light at the nanoscale. The practical applications of these crystals in devices rely strongly on deterministic engineering of their spatially localized electromagnetic field distributions, which has remained challenging. This study demonstrates that polariton interference can be enhanced and tailored by patterning the vdW crystal {alpha}-MoO3 into microstructures that support highly in-plane anisotropic phonon polaritons. The orientation of the polaritonic in-plane isofrequency curve relative to the microstructure edges is a critical parameter governing the polariton interference, rendering the configuration of infrared electromagnetic field localizations by enabling the tuning of the microstructure size and shape and the excitation frequency. Thus, our study presents an effective rationale for engineering infrared light flow in planar photonic devices.
Infrared (IR) technologies have become increasingly relevant as they offer a wide range of applications, from thermal imaging to chemical and biological vibrational spectroscopy. Substrate materials, such as calcium fluoride and zinc selenide, are commonly used for IR optics. Unfortunately, they are typically fragile, hygroscopic and expensive, thus producing potential problems during device fabrication and in the long-term functional operation. Here, we introduce yttria-stabilized zirconia (YSZ) ceramic as a flexible and stable platform to implement next generation IR nano-optic devices. In particular, we have combined YSZ with metallic nano-structures and graphene to demonstrate new plasmonics, polarizers and transparent heating substrates. The proposed YSZ-based platforms enable high temperature processing that also withstand harsh environments because of its excellent mechanical, thermal and chemical stability. In addition to the functional capability of making foldable and bendable devices, the demonstrated mechanical flexibility offers the possibility of roll-to-roll processing for low cost and large scale fabrication processes. Our work offers compelling evidence that ultrathin YSZ is a unique substrate for IR applications, given all the combined features, including mechanical flexibility, durability, transparency and easy processing, which are not available from other available material alternatives.
The low efficiency of Raman spectroscopy can be overcome by placing the active molecules in the vicinity of scatterers, typically rough surfaces or nanostructures with various shapes. This surface-enhanced Raman scattering (SERS) leads to substantial enhancement that depends on the scatterer that is used. In this work, we find fundamental upper bounds on the Raman enhancement for arbitrary-shaped scatterers, depending only on its material constants and the separation distance from the molecule. According to our metric, silver is optimal in visible wavelengths while aluminum is better in the near-UV region. Our general analytical bound scales as the volume of the scatterer and the inverse sixth power of the distance to the active molecule. Numerical computations show that simple geometries fall short of the bounds, suggesting further design opportunities for future improvement. For periodic scatterers, we use two formulations to discover different bounds, and the tighter of the two always must apply. Comparing these bounds suggests an optimal period depending on the volume of the scatterer.
Recent experiments have observed that the chemical and photophysical properties of molecules can be modified inside an optical Fabry-Perot microcavity under collective vibrational strong coupling (VSC) conditions, and such modification is currently not well understood by theory. In an effort to understand the origin of such cavity induced phenomena, some recent studies have focused on the effect of the cavity environment on the nonlinear optical response of the molecular subsystem. Here, we use a recently proposed protocol for classical cavity molecular dynamics (CavMD) simulations to numerically investigate the linear and nonlinear response of liquid carbon dioxide under such VSC conditions following an optical pulse excitation. We find that applying a strong pulse of excitation to the lower hybrid light-matter state, i.e., the lower polariton (LP), can lead to an overall molecular nonlinear absorption which is enhanced by up to two orders of magnitude relative to the excitation outside the cavity. This polariton-enhanced multiphoton absorption also causes an ultrashort LP lifetime (0.2 ps) under strong illumination. Unlike usual polariton relaxation processes -- whereby polaritonic energy transfers directly to the manifold of singly excited vibrational dark states -- under the present mechanism, the LP transfers energy directly to the manifold of higher vibrationally excited dark states; these highly excited dark states subsequently relax to the manifold of singly excited states with a lifetime of tens of ps. Because the present mechanism is generic in nature, we expect these numerical predictions to be experimentally observed in different molecular systems and in cavities with different volumes.
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