Engineered optical metamaterials present a unique platform for biosensing applications owing to their ability to confine light to nanoscale regions and to their spectral selectivity. Infrared plasmonic metamaterials are especially attractive because their resonant response can be accurately tuned to that of the vibrational modes of the target biomolecules. Here we introduce an infrared plasmonic surface based on a Fano-resonant asymmetric metamaterial exhibiting sharp resonances caused by the interference between subradiant and superradiant plasmonic resonances. Owing to the metamaterial's asymmetry, the frequency of the subradiant resonance can be precisely determined and matched to the molecule's vibrational fingerprints. A multipixel array of Fano-resonant asymmetric metamaterials is used as a platform for multispectral biosensing of nanometre-scale monolayers of recognition proteins and their surface orientation, as well as for detecting chemical binding of target antibodies to recognition proteins.
surface plasmons ͉ SEIRA ͉ surface enhancements ͉ near-field effects ͉ infrared absorption spectroscopy
Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules’ native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology.
Metamaterial-based perfect absorbers utilize intrinsic loss, with the aid of appropriate structural design, to achieve near unity absorption at a certain wavelength. For most of the reported absorbers, the absorption occurs only at a single wavelength where plasmon resonances are excited in the nanostructures. Here we introduce a dual-band perfect absorber based on a gold nanocross structure. Two bands of maximum absorption of 94% are experimentally accomplished by breaking the symmetry of the cross structure. Furthermore, we demonstrate the two bands can be readily tuned throughout the mid-infrared with their associated resonances giving rise to large near-field enhancements. These features are ideal for multiband surface-enhanced infrared spectroscopy applications. We experimentally demonstrate this application by simultaneously detecting two molecular vibrational modes of a 4 nm thick polymer film utilizing our proposed absorber. Furthermore, in response to variations in the interaction strength between the plasmonic and molecular dipoles, we observe an anticrossing behavior and modification in the spectral line shape of the molecular absorption peak, which are characteristic of the coupling between the two modes.
Coupled plasmonic resonators have become the subject of significant research interest in recent years as they provide a route to dramatically enhanced light-matter interactions. Often, the design of these coupled mode systems draws intuition and inspiration from analogies to atomic and molecular physics systems. In particular, they have been shown to mimic quantum interference effects, such as electromagnetically induced transparency (EIT) and Fano resonances. This analogy also been used to describe the surface-enhanced absorption effect where a plasmonic resonance is coupled to a weak molecular resonance. These important phenomena are typically described using simple driven harmonic (or linear) oscillators (i.e., mass-on-a-spring) coupled to each other. In this work, we demonstrate the importance of an essential interdependence between the rate at which the system can be driven by an external field and its damping rate through radiative loss. This link is required in systems exhibiting time-reversal symmetry and energy conservation. Not only does it ensure an accurate and physically consistent description of resonant systems but leads directly to interesting new effects. Significantly, we demonstrate this dependence to predict a transition between EIT and electromagnetically induced absorption that is solely a function of the ratio of the radiative to intrinsic loss rates in coupled resonator systems. Leveraging the temporal coupled mode theory, we introduce a unique and intuitive picture that accurately describes these effects in coupled plasmonic/molecular and fully plasmonic systems. We demonstrate our approach's key features and advantages analytically as well as experimentally through surface-enhanced absorption spectroscopy and plasmonic metamaterial applications.
The introduction of high-throughput and high-resolution nanofabrication techniques operating at low cost and low complexity is essential for the advancement of nanoplasmonic and nanophotonic fields. In this paper, we demonstrate a novel fabrication approach based on nanostencil lithography for high-throughput fabrication of engineered infrared plasmonic nanorod antenna arrays. The technique relying on deposition of materials through a shadow mask enables plasmonic substrates supporting spectrally sharp collective resonances. We show that reflectance spectra of these antenna arrays are comparable to that of arrays fabricated by electron beam lithography. We also show that nanostencils can be reused multiple times to fabricate a series of infrared nanoantenna arrays with identical optical responses. Finally, we demonstrate fabrication of plasmonic nanostructures in a variety of shapes with a single metal deposition step on different substrates, including nonconducting ones. Our approach, by enabling the reusability of the stencil and offering flexibility on the substrate choice and nanopattern design, could facilitate the transition of plasmonic technologies to the real-world applications.
It is generally accepted that the lifetimes of the localized plasmonic excitations are inherently controlled by the type of the metals and the shape of the nanoparticles. However, extended plasmonic lifetimes and enhanced near-fields in nanoparticle arrays can be achieved as a result of collective excitation of plasmons. In this article, we demonstrate significantly longer plasmon lifetimes and stronger near-field enhancements by embedding the nanoantenna arrays into the substrate. Our approach offers a more homogeneous dielectric background allowing stronger diffractive couplings among plasmonic particles leading to strong suppression of the radiative damping. We observe near-field enhancements well beyond than those achievable with isolated nanoparticles. Enhanced fields obtained in these structures could be attractive for biosensing and non-linear photonics applications.
Mid-infrared absorption spectroscopy is a powerful tool for optically probing the molecular structure of biological samples. However, using conventional approaches, IR measurements on small quantities of molecules are extremely challenging due to sensitivity limitations. The strong IR absorption of liquid water presents additional obstacles to performing measurements in biomolecules' native, aqueous environments. In this review we discuss the application of engineered plasmonic nanoantennas to overcoming these challenges. We provide overviews and highlight the key concepts of our recent work in designing infrared antennas and applying them to enhance the absorption of minute quantities of biomolecules as well as new fabrication methods for their high throughput and low-cost manufacturing.
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