Correcting thermal-emission-induced detector saturation in infrared spectroscopy.

We found that temperature-dependent infrared spectroscopy measurements (i.e., reflectance or transmittance) using a Fourier-transform spectrometer can have substantial errors, especially for elevated sample temperatures and collection using an objective lens. These errors can arise as a result of partial detector saturation due to thermal emission from the measured sample reaching the detector, resulting in nonphysical apparent reduction of reflectance or transmittance with increasing sample temperature. Here, we demonstrate that these temperature-dependent errors can be corrected by implementing several levels of optical attenuation that enable convergence testing of the measured reflectance or transmittance as the thermal-emission signal is reduced, or by applying correction factors that can be inferred by looking at the spectral regions where the sample is not expected to have a substantial temperature dependence.

Giant Modulation of Refractive Index from Picoscale Atomic Displacements.

It is shown that structural disorder-in the form of anisotropic, picoscale atomic displacements-modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS3, a quasi-1D hexagonal chalcogenide. Single-crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6 chains along the c-axis, and threefold degenerate Ti displacements in the a-b plane. 47/49Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity.

Metasurface-Enhanced Mid-Infrared Spectrochemical Imaging of Tissues.

Label-free and nondestructive mid-infrared vibrational hyperspectral imaging is an essential tissue analysis tool, providing spatially resolved biochemical information critical to understanding physiological and pathological processes. However, the chemically complex and spatially heterogeneous composition of tissue specimens and the inherently weak interaction of infrared light with biomolecules limit the analytical performance of infrared absorption spectroscopy. Here, an advanced mid-infrared spectrochemical tissue imaging modality is introduced using metasurfaces that support strong surface-localized electromagnetic fields to capture quantitative molecular maps of large-area murine brain tissue sections. The approach leverages polarization-multiplexed multi-resonance plasmonic metasurfaces to simultaneously detect various functional biomolecules. The surface-enhanced mid-infrared spectral imaging method eliminates the non-specific effects of bulk tissue morphology on quantitative spectral analysis and improves chemical selectivity. This study shows that metasurface enhancement increases the retrieval of amide I and II bands associated with protein secondary structures. Moreover, it is demonstrated that plasmonic metasurfaces enhance the chemical contrast in infrared images and enable detection of ultrathin tissue regions that are not otherwise visible to conventional mid-infrared spectral imaging. While this work uses murine brain tissue sections, the chemical imaging method is well-suited for other tissue types, which broadens its potential impact for translational research and clinical histopathology.

Colossal Optical Anisotropy from Atomic-Scale Modulations.

Materials with large birefringence (Δn, where n is the refractive index) are sought after for polarization control (e.g., in wave plates, polarizing beam splitters, etc.), nonlinear optics, micromanipulation, and as a platform for unconventional light-matter coupling, such as hyperbolic phonon polaritons. Layered 2D materials can feature some of the largest optical anisotropy; however, their use in most optical systems is limited because their optical axis is out of the plane of the layers and the layers are weakly attached. This work demonstrates that a bulk crystal with subtle periodic modulations in its structure-Sr9/8 TiS3 -is transparent and positive-uniaxial, with extraordinary index ne = 4.5 and ordinary index no = 2.4 in the mid- to far-infrared. The excess Sr, compared to stoichiometric SrTiS3 , results in the formation of TiS6 trigonal-prismatic units that break the chains of face-sharing TiS6 octahedra in SrTiS3 into periodic blocks of five TiS6 octahedral units. The additional electrons introduced by the excess Sr form highly oriented electron clouds, which selectively boost the extraordinary index ne and result in record birefringence (Δn > 2.1 with low loss). The connection between subtle structural modulations and large changes in refractive index suggests new categories of anisotropic materials and also tunable optical materials with large refractive-index modulation.

Coiled Optical Nanofiber for Optofluidic Absorbance Detection.

A challenge for optofluidic absorbance detection is the high concentration limit of detection due to the short optical path length. Herein, we introduce a concept of utilizing the coiled optical nanofiber for highly sensitive and robust optofluidic absorbance detection. Investigated by measuring the absorbance of FeCl3 solutions, the sensor shows a detection limit down to 10 µM with excellent reversibility in a concentration range of 0-5 mM. The sensitivity is 10-fold higher than that of standard absorbance measurement by using a 1 cm cuvette. Also, highly sensitive chloramphenicol sensing was demonstrated by using the enzyme-linked immunosorbent assay (ELISA) method, achieving a detection limit below 0.5 ng/L. The higher sensitivity and lower detection limit are caused by the large fractional power of evanescent field outside the nanofiber and the long detection length, which can effectively improve the absorption of the evanescent field, while the excellent reversibility is caused by the support of a polydimethylsiloxane (PDMS) pillar rather than by suspending the nanofiber in the microchannel. We envision that the present work may open up new opportunities for ultrasensitive chemical and biological sensing.