All-optical control of high-purity trions in nanoscale waveguide.

The generation of high-purity localized trions, dynamic exciton-trion interconversion, and their spatial modulation in two-dimensional (2D) semiconductors are building blocks for the realization of trion-based optoelectronic devices. Here, we present a method for the all-optical control of the exciton-to-trion conversion process and its spatial distributions in a MoS2 monolayer. We induce a nanoscale strain gradient in a 2D crystal transferred on a lateral metal-insulator-metal (MIM) waveguide and exploit propagating surface plasmon polaritons (SPPs) to localize hot electrons. These significantly increase the electrons and efficiently funnel excitons in the lateral MIM waveguide, facilitating complete exciton-to-trion conversion even at ambient conditions. Additionally, we modulate the SPP mode using adaptive wavefront shaping, enabling all-optical control of the exciton-to-trion conversion rate and trion distribution in a reversible manner. Our work provides a platform for harnessing excitonic quasiparticles efficiently in the form of trions at ambient conditions, enabling high-efficiency photoconversion.

Glasswing-Butterfly-Inspired Multifunctional Scleral Lens and Smartphone Raman Spectrometer for Point-of-Care Tear Biomarker Analysis.

Augmenting contact lenses with sensing capabilities requires incorporating multiple functionalities within a diminutive device. Inspired by multifunctional biophotonic nanostructures of glasswing butterflies, a nanostructured scleral lens with enhanced optical, bactericidal, and sensing capabilities is reported. When used in conjunction with a smartphone-integrated Raman spectrometer, the feasibility of point-of-care applications is demonstrated. The bioinspired nanostructures made on parylene films are mounted on the anterior and posterior side of a scleral lens to create a nanostructured lens. Compared to unstructured parylene, nanostructured parylene minimizes glare by 4.3-fold at large viewing angles up to 80o . When mounted on a scleral lens, the nanostructures block 2.8-fold more ultraviolet (UVA) light while offering 1.1-fold improved transmission in the visible regime. Furthermore, the nanostructures exhibit potent bactericidal activity against Escherichia coli, killing 89% of tested bacteria within 4 h. The same nanostructures, when gold-coated, are used to perform rapid label-free multiplex detection of lysozyme and lactoferrin, the protein biomarkers of the chronic dry eye disease, in whole human tears using drop-coating deposition Raman spectroscopy. The detection of both proteins in whole human tear samples from different subjects using the nanostructured lens produced excellent correlation with commercial enzyme-based assays while simultaneously displaying a 1.5-fold lower standard deviation.

Landau-damping-induced limits to light-matter interactions in sub-10-nm planar plasmonic nanocavities.

Landau damping has previously been shown to be the dominant nonlocal effect in sub-10nm plasmonic nanostructures, although its effects on the performance of plasmonic nanocavities are still poorly understood. In this work, the effects of Landau damping in sub-10-nm planar plasmonic nanocavities are analyzed theoretically, and it is shown that while Landau damping does not affect the confinement of the cavity modes, it decreases the quality factor 10-fold due to the introduction of extra loss for sub-10nm gap sizes. As compared to purely classical models, this results in a suppression in the Purcell factor by 10 fold, the spontaneous emission rate by almost two orders of magnitude, and the required oscillator strength to achieve strong light-matter coupling by two orders of magnitude as the gap is reduced to ∼0.5nm. Therefore, it is crucial to consider Landau damping in plasmonic-nanocavity design because it breaks the classical norm of achieving higher light-matter interaction strength in sub-10-nm gap-plasmon nanocavities.

Bioinspired Disordered Flexible Metasurfaces for Human Tear Analysis Using Broadband Surface-Enhanced Raman Scattering.

Flexible surface-enhanced Raman scattering (SERS) has received attention as a means to move SERS-based broadband biosensing from bench to bedside. However, traditional flexible periodic nano-arrangements with sharp plasmonic resonances or their random counterparts with spatially varying uncontrollable enhancements are not reliable for practical broadband biosensing. Here, we report bioinspired quasi-(dis)ordered nanostructures presenting a broadband yet tunable application-specific SERS enhancement profile. Using simple, scalable biomimetic fabrication, we create a flexible metasurface (flex-MS) of quasi-(dis)ordered metal-insulator-metal (MIM) nanostructures with spectrally variable, yet spatially controlled electromagnetic hotspots. The MIM is designed to simultaneously localize the electromagnetic signal and block background Raman signals from the underlying polymeric substrate-an inherent problem of flexible SERS. We elucidate the effect of quasi-(dis)ordering on broadband tunable SERS enhancement and employ the flex-MS in a practical broadband SERS demonstration to detect human tear uric acid within its physiological concentration range (25-150 µM). The performance of the flex-MS toward noninvasively detecting whole human tear uric acid levels ex vivo is in good agreement with a commercial enzyme-based assay.

Aluminum Metasurface with Hybrid Multipolar Plasmons for 1000-Fold Broadband Visible Fluorescence Enhancement and Multiplexed Biosensing.

Aluminum (Al)-based nanoantennae traditionally suffer from weak plasmonic performance in the visible range, necessitating the application of more expensive noble metal substrates for rapidly expanding biosensing opportunities. We introduce a metasurface comprising Al nanoantennae of nanodisks-in-cavities that generate hybrid multipolar lossless plasmonic modes to strongly enhance local electromagnetic fields and increase the coupled emitter's local density of states throughout the visible regime. This results in highly efficient electromagnetic field confinement in visible wavelengths by these nanoantennae, favoring real-world plasmonic applications of Al over other noble metals. Additionally, we demonstrate spontaneous localization and concentration of target molecules at metasurface hotspots, leading to further improved on-chip detection sensitivity and a broadband fluorescence-enhancement factor above 1000 for visible wavelengths with respect to glass chips commonly used in bioassays. Using the metasurface and a multiplexing technique involving three visible wavelengths, we successfully detected three biomarkers, insulin, vascular endothelial growth factor, and thrombin relevant to diabetes, ocular and cardiovascular diseases, respectively, in a single 10 µL droplet containing only 1 fmol of each biomarker.

Enhanced broadband fluorescence detection of nucleic acids using multipolar gap-plasmons on biomimetic Au metasurfaces.

Recent studies on metal-insulator-metal-based plasmonic antennas have shown that emitters could couple with higher-order gap-plasmon modes in sub-10-nm gaps to overcome quenching. However, these gaps are often physically inaccessible for functionalization and are not scalably manufacturable. Here, using a simple biomimetic batch-fabrication, a plasmonic metasurface is created consisting of closely-coupled nanodisks and nanoholes in a metal-insulator-metal arrangement. The quadrupolar mode of this system exhibits strong broadband resonance in the visible-near-infrared regime with minimal absorptive losses and effectively supresses quenching, making it highly suitable for broadband plasmon-enhanced fluorescence. Functionalizing the accessible insulator nanogap, analytes are selectively immobilized onto the plasmonic hotspot enabling highly-localized detection. Sensing the streptavidin-biotin complex, a 91-, 288-, 403- and 501-fold fluorescence enhancement is observed for Alexa Fluor 555, 647, 750 and 790, respectively. Finally, the detection of single-stranded DNA (gag, CD4 and CCR5) analogues of genes studied in the pathogenesis of HIV-1 between 10 pM-10 µM concentrations and then CD4 mRNA in the lysate of transiently-transfected cells with a 5.4-fold increase in fluorescence intensity relative to an untransfected control is demonstrated. This outcome promises the use of biomimetic Au metasurfaces as platforms for robust detection of low-abundance nucleic acids.

Multifunctional biophotonic nanostructures inspired by the longtail glasswing butterfly for medical devices.

Numerous living organisms possess biophotonic nanostructures that provide colouration and other diverse functions for survival. While such structures have been actively studied and replicated in the laboratory, it remains unclear whether they can be used for biomedical applications. Here, we show a transparent photonic nanostructure inspired by the longtail glasswing butterfly (Chorinea faunus) and demonstrate its use in intraocular pressure (IOP) sensors in vivo. We exploit the phase separation between two immiscible polymers (poly(methyl methacrylate) and polystyrene) to form nanostructured features on top of a Si3N4 substrate. The membrane thus formed shows good angle-independent white-light transmission, strong hydrophilicity and anti-biofouling properties, which prevent adhesion of proteins, bacteria and eukaryotic cells. We then developed a microscale implantable IOP sensor using our photonic membrane as an optomechanical sensing element. Finally, we performed in vivo testing on New Zealand white rabbits, which showed that our device reduces the mean IOP measurement variation compared with conventional rebound tonometry without signs of inflammation.

Rainbow peacock spiders inspire miniature super-iridescent optics.

Colour produced by wavelength-dependent light scattering is a key component of visual communication in nature and acts particularly strongly in visual signalling by structurally-coloured animals during courtship. Two miniature peacock spiders (Maratus robinsoni and M. chrysomelas) court females using tiny structured scales (~ 40 × 10 µm2) that reflect the full visual spectrum. Using TEM and optical modelling, we show that the spiders' scales have 2D nanogratings on microscale 3D convex surfaces with at least twice the resolving power of a conventional 2D diffraction grating of the same period. Whereas the long optical path lengths required for light-dispersive components to resolve individual wavelengths constrain current spectrometers to bulky sizes, our nano-3D printed prototypes demonstrate that the design principle of the peacock spiders' scales could inspire novel, miniature light-dispersive components.

Bio-inspired, large scale, highly-scattering films for nanoparticle-alternative white surfaces.

Inspired by the white beetle of the genus Cyphochilus, we fabricate ultra-thin, porous PMMA films by foaming with CO2 saturation. Optimising pore diameter and fraction in terms of broad-band reflectance results in very thin films with exceptional whiteness. Already films with 60 µm-thick scattering layer feature a whiteness with a reflectance of 90%. Even 9 µm thin scattering layers appear white with a reflectance above 57%. The transport mean free path in the artificial films is between 3.5 µm and 4 µm being close to the evolutionary optimised natural prototype. The bio-inspired white films do not lose their whiteness during further shaping, allowing for various applications.

Scalable and controlled self-assembly of aluminum-based random plasmonic metasurfaces.

Subwavelength metal-dielectric plasmonic metasurfaces enable light management beyond the diffraction limit. However, a cost-effective and reliable fabrication method for such structures remains a major challenge hindering their full exploitation. Here, we propose a simple yet powerful manufacturing route for plasmonic metasurfaces based on a bottom-up approach. The fabricated metasurfaces consist of a dense distribution of randomly oriented nanoscale scatterers composed of aluminum (Al) nanohole-disk pairs, which exhibit angle-independent scattering that is tunable across the entire visible spectrum. The macroscopic response of the metasurfaces is controlled via the properties of an isolated Al nanohole-disk pair at the nanoscale. In addition, the optical field confinement at the scatterers and their random distribution of sizes result in a strongly enhanced Raman signal that enables broadly tunable excitation using a single substrate. This unique combination of a reliable and lithography-free methodology with the use of aluminum permits the exploitation of the full potential of random plasmonic metasurfaces for diagnostics and coloration.

Colour formation on the wings of the butterfly Hypolimnas salmacis by scale stacking.

The butterfly genus Hypolimnas features iridescent blue colouration in some areas of its dorsal wings. Here, we analyse the mechanisms responsible for such colouration on the dorsal wings of Hypolimnas salmacis and experimentally demonstrate that the lower thin lamina in the white cover scales causes the blue iridescence. This outcome contradicts other studies reporting that the radiant blue in Hypolimnas butterflies is caused by complex ridge-lamellar architectures in the upper lamina of the cover scales. Our comprehensive optical study supported by numerical calculation however shows that scale stacking primarily induces the observed colour appearance of Hypolimnas salmacis.

The role of random nanostructures for the omnidirectional anti-reflection properties of the glasswing butterfly.

The glasswing butterfly (Greta oto) has, as its name suggests, transparent wings with remarkable low haze and reflectance over the whole visible spectral range even for large view angles of 80°. This omnidirectional anti-reflection behaviour is caused by small nanopillars covering the transparent regions of its wings. In difference to other anti-reflection coatings found in nature, these pillars are irregularly arranged and feature a random height and width distribution. Here we simulate the optical properties with the effective medium theory and transfer matrix method and show that the random height distribution of pillars significantly reduces the reflection not only for normal incidence but also for high view angles.

Theoretical and experimental analysis of the structural pattern responsible for the iridescence of Morpho butterflies.

Morpho butterflies are well-known for their iridescence originating from nanostructures in the scales of their wings. These optical active structures integrate three design principles leading to the wide angle reflection: alternating lamellae layers, "Christmas tree" like shape, and offsets between neighboring ridges. We study their individual effects rigorously by 2D FEM simulations of the nanostructures of the Morpho sulkowskyi butterfly and show how the reflection spectrum can be controlled by the design of the nanostructures. The width of the spectrum is broad (≈ 90 nm) for alternating lamellae layers (or "brunches") of the structure while the "Christmas tree" pattern together with a height offset between neighboring ridges reduces the directionality of the reflectance. Furthermore, we fabricated the simulated structures by e-beam lithography. The resulting samples mimicked all important optical features of the original Morpho butterfly scales and feature the intense blue iridescence with a wide angular range of reflection.