Self-assembled plasmonics for angle-independent structural color displays with actively addressed black states.

Nanostructured plasmonic materials can lead to the extremely compact pixels and color filters needed for next-generation displays by interacting with light at fundamentally small length scales. However, previous demonstrations suffer from severe angle sensitivity, lack of saturated color, and absence of black/gray states and/or are impractical to integrate with actively addressed electronics. Here, we report a vivid self-assembled nanostructured system which overcomes these challenges via the multidimensional hybridization of plasmonic resonances. By exploiting the thin-film growth mechanisms of aluminum during ultrahigh vacuum physical vapor deposition, dense arrays of particles are created in near-field proximity to a mirror. The sub-10-nm gaps between adjacent particles and mirror lead to strong multidimensional coupling of localized plasmonic modes, resulting in a singular resonance with negligible angular dispersion and ∼98% absorption of incident light at a desired wavelength. The process is compatible with arbitrarily structured substrates and can produce wafer-scale, diffusive, angle-independent, and flexible plasmonic materials. We then demonstrate the unique capabilities of the strongly coupled plasmonic system via integration with an actively addressed reflective liquid crystal display with control over black states. The hybrid display is readily programmed to display images and video.

Buckling and twisting of advanced materials into morphable 3D mesostructures.

Recently developed methods in mechanically guided assembly provide deterministic access to wide-ranging classes of complex, 3D structures in high-performance functional materials, with characteristic length scales that can range from nanometers to centimeters. These processes exploit stress relaxation in prestretched elastomeric platforms to affect transformation of 2D precursors into 3D shapes by in- and out-of-plane translational displacements. This paper introduces a scheme for introducing local twisting deformations into this process, thereby providing access to 3D mesostructures that have strong, local levels of chirality and other previously inaccessible geometrical features. Here, elastomeric assembly platforms segmented into interconnected, rotatable units generate in-plane torques imposed through bonding sites at engineered locations across the 2D precursors during the process of stress relaxation. Nearly 2 dozen examples illustrate the ideas through a diverse variety of 3D structures, including those with designs inspired by the ancient arts of origami/kirigami and with layouts that can morph into different shapes. A mechanically tunable, multilayered chiral 3D metamaterial configured for operation in the terahertz regime serves as an application example guided by finite-element analysis and electromagnetic modeling.

DNA-Modified Plasmonic Sensor for the Direct Detection of Virus Biomarkers from the Blood.

The rapid spread of viral infections demands early detection strategies to minimize proliferation of the disease. Here, we demonstrate a plasmonic biosensor to detect Dengue virus, which was chosen as a model, via its nonstructural protein NS1 biomarker. The sensor is functionalized with a synthetic single-stranded DNA oligonucleotide and provides high affinity toward NS1 protein present in the virus genome. We demonstrate the detection of NS1 protein at a concentration of 0.1-10 µg/mL in bovine blood using an on-chip microfluidic plasma separator integrated with the plasmonic sensor which covers the clinical threshold of 0.6 µg/mL of high risk of developing Dengue hemorrhagic fever. The conceptual and practical demonstration shows the translation feasibility of these microfluidic optical biosensors for early detection of a wide range of viral infections, providing a rapid clinical diagnosis of infectious diseases directly from minimally processed biological samples at point of care locations.

Wireless optoelectronic photometers for monitoring neuronal dynamics in the deep brain.

Capabilities for recording neural activity in behaving mammals have greatly expanded our understanding of brain function. Some of the most sophisticated approaches use light delivered by an implanted fiber-optic cable to optically excite genetically encoded calcium indicators and to record the resulting changes in fluorescence. Physical constraints induced by the cables and the bulk, size, and weight of the associated fixtures complicate studies on natural behaviors, including social interactions and movements in environments that include obstacles, housings, and other complex features. Here, we introduce a wireless, injectable fluorescence photometer that integrates a miniaturized light source and a photodetector on a flexible, needle-shaped polymer support, suitable for injection into the deep brain at sites of interest. The ultrathin geometry and compliant mechanics of these probes allow minimally invasive implantation and stable chronic operation. In vivo studies in freely moving animals demonstrate that this technology allows high-fidelity recording of calcium fluorescence in the deep brain, with measurement characteristics that match or exceed those associated with fiber photometry systems. The resulting capabilities in optical recordings of neuronal dynamics in untethered, freely moving animals have potential for widespread applications in neuroscience research.

Enzyme-Free Plasmonic Biosensor for Direct Detection of Neurotransmitter Dopamine from Whole Blood.

Complex biological fluids without pretreatment, separation, or purification impose stringent limitations on the practical deployment of label-free plasmonic biosensors for advanced assays needed in point of care applications. In this work, we present an enzyme-free plasmonic neurotransmitter dopamine biosensor integrated with a microfluidic plasma separator. This integrated device allows the in-line separation of plasma directly from the bloodstream and channels it to the active detection area, where inorganic cerium oxide nanoparticles function as local selective dopamine binding sites through strong surface redox reaction. A thorough understanding and engineering of the nanoparticles is carried out to maximize its dopamine sensitivity and selectivity. We obtain detection of dopamine at 100 fM concentration in simulated body fluid and 1 nM directly from blood without any prior sample preparation. The detection selectivity is found to be at least five-times higher compared to the common interfering species. This demonstration shows the feasibility of the practical implementation of the proposed plasmonic system in detection of variety of biomarkers directly from the complex biological fluids.

Novel liquid crystal photonic devices enabled by two-photon polymerization [Invited].

In addition to displays, liquid crystals (LCs) have also found widespread applications in photonic devices, such as adaptive lens, adaptive optics, and sensors, because of their responses to electric field, temperature, and light. As the fabrication technique advances, more sophisticated devices can be designed and created. In this review, we report recent advances of two-photon polymerization-based direct-laser writing enabled LC devices. Firstly, we describe the basic working principle of two-photon polymerization. With this powerful fabrication technique, we can generate anchoring energy by surface morphology to align LC directors on different form factors. To prove this concept, we demonstrate LC alignment on planar, curvilinear surfaces as well as in three-dimensional volumes. Based on the results, we further propose a novel, ultra-broadband, twisted-nematic diffractive waveplate that can potentially be fulfilled by this technique. Next, we briefly discuss the current status of direct-laser writing on LC reactive mesogens and its potential applications. Finally, we present two design challenges: fabrication yield and polymer relaxation/deformation, remaining to be overcome.

Adaptive liquid crystal microlens array enabled by two-photon polymerization.

A tunable-focus liquid crystal microlens array is demonstrated and characterized. Using two-photon polymerization based direct-laser writing, a polymerized microlens array is fabricated on one substrate. Such a microlens array creates inhomogeneous electric field distribution and homogeneous-like liquid-crystal alignment, simultaneously. The phase profile and thus the focal length can be tuned dynamically by the applied voltage. We also further investigate the focusing property and the imaging capability of the fabricated sample. Using the adaptive microlens array as an example, we demonstrate that directly forming a curvilinear surface with liquid-crystal alignment is feasible. In addition to adaptive lens, this direct-laser writing method is also a powerful tool for making other tunable photonic devices.

Multi-spectral frequency selective mid-infrared microbolometers.

Frequency selective detection of low energy photons is a scientific challenge using natural materials. A hypothetical surface which functions like a light funnel with very low thermal mass in order to enhance photon collection and suppress background thermal noise is the ideal solution to address both low temperature and frequency selective detection limitations of present detection systems. Here, we present a cavity-coupled quasi-three dimensional plasmonic crystal which induces impedance matching to the free space giving rise to extraordinary transmission through the sub-wavelength aperture array like a "light funnel" in coupling low energy incident photons resulting in frequency selective perfect (~100%) absorption of the incident radiation and zero back reflection. The peak wavelength of absorption of the incident light is almost independent of the angle of incidence and remains within 20% of its maximum (100%) up to θi≤45˚. This perfect absorption results from the incident light-driven localized edge "micro-plasma" currents on the lossy metallic surfaces. The wide-angle light funneling is validated with experimental measurements. Further, a super-lattice based electronic biasing circuit converts the absorbed narrow linewidth (Δλ/λ0< 0.075) photon energy inside the sub-wavelength thick film (< λ/100) to voltage output with high signal to noise ratio close to the theoretical limit. Such artificial plasmonic surfaces enable flexible scaling of light funneling response to any wavelength range by simple dimensional changes paving the path towards room temperature frequency selective low energy photon detection.

Cavity-induced hybrid plasmon excitation for perfect infrared absorption.

Photonic microcavity coupling of a subwavelength hole-disk array, a two-element metal/dielectric composite structure with enhanced extraordinary transmission, leads to 100% coupling of incident light to the cavity system and subsequent absorption. This light-funneling process arises from the temporal and spatial coupling of the broadband localized surface plasmon resonance on the coupled hole-disk array and the photonic modes of the optical cavity, which induces spectral narrowing of the perfect absorption of light. A simple nanoimprint lithography-based large-area fabrication process paves the path towards practical implementation of plasmonic cavity-based devices and sensors.

Switchable Pancharatnam-Berry microlens array with nano-imprinted liquid crystal alignment.

We report a rapid nano-imprinting technique to pattern the liquid crystal alignment of a Pancharatnam-Berry phase microlens array. Through implementing a single-side aligned cell, we demonstrate a switchable microlens array with fast response time and low operation voltage. Further investigation of focusing property as well as imaging capability ensure the good quality of the microlens array. Besides planar structures, this method is also promising for patterning liquid crystal alignment on curvilinear surfaces.

Superchiral Light Generation on Degenerate Achiral Surfaces.

A novel route of superchiral near-field generation is demonstrated based on geometrically achiral systems supporting degenerate and spatially superimposed plasmonic modes. Such systems generate a single-handed chiral near field with simultaneous zero far-field circular dichroism. The phenomenon is theoretically elucidated with a rotating dipole model, which predicts a uniform single-handed chiral near field that flips handedness solely by reversing the handedness of the source. This property allows detection of pure background free molecular chirality through near-field light-matter interaction, which is experimentally demonstrated in the precise identification of both handedness of a chiral molecule on a single substrate with about four orders of magnitude enhancement in detection sensitivity compared to its conventional volumetric counterpart.

Hybrid cavity-coupled plasmonic biosensors for low concentration, label-free and selective biomolecular detection.

Simple optical techniques that can accurately and selectively identify organic and inorganic material in a reproducible manner are of paramount importance in biological sensing applications. In this work, we demonstrate that a nanoimprinted plasmonic pattern with locked-in dimensions supports sharp deterministic hybrid resonances when coupled with an optical cavity suitable for high sensitive surface detection. The surface sensing property of this hybrid system is quantified by precise atomic layer growth of aluminum oxide using the atomic layer deposition technique. The analyte specific sensing ability is demonstrated in the detection of two dissimilar analytes, inorganic amine-coated iron oxide nanoparticles and organic streptavidin protein. Femto to nanomolar detection limits were achieved with the proposed coupled plasmonic system based on the versatile and robust soft nanoimprinting technique, which promises practical low cost biosensors.

Multi-spectral infrared spectroscopy for robust plastic identification.

The identification and classification of plastics plays an important role in waste management and recycling processes. Present electrical and optical sorting techniques lack the required resolution for accurate identification in a high throughput manner for a diverse set of plastics commonly found in municipal waste. In this work a multi-spectral infrared spectroscopic technique is employed to construct a unique fingerprint library of 12 plastic resin groups that are commonly encountered in municipal waste. We test the proposed method in a blind plastic identification experiment, which shows excellent unbiased identification accuracy. This simple optical technique in combination with the multi-spectral library will enable high throughput and accurate detection of various plastics from recovered solid waste.

Hybrid coupling mechanism in a system supporting high order diffraction, plasmonic, and cavity resonances.

The interactions between plasmonic and photonic modes of a cavity-coupled plasmonic crystal are studied in diffraction and diffractionless regimes, which lead us to the understanding of coherent interactions between electron plasma, higher order cavity, and diffraction modes. The strong interaction between plasmonic and photonic modes is shown to enhance as well as suppress surface plasmon resonance based on cavity phase relation. Numerical and analytical approaches are developed to accurately explain the physics of the interactions evident in their characteristic dispersion graphs. Further experimental measurements confirm the theoretical predictions.

Tunable plasmonic superchiral light for ultrasensitive detection of chiral molecules.

The accurate detection, classification, and separation of chiral molecules are pivotal for advancing pharmaceutical and biomolecular innovations. Engineered chiral light presents a promising avenue to enhance the interaction between light and matter, offering a noninvasive, high-resolution, and cost-effective method for distinguishing enantiomers. Here, we present a nanostructured platform for surface-enhanced infrared absorption-induced vibrational circular dichroism (VCD) based on an achiral plasmonic system. This platform enables precise measurement, differentiation, and quantification of enantiomeric mixtures, including concentration and enantiomeric excess determination. Our experimental results exhibit a 13 orders of magnitude higher detection sensitivity for chiral enantiomers compared to conventional VCD spectroscopic techniques, accounting for respective path lengths and concentrations. The tunable spectral characteristics of this achiral plasmonic system facilitate the detection of a diverse range of chiral compounds. The platform's simplicity, tunability, and exceptional sensitivity holds remarkable potential for enantiomer classification in drug design, pharmaceuticals, and biological applications.

Roadmap for Optical Metasurfaces.

Metasurfaces have recently risen to prominence in optical research, providing unique functionalities that can be used for imaging, beam forming, holography, polarimetry, and many more, while keeping device dimensions small. Despite the fact that a vast range of basic metasurface designs has already been thoroughly studied in the literature, the number of metasurface-related papers is still growing at a rapid pace, as metasurface research is now spreading to adjacent fields, including computational imaging, augmented and virtual reality, automotive, display, biosensing, nonlinear, quantum and topological optics, optical computing, and more. At the same time, the ability of metasurfaces to perform optical functions in much more compact optical systems has triggered strong and constantly growing interest from various industries that greatly benefit from the availability of miniaturized, highly functional, and efficient optical components that can be integrated in optoelectronic systems at low cost. This creates a truly unique opportunity for the field of metasurfaces to make both a scientific and an industrial impact. The goal of this Roadmap is to mark this "golden age" of metasurface research and define future directions to encourage scientists and engineers to drive research and development in the field of metasurfaces toward both scientific excellence and broad industrial adoption.

Ultralight plasmonic structural color paint.

All present commercial colors are based on pigments. While such traditional pigment-based colorants offer a commercial platform for large-volume and angle insensitiveness, they are limited by their instability in atmosphere, color fading, and severe environmental toxicity. Commercial exploitation of artificial structural coloration has fallen short due to the lack of design ideas and impractical nanofabrication techniques. Here, we present a self-assembled subwavelength plasmonic cavity that overcomes these challenges while offering a tailorable platform for rendering angle and polarization-independent vivid structural colors. Fabricated through large-scale techniques, we produce stand-alone paints ready to be used on any substrate. The platform offers full coloration with a single layer of pigment, surface density of 0.4 g/m2, making it the lightest paint in the world.

Coherent stitching of light in multilayered diffractive optical elements.

Diffractive optical elements serve an important function in many dynamic and static optical systems. Multilayered diffractive elements offer powerful opportunity to harness both phase and amplitude modulation for benefits in diffraction efficiency and beam shaping. However, multilayered combinations have been difficult to fabricate and provide only weak diffraction for phase gratings with low refractive index contrast. Femtosecond laser writing of finely-pitched multilayer volume gratings was optimized in bulk fused silica. We identify and quantify an optimum layer-to-layer separation according to Talbot self-imaging planes and present systematic experimental validation of this new approach to enhance otherwise weakly diffracting volume gratings.

Porosity control in metal-assisted chemical etching of degenerately doped silicon nanowires.

We report the fabrication of degenerately doped silicon (Si) nanowires of different aspect ratios using a simple, low-cost and effective technique that involves metal-assisted chemical etching (MacEtch) combined with soft lithography or thermal dewetting metal patterning. We demonstrate sub-micron diameter Si nanowire arrays with aspect ratios as high as 180:1, and present the challenges in producing solid nanowires using MacEtch as the doping level increases in both p- and n-type Si. We report a systematic reduction in the porosity of these nanowires by adjusting the etching solution composition and temperature. We found that the porosity decreases from top to bottom along the axial direction and increases with etching time. With a MacEtch solution that has a high [HF]:[H(2)O(2)] ratio and low temperature, it is possible to form completely solid nanowires with aspect ratios of less than approximately 10:1. However, further etching to produce longer wires renders the top portion of the nanowires porous.

Formation of high aspect ratio GaAs nanostructures with metal-assisted chemical etching.

Periodic high aspect ratio GaAs nanopillars with widths in the range of 500-1000 nm are produced by metal-assisted chemical etching (MacEtch) using n-type (100) GaAs substrates and Au catalyst films patterned with soft lithography. Depending on the etchant concentration and etching temperature, GaAs nanowires with either vertical or undulating sidewalls are formed with an etch rate of 1-2 µm/min. The realization of high aspect ratio III-V nanostructure arrays by wet etching can potentially transform the fabrication of a variety of optoelectronic device structures including distributed Bragg reflector (DBR) and distributed feedback (DFB) semiconductor lasers, where the surface grating is currently fabricated by dry etching.