Three-dimensional nanoprinting via charged aerosol jets.

Three-dimensional (3D) printing1-9 has revolutionized manufacturing processes for electronics10-12, optics13-15, energy16,17, robotics18, bioengineering19-21 and sensing22. Downscaling 3D printing23 will enable applications that take advantage of the properties of micro- and nanostructures24,25. However, existing techniques for 3D nanoprinting of metals require a polymer-metal mixture, metallic salts or rheological inks, limiting the choice of material and the purity of the resulting structures. Aerosol lithography has previously been used to assemble arrays of high-purity 3D metal nanostructures on a prepatterned substrate26,27, but in limited geometries26-30. Here we introduce a technique for direct 3D printing of arrays of metal nanostructures with flexible geometry and feature sizes down to hundreds of nanometres, using various materials. The printing process occurs in a dry atmosphere, without the need for polymers or inks. Instead, ions and charged aerosol particles are directed onto a dielectric mask containing an array of holes that floats over a biased silicon substrate. The ions accumulate around each hole, generating electrostatic lenses that focus the charged aerosol particles into nanoscale jets. These jets are guided by converged electric-field lines that form under the hole-containing mask, which acts similarly to the nozzle of a conventional 3D printer, enabling 3D printing of aerosol particles onto the silicon substrate. By moving the substrate during printing, we successfully print various 3D structures, including helices, overhanging nanopillars, rings and letters. In addition, to demonstrate the potential applications of our technique, we printed an array of vertical split-ring resonator structures. In combination with other 3D-printing methods, we expect our 3D-nanoprinting technique to enable substantial advances in nanofabrication.

Scalable manufacturing of high-index atomic layer-polymer hybrid metasurfaces for metaphotonics in the visible.

Metalenses are attractive alternatives to conventional bulky refractive lenses owing to their superior light-modulating performance and sub-micrometre-scale thicknesses; however, limitations in existing fabrication techniques, including high cost, low throughput and small patterning area, have hindered their mass production. Here we demonstrate low-cost and high-throughput mass production of large-aperture visible metalenses using deep-ultraviolet argon fluoride immersion lithography and wafer-scale nanoimprint lithography. Once a 12″ master stamp is imprinted, hundreds of centimetre-scale metalenses can be fabricated using a thinly coated high-index film to enhance light confinement, resulting in a substantial increase in conversion efficiency. As a proof of concept, an ultrathin virtual reality device created with the printed metalens demonstrates its potential towards the scalable manufacturing of metaphotonic devices.

Polarization-independent edge detection based on the spin-orbit interaction of light.

In previous edge detection schemes based on the spin-orbit interaction of light, the direction and intensity of the edge-enhanced images are influenced by the incident polarization state. In this study, we develop an edge detection strategy that is insensitive to changes in both the incident polarization and the incident angle. The output intensity and transfer function remain entirely impervious to changes in incident polarization, being explicitly formulated as functions of the incident angle, specifically in terms of cot 2⁡θ i and cot⁡θ i , respectively. This behavior is attributed to the opposing nature of the polarization components E~r H-H and E~r V-V in the x-direction after undergoing mapping through the Glan polarizer, while the sum of polarization components E~r H-V and E~r V-H in the y-direction can be simplified to terms independent of incident polarization. Furthermore, we propose a metasurface design to achieve the required optical properties in order to realize the derived edge detection scheme.

Three-Dimensional Plasmonic Nanocluster-Driven Light-Matter Interaction for Photoluminescence Enhancement and Picomolar-Level Biosensing.

Plasmonic nanoparticle clusters promise to support unique engineered electromagnetic responses at optical frequencies, realizing a new concept of devices for nanophotonic applications. However, the technological challenges associated with the fabrication of three-dimensional nanoparticle clusters with programmed compositions remain unresolved. Here, we present a novel strategy for realizing heterogeneous structures that enable efficient near-field coupling between the plasmonic modes of gold nanoparticles and various other nanomaterials via a simple three-dimensional coassembly process. Quantum dots embedded in the plasmonic structures display ∼56 meV of a blue shift in the emission spectrum. The decay enhancement factor increases as the total contribution of radiative and nonradiative plasmonic modes increases. Furthermore, we demonstrate an ultracompact diagnostic platform to detect M13 viruses and their mutations from femtoliter volume, sub-100 pM analytes. This platform could pave the way toward an effective diagnosis of diverse pathogens, which is in high demand for handling pandemic situations.

Backward Phase-Matched Second-Harmonic Generation from Stacked Metasurfaces.

We demonstrate phase-matched second-harmonic generation (SHG) from three-dimensional metamaterials consisting of stacked metasurfaces. To achieve phase matching, we utilize a novel mechanism based on phase engineering of the metasurfaces at the interacting wavelengths, facilitating phase-matched SHG in the unconventional backward direction. Stacking up to five metasurfaces,we obtain a phase-matched SHG signal, which scales superlinearly with the number of layers. Our results motivate further investigations to achieve higher conversion efficiencies also with more complex wave fronts.

Angle-Resolved Polarimetry with Quasi-Bound States in the Continuum Plasmonic Metamaterials via 3D Aerosol Nanoprinting.

Three-dimensional (3D) plasmonic metamaterials, featuring well-arranged subwavelength nanostructures, facilitate effective coupling between electrical dipoles and incident electromagnetic waves. This coupling allows for unique optical responses including localized surface plasmon resonance (LSPR) and quasi-bound states in the continuum (q-BIC). While 3D plasmonic metamaterials with LSPR and q-BIC have been independently explored for sensors, achieving simultaneous optical responses in the near-infrared region remains challenging. Here, we present 3D plasmonic metamaterials that integrate LSPR and q-BIC within a single π-shaped plasmonic structure, fabricated using a 3D aerosol nanoprinting technique. This printing technique controls the local electrostatic field to precisely position charged metallic nanoaerosols, enabling parallel printing of π-shaped plasmonic structures under ambient conditions. The printed π-shaped plasmonic structures exhibit two distinct optical modes: x-polarization-sensitive LSPR and transverse magnetic mode-sensitive q-BIC within the near-infrared region. Exploiting these dual optical responses, we demonstrate simultaneous polarization detection and incident angle analysis by integrating the π-shaped plasmonic structures into commercial Fourier-transform infrared spectroscopy, termed "numerical aperture-detective polarimetry". This approach holds promise for evaluating alignment in optical and imaging systems with light distribution analysis. Furthermore, the 3D aerosol nanoprinting technique provides an avenue for fabricating 3D plasmonic metamaterials with intricate geometries and optical properties, expanding their potential applications in nano-optics.

Multicolor and 3D Holography Generated by Inverse-Designed Single-Cell Metasurfaces.

Metasurface-generated holography has emerged as a promising route for fully reproducing vivid scenes by manipulating the optical properties of light using ultra-compact devices. However, achieving multiple holographic images using a single metasurface is still difficult due to the capacity limit of a single meta-atom. In this work, an inverse design method based on gradient-descent optimization is presented to encode multiple pieces of holographic information into a single metasurface. The proposed method allows the inverse design of single-cell metasurfaces without the need for complex meta-atom design strategies, facilitating high-throughput fabrication using broadband low-loss materials. By exploiting the proposed design method, both multiplane red-green-blue (RGB) color and three-dimensional (3D) holograms are designed and experimentally demonstrated. Multiplane RGB color holograms with nine distinct holograms are achieved, which demonstrate the state-of-the-art data capacity of a phase-only metasurface. The first experimental demonstration of metasurface-generated 3D holograms with completely independent and distinct images in each plane is also presented. The current research findings provide a viable route for practical metasurface-generated holography by demonstrating the high-density holography produced by a single metasurface. It is expected to ultimately lead to optical storage, display, and full-color imaging applications.

Humidity-Responsive RGB-Pixels via Swelling of 3D Nanoimprinted Polyvinyl Alcohol.

Humidity-responsive structural coloration is actively investigated to realize real-time humidity sensors for applications in smart farming, food storage, and healthcare management. Here, humidity-tunable nano pixels are investigated with a 700 nm resolution that demonstrates full standard RGB (sRGB) gamut coverage with a millisecond-response time. The color pixels are designed as Fabry-Pérot (F-P) etalons which consist of an aluminum mirror substrate, humidity-responsive polyvinyl alcohol (PVA) spacer, and a top layer of disordered silver nanoparticles (NPs). The measured volume change of the PVA reaches up to 62.5% when the relative humidity (RH) is manipulated from 20 to 90%. The disordered silver NP layer permits the penetration of water molecules into the PVA layer, enhancing the speed of absorption and swelling down to the millisecond level. Based on the real-time response of the hydrogel-based F-P etalons with a high-throughput 3D nanoimprint technique, a high-resolution multicolored color print that can have potential applications in display technologies and optical encryption, is demonstrated.

Integrated metasurfaces for re-envisioning a near-future disruptive optical platform.

Metasurfaces have been continuously garnering attention in both scientific and industrial fields, owing to their unprecedented wavefront manipulation capabilities using arranged subwavelength artificial structures. To date, research has mainly focused on the full control of electromagnetic characteristics, including polarization, phase, amplitude, and even frequencies. Consequently, versatile possibilities of electromagnetic wave control have been achieved, yielding practical optical components such as metalenses, beam-steerers, metaholograms, and sensors. Current research is now focused on integrating the aforementioned metasurfaces with other standard optical components (e.g., light-emitting diodes, charged-coupled devices, micro-electro-mechanical systems, liquid crystals, heaters, refractive optical elements, planar waveguides, optical fibers, etc.) for commercialization with miniaturization trends of optical devices. Herein, this review describes and classifies metasurface-integrated optical components, and subsequently discusses their promising applications with metasurface-integrated optical platforms including those of augmented/virtual reality, light detection and ranging, and sensors. In conclusion, this review presents several challenges and prospects that are prevalent in the field in order to accelerate the commercialization of metasurfaces-integrated optical platforms.

Reaching the highest efficiency of spin Hall effect of light in the near-infrared using all-dielectric metasurfaces.

The spin Hall effect of light refers to a spin-dependent transverse splitting of light at a planar interface. Previous demonstrations to enhance the splitting have suffered from exceedingly low efficiency. Achievements of the large splitting with high efficiency have been reported in the microwave, but those in the optical regime remain elusive. Here, an approach to attain the large splitting with high efficiency in the near-infrared is proposed and experimentally demonstrated at 800 nm by using a dielectric metasurface. Modulation of the complex transmission of the metasurface leads to the shifts that reach 10λ along with efficiencies over 70% under two linear polarizations. Our work extends the recent attempts to achieve the large and efficient spin Hall effect of light, which have been limited only to the microwave, to the optical regime.

Enhancement of Luminous Intensity Emission from Incoherent LED Light Sources within the Detection Angle of 10° Using Metalenses.

In this work, we present metalenses (MLs) designed to enhance the luminous intensity of incoherent light-emitting diodes (LEDs) within the detection angles of 0° and 10°. The detection angle of 0° refers to the center of the LED. Because the light emitted from LEDs is incoherent and expressed as a surface light source, they are numerically described as a set of point sources and calculated using incoherent summation. The titanium dioxide (TiO2) and amorphous silicon (a-Si) nanohole meta-atoms are designed; however, the full 2π phase coverage is not reached. Nevertheless, because the phase modulation at the edge of the ML is important, an ML is successfully designed. The typical phase profile of the ML enhances the luminous intensity at the center, and the phase profile is modified to increase the luminous intensity in the target detection angle region. Far field simulations are conducted to calculate the luminous intensity after 25 m of propagation. We demonstrate an enhancement of the luminous intensity at the center by 8551% and 2115% using TiO2 and a-Si MLs, respectively. Meanwhile, the TiO2 and a-Si MLs with the modified phase profiles enhance the luminous intensity within the detection angle of 10° by 263% and 30%, respectively.

Three-dimensional artificial chirality towards low-cost and ultra-sensitive enantioselective sensing.

Artificial chiral structures have potential applications in the field of enantioselective signal sensing. Advanced nanofabrication methods enable a large diversity in geometric structures and broad selectivity of materials, which can be exploited to manufacture artificial three-dimensional chiral structures. Various chiroptical phenomena exploiting spin and orbital angular momentum at the nanoscale have been continuously exploited as a way to effectively detect enantiomers. This review introduces precisely controlled bottom-up and large-area top-down metamaterial fabrication methods to solve the limitations of high manufacturing cost and low production speed. Particle synthesis, self-assembly, glanced angled vapor deposition, and three-dimensional plasmonic nanostructure printing are introduced. Furthermore, emerging sensitive chiral sensing methods such as cavity-enhanced chirality, photothermal circular dichroism, and helical dichroism of single particles are discussed. The continuous progress of nanofabrication technology presents the strong potential for developing artificial chiral structures for applications in biomedical, pharmaceutical, nanophotonic systems.

Tunable metasurfaces via the humidity responsive swelling of single-step imprinted polyvinyl alcohol nanostructures.

The application of hydrogels in nanophotonics has been restricted due to their low fabrication feasibility and refractive index. Nevertheless, their elasticity and strength are attractive properties for use in flexible, wearable-devices, and their swelling characteristics in response to the relative humidity highlight their potential for use in tunable nanophotonics. We investigate the use of nanostructured polyvinyl alcohol (PVA) using a one-step nanoimprinting technique for tunable and erasable optical security metasurfaces with multiplexed structural coloration and metaholography. The resolution of the PVA nanoimprinting reaches sub-100 nm, with aspect ratios approaching 10. In response to changes in the relative humidity, the PVA nanostructures swell by up to ~35.5%, providing precise wavefront manipulation of visible light. Here, we demonstrate various highly-secure multiplexed optical encryption metasurfaces to display, hide, or destroy encrypted information based on the relative humidity both irreversibly and reversibly.

Three-dimensional plasmonic nanoclusters driven by co-assembly of thermo-plasmonic nanoparticles and colloidal quantum dots.

Metallic nanoparticles that support localized surface plasmons have emerged as fundamental iconic building blocks for nanoscale photonics. Self-assembled clustering of plasmonic nanoparticles with controlled near-field interactions offers an interesting novel route to manipulate the electromagnetic fields at a subwavelength scale. Various bottom-up, self-assembly manners have been successfully devised to build plasmonic nanoparticle clusters displaying attractive optical properties. However, the incapability to configure on-demand architectures limits its practical reliability uses for scalable nanophotonic devices. Furthermore, a critical challenge has been addressing the accurate positioning of functional nanoparticles, including catalytic nanoparticles, dielectric nanoparticles, and quantum dots (QDs) in the clustered plasmonic hotspots. This work proposes a micropipette-based self-assembly method to fabricate three-dimensional architectures composed of colloidal clusters. The heterogeneous colloidal clusters comprising metallic nanoparticles and QDs are fabricated in one step by the micropipette-based self-assembly method. A plasmonic clustered pillar embedding QDs exhibited excellent photoluminescence characteristics compared to a collapsed pillar. The experimental and theoretical demonstration of the localized surface plasmon resonance and thermo-plasmonic properties of the colloidal clusters was performed.

Nearly Perfect Transmissive Subtractive Coloration through the Spectral Amplification of Mie Scattering and Lattice Resonance.

Silicon has been utilized in metasurfaces to produce structural color filters due to its compatibility with mature and cost-effective methods for complementary metal oxide semiconductor devices. In this work, we propose and demonstrate efficiency- and scattering-enhanced structural color filters using all-dielectric metasurfaces made up of engineered hydrogenated amorphous silicon (a-Si:H) nanoblocks. Wavelength-dependent filtering is achieved by Mie scattering as each structure individually supports the electric dipole (ED) and magnetic dipole (MD) resonances. The ED and MD resonances are identified by observing the field profiles of the resonance calculated by finite element method (FEM) simulations. To enhance the efficiency and scattering response of the all-dielectric metasurfaces, the proposed structural color filters are designed with consideration of the lattice resonances and scattering directivity. The spectral positions of the transmission dips and peaks are rigorously analyzed in accordance with the Mie theory and multipole expansion. The transmission spectra exhibit 100% transmission where Kerker's first condition is satisfied, while the lattice resonances amplify the ED and MD scattering responses throughout the entire visible regime. Various colors are generated by varying the resonance peak, which is controlled by varying the geometric parameters of a-Si:H nanoblocks. The proposed structural color printing devices are expected to have applications in dynamic color displays, imaging devices, and photorealistic color printing.

Revealing Structural Disorder in Hydrogenated Amorphous Silicon for a Low-Loss Photonic Platform at Visible Frequencies.

The high refractive index of hydrogenated amorphous silicon (a-Si:H) at optical frequencies is an essential property for the efficient modulation of the phase and amplitude of light. However, substantial optical loss represented by its high extinction coefficient prevents it from being utilized widely. Here, the bonding configurations of a-Si:H are investigated, in order to manipulate the extinction coefficient and produce a material that is competitive with conventional transparent materials, such as titanium dioxide and gallium nitride. This is achieved by controlling the hydrogenation and silicon disorder by adjusting the chemical deposition conditions. The extinction coefficient of the low-loss a-Si:H reaches a minimum of 0.082 at the wavelength of 450 nm, which is lower than that of crystalline silicon (0.13). Beam-steering metasurfaces are demonstrated to validate the low-loss optical properties, reaching measured efficiencies of 42%, 62%, and 75% at the wavelengths of 450, 532, and 635 nm, respectively. Considering its compatibility with mature complementary metal-oxide-semiconductor processes, the low-loss a-Si:H will provide a platform for efficient photonic operating in the full visible regime.

Capillary-force-induced collapse lithography for controlled plasmonic nanogap structures.

The capillary force effect is one of the most important fabrication parameters that must be considered at the micro/nanoscale because it is strong enough to deform micro/nanostructures. However, the deformation of micro/nanostructures due to such capillary forces (e.g., stiction and collapse) has been regarded as an undesirable and uncontrollable obstacle to be avoided during fabrication. Here, we present a capillary-force-induced collapse lithography (CCL) technique, which exploits the capillary force to precisely control the collapse of micro/nanostructures. CCL uses electron-beam lithography, so nanopillars with various shapes can be fabricated by precisely controlling the capillary-force-dominant cohesion process and the nanopillar-geometry-dominant collapse process by adjusting the fabrication parameters such as the development time, electron dose, and shape of the nanopillars. CCL aims to achieve sub-10-nm plasmonic nanogap structures that promote extremely strong focusing of light. CCL is a simple and straightforward method to realize such nanogap structures that are needed for further research such as on plasmonic nanosensors.

Spectral Modulation through the Hybridization of Mie-Scatterers and Quasi-Guided Mode Resonances: Realizing Full and Gradients of Structural Color.

Metasurfaces made up of subwavelength arrays of Mie scatterers can be engineered to control the optical properties of incident light. The hybridization of the fundamental Mie resonances with lattice resonances greatly enhances the scattering cross-section of individual Mie scatterers. Through careful design of the locations of these hybridized modes using two differently engineered hydrogenated amorphous silicon nanorods, we numerically calculate and experimentally fabricate two examples of full color printing; one with spectral colors comparable to the Adobe RGB gamut, and another with gradients of color. We identify and characterize the mechanisms behind each and provide a framework that can be used to design any all-dielectric metasurfaces of subwavelength Mie scatterers for spectral modulation.

Full and gradient structural colouration by lattice amplified gallium nitride Mie-resonators.

The hybridised resonances between Mie-scatterers and lattice resonances, i.e. quasi-guided mode resonances, are investigated. The scattering of the Mie-resonators is improved by the first order of transmitted diffracted light which is coupled to the lattice formed by the Mie-resonators. The conditions of coupling are dependent on the refractive index of the substrate and the effective refractive index of the unit cell of the resonators. Based on the momentum matching conditions, the cut-off wavelength of coupling and the amount of the amplification can be controlled. As a proof-of-concept application of this framework, gallium nitride metasurfaces are designed to produce metasurfaces that display structural colour. Palettes of full spectral colour and gradients are successfully demonstrated. The hue of the colour can be controlled by changing the periodicity of the unit cell at a fixed filling ratio of Mie-scatterer radius to unit cell periodicity, since the increase in periodicity redshifts the cut-off wavelength of the lattice resonance conditions, identified as the Rayleigh anomaly. The brightness of the colour can be tuned by adjusting the filling ratio of the unit cell. Consequently, the proposed framework may provide a fundamental guideline to design spectral filters made up of low-index Mie-scatterers for various applications.

Electromagnetic chirality: from fundamentals to nontraditional chiroptical phenomena.

Chirality arises universally across many different fields. Recent advancements in artificial nanomaterials have demonstrated chiroptical responses that far exceed those found in natural materials. Chiroptical phenomena are complicated processes that involve transitions between states with opposite parities, and solid interpretations of these observations are yet to be clearly provided. In this review, we present a comprehensive overview of the theoretical aspects of chirality in light, nanostructures, and nanosystems and their chiroptical interactions. Descriptions of observed chiroptical phenomena based on these fundamentals are intensively discussed. We start with the strong intrinsic and extrinsic chirality in plasmonic nanoparticle systems, followed by enantioselective sensing and optical manipulation, and then conclude with orbital angular momentum-dependent responses. This review will be helpful for understanding the mechanisms behind chiroptical phenomena based on underlying chiral properties and useful for interpreting chiroptical systems for further studies.