Spin-Selective Angular Dispersion Control in Dielectric Metasurfaces for Multichannel Meta-Holographic Displays.

Angle-dependent next-generation displays have potential applications in 3D stereoscopic and head-mounted displays, image combiners, and encryption for augmented reality (AR) and security. Metasurfaces enable such exceptional functionalities with groundbreaking achievements in efficient displays over the past decades. However, limitations in angular dispersion control make them unfit for numerous nanophotonic applications. Here, we propose a spin-selective angle-dependent all-dielectric metasurface with a unique design strategy to manifest distinct phase information at different incident angles of light. As a proof of concept, the phase masks of two images are encoded into the metasurface and projected at the desired focal plane under different angles of left circularly polarized (LCP) light. Specifically, the proposed multifunctional metasurface generates two distinct holographic images under LCP illumination at angles of +35 and -35°. The presented holographic displays may provide a feasible route toward multifunctional meta-devices for potential AR displays, encrypted imaging, and information storage applications.

Flexible and Dynamic Light-Guided Electrochemiluminescence for Spatiotemporal Imaging of Photoelectrochemical Processes on Hematite.

Here, we report an electrochemiluminescence (ECL)-based approach for imaging of local photoelectrochemical processes on hematite in a spatially and temporally controlled manner. The local processes were guided by flexible and dynamic light illumination, not requiring any prepatterned conductive features or photomasks, with a digital micromirror device (DMD). The imaging approach was based on light-addressable electrochemical reactions on hematite, resulting in photoinduced ECL emission for spatiotemporally resolved imaging of photoelectrochemical processes selectively guided by light illumination. After clarifying the capability of hematite as a photosensitive electrode, we validated that the illuminated hematite exhibited stable light-guided ECL emission in correspondence with the illuminated area, with a spatial resolution of 0.8 µm and a temporal resolution of 1 µs, even over a long period of 6 h. More importantly, this study exemplified the simple yet effective ECL-based approach for electrochemical visualization of local photoelectrochemical processes guided by flexible and dynamic adjustment of light illumination in a spatiotemporally controlled way.

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.

Ultraviolet-Visible Multifunctional Vortex Metaplates by Breaking Conventional Rotational Symmetry.

Metasurfaces have shown remarkable potential to manipulate many of light's intrinsic properties, such as phase, amplitude, and polarization. Recent advancements in nanofabrication technologies and persistent efforts from the research community result in the realization of highly efficient, broadband, and multifunctional metasurfaces. Simultaneous control of these characteristics in a single-layered metasurface will be an apparent technological extension. Here, we demonstrate a broadband multifunctional metasurface platform with the unprecedented ability to independently control the phase profile for two orthogonal polarization states of incident light over dual-wavelength spectra (ultraviolet to visible). In this work, multiple single-layered metasurfaces composed of bandgap-engineered silicon nitride nanoantennas are designed, fabricated, and optically characterized to demonstrate broadband multifunctional light manipulation ability, including structured beam generation and meta-interferometer implementation. We envision the presented metasurface platform opening new avenues for broadband multifunctional applications including ultraviolet-visible spectroscopy, spatially modulated illumination microscopy, optical data storage, and information encoding.

In Situ Confocal Fluorescence Lifetime Imaging of Nanopore Electrode Arrays with Redox Active Fluorogenic Amplex Red.

Direct imaging of electrochemical processes on electrode surfaces is a central part of understanding spatially heterogeneous electrochemical processes on the surfaces. Herein, we report a strategy for the spatially resolved imaging of local faradaic processes on nanoscale electrochemical interfaces. This strategy is based on fluorescence lifetime imaging microscopy (FLIM) with the use of Amplex Red as a fluorogenic redox probe. After verifying the capability of Amplex Red for fluorescence lifetime imaging, we demonstrated the turn-on FLIM-based imaging of faradaic processes on the electrochemical interfaces of different dimensions. In particular, we achieved spatially resolved visualization of the local electrochemical processes occurring on even nanopore electrode arrays as well as conventional microelectrodes, including disk-shaped ultramicroelectrodes and interdigitated array microelectrodes.

Turn-On Fluorescence Sensing of Oxygen with Dendrimer-Encapsulated Platinum Nanoparticles as Tunable Oxidase Mimics for Spatially Resolved Measurement of Oxygen Gradient in a Human Gut-on-a-Chip.

Turn-on type fluorescence sensing of O2 is considered a promising approach to developing ways to measure O2 in microenvironments with spatially distributed O2 levels. As a class of nanomaterials with a high degree of control over composition and structure, dendrimer-encapsulated nanoparticles (DENs) are promising candidates to mimic biological enzymes. Here, we report a strategy to monitor spatially distributed O2 across a three-dimensional (3D) human intestinal epithelial layer in a gut-on-a-chip in a turn-on fluorescence sensing manner. The strategy is based on the oxidase-mimetic activity of Pt DENs for catalytic oxidation of nonfluorescent Amplex Red to highly fluorescent resorufin in the presence of O2. We synthesized Pt DENs using two different types of dendrimers (i.e., amine-terminated or hydroxyl-terminated generation 6 polyamidoamine (PAMAM) dendrimers) with six different Pt2+/dendrimer ratios (i.e., 55, 200, 220, 550, 880, and 1320). After clarifying the intrinsic oxidase-mimetic activity of Pt DENs, we determined tunable oxidase-mimetic activity of Pt DENs, especially with fine-tuning the ratios of the Pt precursor ions and dendrimers. Particularly, the optimal Pt DENs having a Pt2+/dendrimer ratio of 1320 exhibited an ∼117-fold increase in the oxidase-mimetic activity for catalyzing the aerobic oxidation of Amplex Red to resorufin compared to one having a Pt2+/dendrimer ratio of 200. This study exemplified a simple yet effective approach for spatially resolved imaging of O2 using metal nanoparticle-based oxidase mimics in microphysiological environments like a human gut-on-a-chip.

Three-Dimensional TEM Study of Dendrimer-Encapsulated Pt Nanoparticles for Visualizing Structural Characteristics of the Whole Organic-Inorganic Hybrid Nanostructure.

Here, we report three-dimensional (3-D) visualization of dendrimer-encapsulated Pt nanoparticles (Pt DENs) by using 3-D electron tomography to reveal intricate structural characteristics of their whole organic-inorganic hybrid nanostructure. We reconstructed the 3-D spatial volume of Pt DENs by back-projecting a tilt series of two-dimensional (2-D) projections of Pt nanoparticles encapsulated inside dendrimers negatively stained with uranyl acetate. The direct 3-D visualization of Pt DENs elucidated their encapsulation characteristics with the spatial imaging of Pt nanoparticles embraced inside dendrimers in three dimensions. The encapsulation characteristics of Pt DENs were further verified with selective electrochemical poisoning experiments. In addition, quantitative 3-D structural characterization of Pt DENs provided more accurate and precise size distributions of nanoparticles than those obtained from conventional 2-D transmission electron microscopy analysis relying only on a 3-D structure projected on a 2-D plane.

Formic acid dehydrogenation over PdNi alloys supported on N-doped carbon: synergistic effect of Pd-Ni alloying on hydrogen release.

Bimetallic Pd1Nix alloys supported on nitrogen-doped carbon (Pd1Nix/N-C, x = 0.37, 1.3 and 3.6) exhibit higher activities than Pd/N-C towards dehydrogenation of formic acid (HCO2H, FA). Density functional theory (DFT) calculations provided electronic and atomic structures, energetics and reaction pathways on Pd(111) and Pd1Nix(111) surfaces of different Pd/Ni compositions. A density of states (DOS) analysis disclosed the electronic interactions between Pd and Ni revealing novel active sites for FA dehydrogenation. Theoretical analysis of FA dehydrogenation on Pd1Nix(111) (x = 0.33, 1 and 3) shows that the Pd1Ni1(111) surface provides optimum H2-release efficiency via a favorable 'HCOO pathway', in which a hydrogen atom and one of the two oxygen atoms of FA interact directly with surface Ni atoms producing adsorbed CO2 and H2. The enhanced efficiency is also attributed to the blocking of an unfavorable 'COOH pathway' through which a C-O bond is broken and side products of CO and H2O are generated.

Chiroptical Metasurfaces: Principles, Classification, and Applications.

Chiral materials, which show different optical behaviors when illuminated by left or right circularly polarized light due to broken mirror symmetry, have greatly impacted the field of optical sensing over the past decade. To improve the sensitivity of chiral sensing platforms, enhancing the chiroptical response is necessary. Metasurfaces, which are two-dimensional metamaterials consisting of periodic subwavelength artificial structures, have recently attracted significant attention because of their ability to enhance the chiroptical response by manipulating amplitude, phase, and polarization of electromagnetic fields. Here, we reviewed the fundamentals of chiroptical metasurfaces as well as categorized types of chiroptical metasurfaces by their intrinsic or extrinsic chirality. Finally, we introduced applications of chiral metasurfaces such as multiplexing metaholograms, metalenses, and sensors.

Pd2+ -Initiated Formic Acid Decomposition: Plausible Pathways for C-H Activation of Formate.

Formic acid (HCOOH, FA) has long been considered as a promising hydrogen-storage material due to its efficient hydrogen release under mild conditions. In this work, FA decomposes to generate CO2 and H2 selectively in the presence of aqueous Pd2+ complex solutions at 333 K. Pd(NO3 )2 was the most effective in generating H2 among various Pd2+ complexes explored. Pd2+ complexes were in situ reduced to Pd0 species by the mixture of FA and sodium formate (SF) during the course of the reaction. Since C-H activation reaction of Pd2+ -bound formate is occurred for both Pd2+ reduction and H2 /CO2 gas generation, FA decomposition pathways using several Pd2+ species were explored using density functional theory (DFT) calculations. Rotation of formate bound to Pd2+ , ß-hydride elimination, and subsequent CO2 and H2 elimination by formic acid were examined, providing different energies for rate determining step depending on the ligand electronics and geometries coordinated to the Pd2+ complexes. Finally, Pd2+ reduction toward Pd0 pathways were explored computationally either by generated H2 or reductive elimination of CO2 and H2 gas.

Repetitively Coupled Chemical Reduction and Galvanic Exchange as a Synthesis Strategy for Expanding Applicable Number of Pt Atoms in Dendrimer-Encapsulated Pt Nanoparticles.

In this study, we report the controllable synthesis of dendrimer-encapsulated Pt nanoparticles (Pt DENs) utilizing repetitively coupled chemical reduction and galvanic exchange reactions. The synthesis strategy allows the expansion of the applicable number of Pt atoms encapsulated inside dendrimers to more than 1000 without being limited by the fixed number of complexation sites for Pt2+ precursor ions in the dendrimers. The synthesis of Pt DENs is achieved in a short period of time (i.e., ∼10 min) simply by the coaddition of appropriate amounts of Cu2+ and Pt2+ precursors into aqueous dendrimer solution and subsequent addition of reducing agents such as BH4-, resulting in fast and selective complexation of Cu2+ with the dendrimers and subsequent chemical reduction of the complexed Cu2+ while uncomplexed Pt2+ precursors remain oxidized. Interestingly, the chemical reduction of Cu2+, leading to the formation of Cu nanoparticles encapsulated inside the dendrimers, is coupled with the galvanic exchange of the Cu nanoparticles with the nearby Pt2+. This coupling repetitively proceeds until all of the added Pt2+ ions form into Pt nanoparticles encapsulated inside the dendrimers. In contrast to the conventional method utilizing direct chemical reduction, this repetitively coupled chemical reduction and galvanic exchange enables a substantial increase in the applicable number of Pt atoms up to 1320 in Pt DENs while maintaining the unique features of DENs.

Tunability of the Adsorbate Binding on Bimetallic Alloy Nanoparticles for the Optimization of Catalytic Hydrogenation.

In this paper, we show that PtAu and PdAu random alloy dendrimer-encapsulated nanoparticles with an average size of ∼1.6 nm have different catalytic activity trends for allyl alcohol hydrogenation. Specifically, PtAu nanoparticles exhibit a linear increase in activity with increasing Pt content, whereas PdAu dendrimer-encapsulated nanoparticles show a maximum activity at a Pd content of ∼60%. Both experimental and theoretical results suggest that this contrasting behavior is caused by differences in the strength of H binding on the PtAu and PdAu alloy surfaces. The results have significant implications for predicting the catalytic performance of bimetallic nanoparticles on the basis of density functional theory calculations.

Tailoring Catalytic Activity of Pt Nanoparticles Encapsulated Inside Dendrimers by Tuning Nanoparticle Sizes with Subnanometer Accuracy for Sensitive Chemiluminescence-Based Analyses.

Here, we report the size-dependent catalysis of Pt dendrimer-encapsulated nanoparticles (DENs) having well-defined sizes over the range of 1-3 nm with subnanometer accuracy for the highly enhanced chemiluminescence of the luminol/H2O2 system. This size-dependent catalysis is ascribed to the differences in the chemical states of the Pt DENs as well as in their surface areas depending on their sizes. Facile and versatile applications of the Pt DENs in diverse oxidase-based assays are demonstrated as efficient catalysts for sensitive chemiluminescence-based analyses.

Functionalization of indium tin oxide electrode with both of dendrimer-encapsulated Pt nanoparticles and chemically converted graphenes for enhanced electrochemiluminescence of luminol/H2O2.

Here, we report highly enhanced electrochemiluminescence (ECL) of luminol in the presence of H2O2 on indium tin oxides (ITOs) modified with both of dendrimer-encapsulated Pt nanoparticles (Pt DENs) and chemically converted graphenes (CCGs). The ITO electrodes were electrochemically modified with size-monodisperse Pt DENs via electrooxidative grafting of the terminal amines of the dendrimers encapsulating Pt nanoparticles. The Pt DEN-modified ITOs were then decorated with CCG sheets via electrostatic attachments of graphene oxides (GOs) and subsequent chemical reduction of the GOs to the CCGs. The resulting CCG-Pt DEN/ITO electrodes exhibited highly catalyzed electrochemical oxidation of luminol/H2O2, leading to significantly enhanced ECL of the luminol/H2O2 system, i.e., ∼15-fold enhancement, compared to ECL emission from bare ITOs even at lower applied potentials, which allowed sensitive ECL-based analysis of H2O2 using the CCG-Pt DEN/ITOs. Graphical abstract We report the highly enhanced electrochemiluminescence of the luminol/H2O2 system on the indium tin oxide electrodes modified with both of Pt nanoparticles and chemically converted graphenes using amine-terminated dendrimers.

Modification of indium tin oxide with dendrimer-encapsulated nanoparticles to provide enhanced stable electrochemiluminescence of Ru(bpy)3(2+)/tripropylamine while preserving optical transparency of indium tin oxide for sensitive electrochemiluminescence-based analyses.

Here, we report highly enhanced stable electrogenerated chemiluminescence (ECL) of Ru(bpy)3(2+) (bpy = 2,2'-bipyridyl) with tripropylamine (TPrA) coreactant on indium tin oxide (ITO) electrodes modified with amine-terminated dendrimers encapsulating catalytic nanoparticles while maintaining optical transparency of ITO and feasibility of the modified ITOs to sensitive ECL-based assays. As model systems, we prepared Pt and Au dendrimer-encapsulated nanoparticles (DENs) using amine-terminated sixth-generation poly(amido amine) dendrimers and subsequently immobilized the DENs onto ITO surfaces via electrooxidative grafting of the terminal amines of dendrimers to the surfaces. The resulting DEN-modified ITOs preserved good optical transparency of ITO and exhibited highly catalyzed electrochemical oxidation of Ru(bpy)3(2+)/TPrA, leading to significantly increased ECL emission. Especially, the Pt DEN-modified ITO electrode provides negligible transmittance drop, i.e., only ∼1.99% over the entire visible region, and exhibited not only much enhanced (i.e., ∼213-fold increase compared to ECL obtained from bare ITO) but also stable ECL emission under consecutive potential scans from 0.00 to 1.10 V for 10 cycles, which allowed ∼329 times more sensitive ECL-based analysis of nicotine using the Pt DEN-modified ITO compared with the use of bare ITO.

Blue luminescence of dendrimer-encapsulated gold nanoclusters.

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl-terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady-state and time-resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au8 and Au13). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.

Tailoring high-refractive-index nanocomposites for manufacturing of ultraviolet metasurfaces.

Nanoimprint lithography (NIL) has been utilized to address the manufacturing challenges of high cost and low throughput for optical metasurfaces. To overcome the limitations inherent in conventional imprint resins characterized by a low refractive index (n), high-n nanocomposites have been introduced to directly serve as meta-atoms. However, comprehensive research on these nanocomposites is notably lacking. In this study, we focus on the composition of high-n zirconium dioxide (ZrO2) nanoparticle (NP) concentration and solvents used to produce ultraviolet (UV) metaholograms and quantify the transfer fidelity by the measured conversion efficiency. The utilization of 80 wt% ZrO2 NPs in MIBK, MEK, and acetone results in conversion efficiencies of 62.3%, 51.4%, and 61.5%, respectively, at a wavelength of 325 nm. The analysis of the solvent composition and NP concentration can further enhance the manufacturing capabilities of high-n nanocomposites in NIL, enabling potential practical use of optical metasurfaces.

A water-soluble label for food products prevents packaging waste and counterfeiting.

Sustainability, humidity sensing and product origin are important features of food packaging. While waste generated from labelling and packaging causes environmental destruction, humidity can result in food spoilage during delivery and counterfeit-prone labelling undermines consumer trust. Here we introduce a food label based on a water-soluble nanocomposite ink with a high refractive index that addresses these issues. By patterning the nanocomposite ink using nanoimprint lithography, the resultant metasurface shows bright and vivid structural colours. This method makes it possible to quickly and inexpensively create patterns on large surfaces. A QR code is also developed that can provide up-to-date information on food products. Microprinting hidden in the QR code protects against counterfeiting, cannot be physically detached or replicated and may be used as a humidity indicator. Our proposed food label can reduce waste while ensuring customers receive accurate product information.

Dynamic Hyperspectral Holography Enabled by Inverse-Designed Metasurfaces with Oblique Helicoidal Cholesterics.

Metasurfaces are flat arrays of nanostructures that allow exquisite control of phase and amplitude of incident light. Although metasurfaces offer new active element for both fundamental science and applications, the challenge still remains to overcome their low information capacity and passive nature. Here, by integrating an inverse-designed-metasurface with oblique helicoidal cholesteric liquid crystal (ChOH), simultaneous spatial and spectral tunable metasurfaces with a high information capacity for dynamic hyperspectral holography, are demonstrated. The inverse design facilitates a single-phase map encoding of ten independent holographic images at different wavelengths. ChOH provides precise spectral modulation with narrow bandwidth and wide tunable regime in response to programmed stimuli, thus enabling dynamic switching of the multicolor holography. The results provide simple and generalizable principles for the rational design of interactive metasurfaces that will find numerous applications, including security platform.

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.