Achromatic Full Stokes Polarimetry Metasurface for Full-Color Polarization Imaging in the Visible Range.

Metasurfaces provide an ultrathin platform for compact, real-time polarimetry. However, their applications in polychromatic scenes are restricted by narrow operating bandwidths that causes spectral information loss. Here, we demonstrate full-color polarization imaging using an achromatic polarimeter consisting of four polarization-dependent metalenses. Leveraging an intelligent design scheme, we achieve effective arbitrary phase compensation and multiobjective matching with a limited database. This system provides broadband achromaticity across wavelengths from 450 to 650 nm, resulting in a relative bandwidth of approximately 0.364 for full Stokes imaging. Experimental reconstruction errors for wavelengths of 450, 550, and 650 nm are 7.5%, 5.9%, and 3.8%, respectively. Performance is evaluated based on both achromatic bandwidth and crosstalk, with our design achieving three times the performance of the current state-of-the-art. The full-color, full-polarization imaging capability of the device is further validated with a customized object. The proposed scheme advances polarization imaging for practical applications.

High-purity and wide-angle reflective structural colors based on an all-dielectric Fabry-Pérot cavity structure.

High-purity structural colors with low fabrication cost are in demand for their commercial applications. Here, we demonstrate an all-dielectric Fabry-Pérot cavity structure consisting of four-layer lossy and lossless dielectric films alternately stacked for producing high-purity and angle-invariant reflective colors. Multiple cavity resonances function together to significantly suppress the undesired reflection with the enhanced optical absorption, leading to a distinct and saturated color with a high efficiency of ∼70%. Besides, due to the high refractive indices of constituent materials, the color appearance of the designed structure can be maintained well at ±50° incident angle for two polarization states. The excellent color performance of the proposed device together with cost-effective manufacturing convenience opens up new avenues for their large-area applications in various areas.

High-performance, large-area flexible SERS substrates prepared by reactive ion etching for molecular detection.

In the realm of molecular detection, the surface-enhanced Raman scattering (SERS) technique has garnered increasing attention due to its rapid detection, high sensitivity, and non-destructive characteristics. However, conventional rigid SERS substrates are either costly to fabricate and challenging to prepare over a large area, or they exhibit poor uniformity and repeatability, making them unsuitable for inspecting curved object surfaces. In this work, we present a flexible SERS substrate with high sensitivity as well as good uniformity and repeatability. First, the flexible polydimethylsiloxane (PDMS) substrate is manually formulated and cured. SiO2/Ag layer on the substrate can be obtained in a single process by using ion beam sputtering. Then, reactive ion etching is used to etch the upper SiO2layer of the film, which directly leads to the desired densely packed nanostructure. Finally, a layer of precious metal is deposited on the densely packed nanostructure by thermal evaporation. In our proposed system, the densely packed nanostructure obtained by etching the SiO2layer directly determines the SERS ability of the substrate. The bottom layer of silver mirror can reflect the penetrative incident light, the spacer layer of SiO2and the top layer of silver thin film can further localize the light in the system, which can realize the excellent absorption of Raman laser light, thus enhancing SERS ability. In the tests, the prepared substrates show excellent SERS performance in detecting crystalline violet with a detection limit of 10-11M. The development of this SERS substrate is anticipated to offer a highly effective and convenient method for molecular substance detection.

Reliable fabrication of 3D freestanding nanostructures via all dry stacking of incompatible photoresist.

Three-dimensional (3D) free-standing nanostructures based on electron-beam lithography (EBL) have potential applications in many fields with extremely high patterning resolution and design flexibility with direct writing. In numerous EBL processes designed for the creation of 3D structures, the multilayer resist system is pivotal due to its adaptability in design. Nevertheless, the compatibility of solvents between different layers of resists often restricts the variety of feasible multilayer combinations. This paper introduces an innovative approach to address the bottleneck issue by presenting a novel concept of multilayer resist dry stacking, which is facilitated by a near-zero adhesion strategy. The poly(methyl methacrylate) (PMMA) film is stacked onto the hydrogen silsesquioxane (HSQ) resist using a dry peel and release technique, effectively circumventing the issue of HSQ solubilization by PMMA solvents typically encountered during conventional spin-coating procedures. Simultaneously, a dry lift-off technique can be implemented by eschewing the use of organic solvents during the wet process. This pioneering method enables the fabrication of high-resolution 3D free-standing plasmonic nanostructures and intricate 3D free-standing nanostructures. Finally, this study presents a compelling proof of concept, showcasing the integration of 3D free-standing nanostructures, fabricated via the described technique, into the realm of Fabry-Perot cavity resonators, thereby highlighting their potential for practical applications. This approach is a promising candidate for arbitrary 3D free-standing nanostructure fabrication, which has potential applications in nanoplasmonics, nanoelectronics, and nanophotonics.

Ultrathin Lithiophilic 3D Arrayed Skeleton Enabling Spatial-Selection Deposition for Dendrite-Free Lithium Anodes.

Lithium metal batteries are promising to become a new generation of energy storage batteries. However, the growth of Li dendrites and the volume expansion of the anode are serious constraints to their commercial implementation. Herein, a controllable strategy is proposed to construct an ultrathin 3D hierarchical host of honeycomb copper micromesh loaded with lithiophilic copper oxide nanowires (CMMC). The uniquely designed 3D hierarchical arrayed skeletons demonstrate a surface-preferred and spatial-selective effect to homogenize local current density and relieve the volume expansion, effectively suppressing the dendrite growth. Employing the constructed CMMC current collector in a half-cell, >400 cycles with 99% coulombic efficiency at 0.5 mA cm-2 is performed. The symmetric battery cycles stably for >2000 h, and the full battery delivers a capacity of 166.6 mAh g-1 . This facile and controllable approach provides an effective strategy for constructing high-performance lithium metal batteries.

Topologically optimized concentric-nanoring metalens with 1 mm diameter, 0.8†NA and 600†nm imaging resolution in the visible.

Metalenses can achieve diffraction-limited focusing via localized phase modification of the incoming light beam. However, the current metalenses face to the restrictions on simultaneously achieving large diameter, large numerical aperture, broad working bandwidth and the structure manufacturability. Herein, we present a kind of metalenses composed of concentric nanorings that can address these restrictions using topology optimization approach. Compared to existing inverse design approaches, the computational cost of our optimization method is greatly reduced for large-size metalenses. With its design flexibility, the achieved metalens can work in the whole visible range with millimeter size and a numerical aperture of 0.8 without involving high-aspect ratio structures and large refractive index materials. Electron-beam resist PMMA with a low refractive index is directly used as the material of the metalens, enabling a much more simplified manufacturing process. Experimental results show that the imaging performance of the fabricated metalens has a resolution better than 600 nm corresponding to the measured FWHM of 745 nm.

Tunable Polarization-Multiplexed Achromatic Dielectric Metalens.

Tunable metasurfaces provide a compact and efficient strategy for optical active wavefront shaping. Varifocal metalens is one of the most important applications. However, the existing tunable metalens rarely serves broadband wavelengths restricting their applications in broadband imaging and color display due to chromatic aberration. Herein, an electrically tunable polarization-multiplexed achromatic metalens integrated with twisted nematic liquid crystals (TNLCs) in the visible region is demonstrated. The phase profiles at different wavelengths under two orthogonal polarization channels are customized by the particle swarm optimization algorithm and matched with the dielectric metaunits database to achieve polarization-multiplexed achromatic performance. By combining the broadband linear polarization conversion ability of TNLC, the tunability of varifocal achromatic metalens is realized by applying different voltages. Further, the electrically tunable customized dispersion-manipulated metalens and switchable color metaholograms are demonstrated. The proposed devices will accelerate the application of metasurfaces in broadband zoom imaging, AR/VR displays and spectral detection.

Freestanding 3D Metallic Micromesh for High-Performance Flexible Transparent Solid-State Zinc Batteries.

Flexible transparent energy supplies are extremely essential to the fast-growing flexible electronic systems. However, the general developed flexible transparent energy storage devices are severely limited by the challenges of low energy density, safety issues, and/or poor compatibility. In this work, a freestanding 3D hierarchical metallic micromesh with remarkble optoelectronic properties (T = 89.59% and Rs = 0.23 Ω sq-1 ) and super-flexibility is designed and manufactured for flexible transparent alkaline zinc batteries. The 3D Ni micromesh supported Cu(OH)2 @NiCo bimetallic hydroxide flexible transparent electrode (3D NM@Cu(OH)2 @NiCo BH) is obtained by a combination of photolithography, chemical etching, and electrodeposition. The negative electrode is constructed by electrodeposition of electrochemically active zinc on the surface of Ni@Cu micromesh (Ni@Cu@Zn MM). The metallic micromesh with 3D hierarchical nanoarchitecture can not only ensure low sheet resistance, but also realize high mass loading of active materials and short electron/ion transmission path, which can guarantee high energy density and high-rate capability of the transparent devices. The flexible transparent 3D NM@Cu(OH)2 @NiCo BH electrode realizes a specific capacity of 66.03 µAh cm-2 at 1 mA cm-2 with a transmittance of 63%. Furthermore, the assembled solid-state NiCo-Zn alkaline battery exhibits a desirable energy density/power density of 35.89 µWh cm-2 /2000.26 µW cm-2 with a transmittance of 54.34%.

Nanoporous Intermetallic SnTe Enables Efficient Electrochemical CO2 Reduction into Formate via Promoting the Fracture of Metal-Oxygen Bonding.

Electrochemical reduction of CO2 into formate product is considered the most practical significance link in the carbon cycle. Developing cheap and efficient electrocatalysts with high selectivity for formate on a wide operated potential window is desirable yet challenging. Herein, nanoporous ordered intermetallic tin-tellurium (SnTe) is synthesized with a greater reduction performance for electrochemical CO2 to formate reduction compared to bare Sn. This nanoporous SnTe achieves 93% Faradaic efficiency for formate production and maintains over 90% Faradaic efficiency at a wide voltage range from -1.0 to -1.3 V versus reversible hydrogen electrode (RHE), together with 60 h stability. Combining operando Raman spectroscopy studies with density functional theory calculations reveals that strong orbital interaction between Sn and neighboring tellurium (Te) in the intermetallic SnTe can lower the barriers of the oxygen cutoff hydrogenation and desorption steps by promoting the fracture of bond between metal and oxygen, leading to the significant enhancement of formate production.

Suspended 3D metallic dimers with sub-10 nm gap for high-sensitive SERS detection.

The suspended metallic nanostructures with tiny gaps have certain advantages in surface-enhanced Raman scattering (SERS) due to the coaction of the tiny metallic nanogaps and the substrate-decoupled electromagnetism resonant modes. In this study, we used the lithographic HSQ/PMMA electron-beam bilayer resist exposure combined with a deposition-induced nanogap-narrowing process to define elevated suspended metallic nanodimers with tiny gaps for surface-enhanced Raman spectroscopy detection. By adjusting the deposited metal thickness, the metallic dimers with sub-10 nm gaps can be reliably obtained. These dimers with tunable nanogaps successfully served as excellent SERS substrates, exhibiting remarkable high-sensitivity detection ability for crystal violet molecules. Systematic experiments and simulations were conducted to explain the origin of the improved SERS performance. The results showed that the 3D elevated suspended metallic dimers could achieve a higher SERS enhancement factor than the metallic dimers on HSQ pillars and a common Si substrate, demonstrating that this kind of suspended metallic dimer is a promising route for high-sensitive SERS detection and other plasmonic applications.

Sub-5 nm Lithography with Single GeV Heavy Ions Using Inorganic Resist.

In this work, we demonstrate a process having the capability to realize single-digit nanometer lithography using single heavy ions. By adopting 2.15 GeV 86Kr26+ ions as the exposure source and hydrogen silsesquioxane (HSQ) as a negative-tone inorganic resist, ultrahigh-aspect-ratio nanofilaments with sub-5 nm feature size, following the trajectory of single heavy ions, were reliably obtained. Control experiments and simulation analysis indicate that the high-resolution capabilities of both HSQ resist and the heavy ions contribute the sub-5 nm fabrication result. Our work on the one hand provides a robust evidence that single heavy ions have the potential for single-digit nanometer lithography and on the other hand proves the capability of inorganic resists for reliable sub-5 nm patterning. Along with the further development of heavy-ion technology, their ultimate patterning resolution is supposed to be more accessible for device prototyping and resist evaluation at the single-digit nanometer scale.

Enhancing Plasmonic Spectral Tunability with Anomalous Material Dispersion.

The field confinement of plasmonic systems enables spectral tunability under structural variations or environmental perturbations, which is the principle for various applications including nanorulers, sensors, and color displays. Here, we propose and demonstrate that materials with anomalous dispersion, such as Ge in the visible, improve spectral tunability. We introduce our proposal with a semianalytical guided mode picture. Using Ge-based film (Ag/Au)-coupled gap plasmon resonators, we implement two architectures and demonstrate the improved tunability with single-particle dark-field scattering, ensemble reflection, and color generation. We observe three-fold enhancement of tunability with Ge nanodisks compared with that of Si, a normal-dispersion material in the visible. The structural color generation of large array systems, made of inversely fabricated Ge-Ag resonators, exhibits a wide gamut. Our results introduce anomalous material dispersion as an extra degree of freedom to engineer the spectral tunability of plasmonic systems, especially relevant for actively tunable plasmonics and metasurfaces.

Electrically Tunable Multifunctional Polarization-Dependent Metasurfaces Integrated with Liquid Crystals in the Visible Region.

Metasurfaces open up new avenues for designing planar optics, enabling compact dynamic metadevices. Numerous dynamic strategies have been proposed, among which liquid crystal (LC) based metasurfaces are expected due to the maturity of LC materials. However, existing schemes rarely exploit the polarization manipulation capabilities of metasurfaces and the limited performance hinders the development of practical addressable devices. Here, we demonstrate an electrically tunable multifunctional polarization-dependent metasurface integrated with LCs in the visible range. By a combination of the helicity-dependent metasurface and the birefringent LCs, continuous intensity tuning and switching of two helicity channels are realized. Electrically tunable mono- and multicolor switchable metaholograms and dynamic varifocal metalenses are demonstrated with a simple and performance-enhancing integration scheme. Further, electrically addressable dynamic metasurfaces are achieved. The proposed modulation and integration schemes pave the way for addressable dynamic metasurface devices in various applications, such as space light modulators, light detection and ranging systems, and holographic displays.

Nanoporous B13 C2 towards Highly Efficient Electrochemical Nitrogen Fixation.

The electrochemical nitrogen fixation under mild conditions is a promising alternative to the current nitrogen industry with high energy consumption and greenhouse gas emission. Here, a nanoporous boron carbide (np-B13 C2 ) catalyst is reported for electrochemical nitrogen fixation, which is fabricated by the combination of metallurgical alloy design and chemical etching. The resulting np-B13 C2 exhibits versatile catalytic activities towards N2 reduction reactions (NRR) and N2 oxidation reaction (NOR). A high NH3 yield of 91.28 µg h-1 mgcat.-1 and Faradaic efficiency (FE) of 35.53% at -0.05 V versus the reversible hydrogen electrode are obtained for NRR, as well as long-term stability of up to 70 h, making them among the most active NRR electrocatalysts. This catalyst can also achieve a NO3- yield of 165.8 µg h-1  mgcat.-1 and a FE of 8.4% for NOR. In situ Raman spectroscopy and density functional theory calculations reveal that strong coupling between the BC sites modulates the electronic structures of adjacent B atoms of B13 C2 , which enables the B sites to effectively adsorb and activate chemical inert N2 molecules, resulting in lowered energy required by the potential-determining step. Besides, the introduction of carbon can increase the inherent conductivity and reduce the binding energy of the reactants, thus improving N2 fixation performance.

High-Resolution Van der Waals Stencil Lithography for 2D Transistors.

2D semiconductors have attracted tremendous attention as an atomically thin channel for transistors with superior immunity to short-channel effects. However, with atomic thin structure, the delicate 2D lattice is not fully compatible with conventional lithography processes that typically involve high-energy photon/electron radiation and unavoidable polymer residues, posing a key limitation for high performance 2D transistors. Here, a novel van der Waals (vdW) stencil lithography technique based on dry mask lamination process is developed. By pre-fabricating polymethyl methacrylate (PMMA) resist with designed patterns, the whole PMMA mask layers could be mechanically released from the sacrifice wafer and physically laminated on top of various 2D semiconductors. The vdW stencil lithography ensures pristine 2D surface without any high-energy electron/photon radiation, polymer residues, or chemical doping effects in conventional lithography process; and the soft nature of PMMA enables intimate contact between the mask and the 2D materials without physical gap, leading to ultra-high resolution down to 60 nm. Together, by applying vdW stencil lithography for 2D semiconductors, high performance transistors are demonstrated. Our method not only demonstrates improved 2D transistor performance without lithography induced damages, but also provides a new vdW stencil lithography technique for 2D materials with high resolution.

Enhancing the stability of polymer nanostructures via ultrathin oxide coatings for nano-optical device applications.

Polymer nanostructures have drawn tremendous attention due to their wide applications in nanotechnology. However, the morphology of the polymer nanostructures is fragile under harsh conditions such as high-power irradiation and organic-solution environments during the fabrication or the measurement processes, significantly limiting their potential applications. In this work, we propose and demonstrate a simple approach to improve the stability of polymer nanostructures by coating a conformal ultrathin oxide film via atomic-layer deposition. Due to the refractory and dense coating of the oxide layer, the stability of polymer structures is enhanced by the prohibition of deformation occurrences from thermally induced reflow and organic solution. As a proof of concept, poly(methyl methacrylate) (PMMA) nanostructures coated with a sub-10-nm TiO2layer are demonstrated, and the structures exhibit high temperature stability at 180 °C and good resistance to soluble damage from organic solutions. Subsequently, the mechanism of the improved thermal stability is analyzed via mechanical simulations. Such an effective approach is proposed to significantly broaden the application of polymer nanostructures as functional elements for optical structures/devices that require excellent thermal and chemical stability.

Fabrication of single-nanometer metallic gaps via spontaneous nanoscale dewetting.

Ultrasmall metallic nanogaps are of great significance for wide applications in various nanodevices. However, it is challenging to fabricate ultrasmall metallic nanogaps by using common lithographic methods due to the limited resolution. In this work, we establish an effective approach for successful formation of ultrasmall metallic nanogaps based on the spontaneous nanoscale dewetting effect during metal deposition. By varying the initial opening size of the exposed resist template, the influence of dewetting behavior could be adjusted and tiny metallic nanogaps can be obtained. We demonstrate that this method is effective to fabricate diverse sub-10 nm gaps in silver nanostructures. Based on this fabrication concept, even sub-5 nm metallic gaps were obtained. SERS measurements were performed to show the molecular detection capability of the fabricated Ag nanogaps. This approach is a promising candidate for sub-10 nm metallic gaps fabrication, thus possessing potential applications in nanoelectronics, nanoplasmonics, and nano-optoelectronics.

Periodic planar Fabry-Perot nanocavities with tunable interference colors based on filling density effects.

Structural colors of high performance and economically feasible fabrication are desired in various applications. Herein, we demonstrate that reflective full-color filters based on the interference effect can be realized in periodic Fabry-Perot (F-P) nanocavity arrays of the same thickness. Enabled by simply adjusting the nanocavity size and array period, the resonant wavelengths can be successively tuned in the whole visible light range, which is mainly attributed to the varied effective refractive index introduced by the different filling density of the F-P nanocavity. Compared to the plasmonic colors utilizing the similar nanostructures, the proposed interference colors offer unique advantages of higher color contrast, wider gamut, and lower fabrication requirements. Besides, these color filters do not involve modulating the vertical dimensions of the F-P nanocavities, which is conducive to the monolithic integration of multicolor optical cavities and their large-area applications in consumable products combined with replica patterning techniques, such as nanoimprinting and soft lithography.

Trichromatic and Tripolarization-Channel Holography with Noninterleaved Dielectric Metasurface.

Metasurfaces hold great potentials for advanced holographic display with extraordinary information capacity and pixel sizes in an ultrathin flat profile. A dual-polarization channel to encode two independent phase profiles or spatially multiplexed meta-holography by interleaved metasurfaces are captivated popular solutions to projecting multiplexed and vectorial images. However, the intrinsic limit of orthogonal polarization-channels, their crosstalk due to coupling between meta-atoms, and interleaving-induced degradation of efficiency and reconstructed image quality set great barriers for sophisticated meta-holography from being widely adopted. Here we report a noninterleaved TiO2 metasurface holography, and three distinct phase profiles are encoded into three orthogonal polarization bases with almost zero crosstalk. The corresponding three independently constructed intensity profiles are therefore assigned to trichromatic (RGB) beams, resulting in high-quality and high-efficiency vectorial meta-holography in the whole visible regime. Our strategy presents an unconventionally advanced holographic scheme by synergizing trichromatic colors and tripolarization channels, simply realized with a minimalist noninterleaved metasurface. Our work unlocks the metasurface's potentials on massive information storage, polarization optics, polarimetric imaging, holographic data encryption, etc.

Operando Identification of the Dynamic Behavior of Oxygen Vacancy-Rich Co3O4 for Oxygen Evolution Reaction.

The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure-activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO-Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH• first for VO-Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co-OOH•. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.