Grating-Integrated Gold Nanograsses Encapsulated with ZIF-8: A Quantitative and Ultrasensitive Surface-Enhanced Raman Scattering Substrate.

We proposed and demonstrated highly sensitive hybrid surface-enhanced Raman scattering (SERS) substrates, which are grating-integrated gold nanograsses (GIGN) that are tip-selectively encapsulated by ZIF-8 nanospheres (GIGN/tip-ZIF). This unique structure is realized through the tip-selective modification of GIGN by polyvinylpyrrolidone (PVP), and then, the tips of the GIGN were encapsulated by ZIF-8 nanospheres. The ZIF-8 nanospheres can adsorb analyte molecules, resulting in the spatial overlap between the analyte molecules and the "hotspots" on the tips of GIGN. Such a unique GIGN/tip-ZIF hybrid SERS substrate exhibits high sensitivity and quantitative detection ability. The detection limits can reach as low as 10-11 M, and the relative standard deviation is 5.59% for 4-aminothiophenol (4-ATP). In a wide range of concentrations from 10-5 to 10-11 M, the SERS intensity and concentration relationship can be fitted as a sigmoidal curve with R2 = 0.988. These indicate that the GIGN/tip-ZIF hybrid SERS substrates have broad applications in detecting toxic and harmful substances in food safety, disease diagnosis, and environmental monitoring.

Transfer-Printing Hydrogel-Based Platform for Moisture-Driven Dynamic Display and Optical Anti-Counterfeiting.

Humidity-responsive materials offer a promising approach to achieving tunable metasurface systems due to their fast and reversible swelling responses to moisture, which enables many important applications, such as real-time humidity sensing, optical switches, dynamic displays, and optical information encryption. However, the humidity-responsive structural coloration generally cannot provide a high spatial resolution and requires a complex patterning process. Here, we present a scalable moisture-driven color-changing Fabry-Pérot (FP)-like cavity composed of a polyvinyl alcohol layer sandwiched between an upper gold nanoparticles assembly and a bottom gold mirror. Through nanoparticle contact printing, we pixelated these cavities with sub-micrometer sizes without crosstalk and achieved an ultrahigh display resolution of ∼400 nm. Meanwhile, these nanoparticle-based FP (NBFP) cavities exhibit more vibrant colors than those of conventional film-based ones due to broadband absorption of the disordered nanoparticle assembly. Moreover, the NBFP cavities exhibit a rapid response (<300 ms), benefiting from the membrane pores formed in the gaps between the adjacent nanoparticles. Finally, we demonstrated the applications of the NBFP cavities in optical anti-counterfeiting and dynamic multi-color printing. These results suggest that our approach will help to realize a colorful, fast, and ultrahigh-resolution dynamic display device in optical security and colorimetric sensing.

Fabricating 3D freestanding metamaterials on elastic substrates via the shadow metal-sputtering and plastic deformation.

3D metamaterials have gained considerable attention owing to their extraordinary optical properties and promising applications beyond natural materials. However, fabricating 3D metamaterials with high resolution and reliable controllability is still a significant challenge. Here, a novel approach to manufacturing various 3D freestanding plasmonic nanostructures on elastic substrates is demonstrated using the shadow metal-sputtering and plastic deformations. A critical step is constructing a freestanding "Γ-shape" gold structural array in poly(methyl methacrylate) (PMMA) hole array via the shadow metal-sputtering and following a multifilm transfer procedure. This "Γ-shape" structural array undergoes plastic deformation to form 3D freestanding metamaterials for removing the PMMA resist by the oxygen plasma. The approach allows accurate manipulations of the morphology, size, curvature, and bend orientation of 3D nanostructures. The spectral response of the 3D cylinder array was experimentally confirmed and understood by the simulations based on the finite element method (FEM). Moreover, the bulk refractive index (RI) sensitivity of up to 858 nm RIU-1 was achieved theoretically for this cylinder array. The proposed approach provides a new possibility to realize the fabrication of 3D freestanding plasmonic metamaterials with high resolution and compatible planar lithography procedures.

Tunable Fabry-Pérot Resonator with Dynamic Structural Color: A Visual and Ultrasensitive Hydrogen Sensor.

Hydrogen detection is crucial for the forthcoming hydrogen economy. Here, we present a visual, ultrasensitive, optical hydrogen sensor based on a tunable Fabry-Pérot (FP) resonator, which can fully release the volume expansion of palladium during hydrogenation and transfer this volume expansion into an optical signal. The FP resonator consists of a suspended polymethylmethacrylate/palladium (PMMA/Pd) bilayer on a gold (Au) square-hole array. The bottom of the gold square hole and hydrogen-sensitive PMMA/Pd bilayer form a dynamically tunable FP resonator. When hydrogen gas (H2) is loaded, the hydrogen-induced lateral expanding stress concavely deforms the suspended bilayer downward to the substrate, narrowing the metal-air-metal gap at the center of the hole, and finally leading to a spectral blue shift. Our experimental results show a giant spectral shift of 279 nm with a reflectance variation of 57% on exposure to 0.6% H2 mixed with air. Such an ultrahigh optical response results in a significant color change, enabling visual hydrogen detection. In addition, the sensor has a H2 detection limit down to 0.1% and good recyclability. These advantages indicate that the sensor has excellent potential for hydrogen sensing applications.

A flexible optical gas pressure sensor as the signal readout for point-of-care immunoassay.

Gas generation-based immunoassay is considered an attractive biosensing platform for the detection of biomarkers by incorporating the target recognition event with a catalyzed gas-generating reaction. Herein, an optical gas pressure sensor based on a silver/polydimethylsiloxane (Ag/PDMS) bilayer system was designed as a signal transducer to read the concentration of the detection target alpha-fetoprotein (AFP) quantitatively. In this proposed pressure-based assay, silicon dioxide (SiO2) nanospheres decorated with platinum (Pt) nanoparticles were coupled to detect antibodies by covalent linkage, and the captured antibodies were conjugated with magnetic beads via streptavidin-biotin interaction, simultaneously. When the AFP was loaded, the Pt-catalyzed hydrogen peroxide (H2O2) decomposition reaction was triggered to induce a significant increase in the reflectance signal of the Ag/PDMS bilayer gas pressure sensor (BGPS) due to a "wrinkled-specular" transition of the Ag film's surface. Under optimal conditions, the pressure-based biosensor exhibited a broad linear detection range from 0.05 to 132 ng mL-1 with a limit of detection (LOD) of 0.016 ng mL-1 for AFP, which satisfies the requirements for the clinical detection of AFP. Besides, the high specificity and detection accuracy of our Ag/PDMS BGPS also proved its feasibility for practical diagnosis.

In Situ Wide-Field Visualization of Palladium Hydrogenation.

Visualizing hydrogenation processes in palladium (Pd) in real-time is important to various hydrogen-involved applications. However, observing hydrogen diffusion of Pd was limited by its small permittivity variation, and the kinetics of lateral diffusion of hydrogen in Pd film was not reported. Here, we proposed an optical microscopy-based visualization of Pd hydrogenation from the diffusion surface to the interior by introducing a fast-response mechanical platform that transforms the hydrogen diffusion into self-organized ordered wrinkles with sharp optical contrast. This platform is a Au/Pd double layer on an elastomer, which results in directional hydrogenation from the sidewall to the interior. The kinetics of hydrogenation in the interior of the palladium along the diffusion direction was monitored in real-time. This platform will enable in situ visualization of atom/ion diffusion on metals that are crucial in energy storage and hydrogen detection.

Suspended Palladium/Polymer Bilayer for High-Contrast and Fast Hydrogen Sensors.

Hydrogen sensing is extremely essential for hydrogen-related applications due to the explosibility of hydrogen gas (H2). Here, we first present a high-contrast and fast optical hydrogen sensor, which is a partially suspended Pd/PMMA bilayer on a PDMS substrate with a microgroove array on the surface. The suspended structure reduces constraints from the substrate on the Pd film, leading to a large wrinkling amplitude and fast response rate during hydrogenation. The PMMA film can protect the Pd film from the poisonous impurities in the air and improve the flexibility of the bilayer. When exposed to 4% H2 mixed with air, the reflectance of the sensor drops down from 43 to 4% at 600 nm wavelength, in which the corresponding reflectance contrast, defined as the ratio of the reflectances before and after exposure to hydrogen, is 10.75. Such a high reflectance variation results from the light scattering induced by the wrinkling of the suspended Pd/PMMA bilayer during hydrogenation. Meanwhile, the sensor has a fast response that the reflectance can decrease from 43 to 33% within 0.6 s. Moreover, the sensor shows good recyclability and hydrogen selectivity. These excellent performances suggest that our suspended Pd/PMMA bilayer has great potential for practical hydrogen detection.

Polarization-insensitive graphene photodetectors enhanced by a broadband metamaterial absorber.

Graphene, combined with plasmonic nanostructures, shows great promise for achieving desirable photodetection properties and functionalities. Here, we theoretically proposed and experimentally demonstrated a graphene photodetector based on the metamaterial absorber in the visible and near-infrared wavebands. The experimental results show that the metamaterial-based graphene photodetector (MGPD) has achieved up to 3751% of photocurrent enhancement relative to an antennasless graphene device at zero external bias. Furthermore, the polarization-independent of photoresponse has resulted from the polarization-insensitive absorption of symmetric square-ring antennas. Moreover, the spectral-dependent photocurrent enhancement, originated from the enhanced light-trapping effect, was experimentally confirmed and understood by the simulated electric field profiles. The design contributes to the development of high-performance graphene photodetectors and optoelectronic devices.

Highly Sensitive and Durable Sea-Urchin-Shaped Silver Nanoparticles Strain Sensors for Human-Activity Monitoring.

High-performance strain sensors, composed of various artificial sensing materials on/in stretchable substrates, show great promise for applications in flexible electronic devices. Here, we demonstrated a highly sensitive and durable strain sensor consisting of a ribbon of close-packed sea-urchin-shaped silver nanoparticles (SUSNs) sandwiched between two layers of poly(dimethylsiloxane) (PDMS). Each of SUSNs possesses high-density and spherically distributed sharp spines over the body, which promotes electron transduction and further improves signal detection. This SUSN-based sensor possesses a desirable integration of high sensitivity (a gauge factor of 60) and large stretchability (up to 25%) at tensile sensing, broadening its application in wearable devices. Moreover, it also shows fast response (48 ms), good reproducibility, and long-term stability (>2500 cycles at 20% strain). It can also be used to detect compressing (sensitivity up to 31.5) and folding-type bending deformations. The sensing mechanism, the resistance of the sensors varying as the deformation load, results from the inter-spine contacts change and the microcracks evolution caused by variation in the gap between SUSNs. The sensor's sensitivity at different degrees of strain was also achieved by controlling the width of the close-packed SUSNs ribbon. For practical demonstration, the SUSN-based sensors could be used as wearable devices for monitoring human activities ranging from subtle deformations to substantial movements.

High-Contrast Dynamic Reflecting System Based on Pneumatic Micro/Nanoscale Surface Morphing.

Cephalopods offer a fascinating dynamic reflecting system to create desired colors and patterns through contracting and releasing their soft skins in response to environmental stimuli. Inspired by this natural display strategy, we designed a novel dynamic reflecting system based on pneumatic micro/nanoscale surface morphing. This system consists of a thin metal skin/elastomer bilayer modulated by a microfluidic-based gas injector. Benefited from the "wrinkled-specular" transition of the metal's surface under a small pneumatic actuation (4 kPa), an unprecedented reflectance contrast of 93 for broad-band (500-750 nm) modulation is achieved. This remarkable response also has excellent cycle stability (>2500 times) and fast response time (∼0.2 s). These advantages enable a robust and ultrasensitive optical gas pressure sensor with a sensitivity of 178 kPa-1, which is 3-4 orders of magnitude higher than those of conventional optical gas pressure sensors based on either a Fabry-Pérot interferometer or a Mach-Zehnder interferometer. Moreover, as proof-of-concept applications, we also experimentally demonstrated a curvature-variable convex mirror and noniridescent dynamic display, suggesting that our pneumatically dynamic reflecting system will potentially broaden the applications in adaptive optical devices, sensors, and displays.

Surface-enhanced Raman scattering induced by the coupling of the guided mode with localized surface plasmon resonances.

Surface-enhanced Raman spectroscopy (SERS) is considered to be a powerful analysis tool for the detection of molecules due to its ultra-high sensitivity and non-destructive nature. Here, we introduce a new type of hybrid SERS substrate, where gold nanorods are assembled on a structured support containing a top dielectric grating, dielectric spacer and gold mirror. Compared with the conventional metal nanoparticle assemblies on a flat support, our hybrid substrate shows an approximately 30-fold enhancement in the SERS signal. Numerical simulations show that such a substantial boost arises from the amplification of the absorption cross sections of the gold nanorods and the heating of the "hot spots" around the gold nanorods by the coupling between the guided mode in the structured support and the localized surface plasmon resonances. This mode coupling can be easily tuned by changing the thickness of the spacer. In addition, this substrate also presents uniform spot-to-spot and sample-to-sample SERS signals of the analyte molecules (relative standard deviations down to 7.4% and 6.1%, respectively). Moreover, the performance of this substrate has been demonstrated with the detection of melamine and cytosine, suggesting its great potential in food safety regulation and bioassays. This grating-mirror-enhanced strategy is available to any other SERS-active nanoparticles synthesized by chemical methods, which might offer new opportunities for improving the performance of the chemically prepared nanoparticles in realistic SERS-related applications.

Flexible plasmonic modulators induced by the thermomechanical effect.

Reconfigurable plasmon-based flexible devices, composed of artificial plasmonic nanostructures on stretchable substrates, show great promise for dynamic functionalities such as tunability, switching and modulation of electromagnetic waves. Here, we theoretically proposed and experimentally demonstrated a simple and efficient flexible plasmonic modulator based on an array of gold nanostructures on a poly(dimethylsiloxane) (PDMS) substrate. Arising from the current-induced local Joule heat, the local expansion of the PDMS substrate widens the gap distances between the neighboring gold wires, which results in a spectral shift of the plasmon resonance. The experimental results show that the plasmon resonance has a blue-shift of 39 nm under a total power consumption of only 10.5 mW, which results in a high modulation depth of up to 30.5% for the modulator. Such a low power consumption can be ascribed to the small active area and excellent thermal isolation of the PDMS. The optical and thermomechanical responses were confirmed and understood by the electromagnetic and thermomechanical co-simulations based on the finite-difference time-domain and finite-element methods. This novel mechanism to manipulate light provides new opportunities for active optical components and integrated circuits.

Layer-by-Layer Assembly of Three-Dimensional Optical Functional Nanostructures.

Nanotransfer printing (nTP) technology can generate highly functional three-dimensional (3D) nanostructures in a low-cost and high-throughput fashion. Nevertheless, the fabrication yield and quality of the transferred nanostructures are often limited by the merging of the surface patterns of replica stamps during transfer printing. Here, an nTP technology was developed to fabricate large-area and crack-free 3D multilayer nanostructures. Instead of directly depositing materials on the patterned flexible stamp in conventional nTPs, we transferred the nanostructures straightforwardly onto an attached polydimethylsiloxane slab by removing a sacrificial water-soluble poly(acrylic acid) film, which can avoid the cracking of metal film and the failures of printing nanostructures onto target substrates. Based on this approach, subwavelength-thick polarization rotators working at infrared wavelengths were fabricated. Excellent performance of linear polarization rotation over a broadband was realized. This nTP approach could complement existing fabrication techniques and benefit the development of various functional nanostructures with complex multilayer hierarchies.

Pd films on soft substrates: a visual, high-contrast and low-cost optical hydrogen sensor.

For the rapid development of the hydrogen economy, a reliable and low-cost hydrogen sensor appears to be extremely important. Here, we first show that a palladium film deposited on polydimethylsiloxane (PDMS) can obtain an exceedingly high-reflectance contrast of 25.78 over the entire visible band upon exposure to 4 vol% hydrogen gas (H2) mixed with nitrogen gas. This high-reflectance contrast results from the surface deformation induced by the volume inflation after exposure to H2, leading to the transition of the near-specular surface to a diffusing surface. In addition, a change in brightness is readable by naked eye upon exposure to H2 with various concentrations from 0.6 to 1 vol% under the illumination of a fluorescent tube. Furthermore, this sensor possesses an excellent recyclability and quick response time of a few seconds. Compared with Pd nanostructure-based hydrogen sensors, this visual, high-contrast and low-cost sensor is of great potential for practical hydrogen sensing.

Metal-Assisted Transfer Strategy for Construction of 2D and 3D Nanostructures on an Elastic Substrate.

Compared with conventional rigid devices, the elastic substrates integrated with functional components offer various advantages, such as flexibility, dynamic tunability, and biocompatibility. However, the reliable formations of 2D nanoparticles, nanogaps, and 3D nanostructures on elastic substrates are still challenging. The conventional transfer method plays an important role in the fabrication of microstructures on elastic substrates; however, it could not fabricate structures with feature size less than a few micrometers. In this article, we have developed a flexible technique based on the "metal-assisted transfer" strategy. The key concept is to introduce a metal film as an assistant layer between nanostructures and silicon substrates to help the fabrication of nanostructures which cannot be successfully transferred in the conventional transfer method. Various 2D nanostructures, which are difficult to achieve on elastic substrates, could be reliably defined using this approach. The desired gap distances and even sub-10 nm metal gaps between adjacent nanoparticles can be controllably achieved. Moreover, 3D nanostructures can be directly assembled from the prestrained 2D precursors based on the developed technique. Comparing with the previous reports, our fabrication method contains only a one-step transfer process without selective bonding or a second transfer process. Significantly, the 3D nanostructures presented here are 2 orders of magnitude smaller than the state-of-the-art mechanically assembled 3D structures in unit cell size. The proposed method may become a mainstream technology for the nano-optics and ultracompact optoelectronic devices due to its multifunctionalities and superior advantages in achieving tunable nanoparticles as well as 3D nanostructures.

Low-loss integrated electrical surface plasmon source with ultra-smooth metal film fabricated by polymethyl methacrylate 'bond and peel' method.

External light sources are mostly employed to functionalize the plasmonic components, resulting in a bulky footprint. Electrically driven integrated plasmonic devices, combining ultra-compact critical feature sizes with extremely high transmission speeds and low power consumption, can link plasmonics with the present-day electronic world. In an effort to achieve this prospect, suppressing the losses in the plasmonic devices becomes a pressing issue. In this work, we developed a novel polymethyl methacrylate 'bond and peel' method to fabricate metal films with sub-nanometer smooth surfaces on semiconductor wafers. Based on this method, we further fabricated a compact plasmonic source containing a metal-insulator-metal (MIM) waveguide with an ultra-smooth metal surface on a GaAs-based light-emitting diode wafer. An increase in propagation length of the SPP mode by a factor of 2.95 was achieved as compared with the conventional device containing a relatively rough metal surface. Numerical calculations further confirmed that the propagation length is comparable to the theoretical prediction on the MIM waveguide with perfectly smooth metal surfaces. This method facilitates low-loss and high-integration of electrically driven plasmonic devices, thus provides an immediate opportunity for the practical application of on-chip integrated plasmonic circuits.

White-light emission from a single heavy atom-free molecule with room temperature phosphorescence, mechanochromism and thermochromism.

Two heavy atom-free luminophores (SHB2t and SDB2t) with simple molecular structures have been synthesized via Suzuki coupling reactions in which both display white-light emission with prompt fluorescence and room temperature phosphorescence (RTP) in the solid state. The impressive RTP of the luminophores is produced by a synergistic effect of the strong intermolecular hydrogen bonding in addition to the spin-orbit coupling of the sulfonyl oxygen atoms and the moderate singlet-triplet energy gaps (ΔEST). These factors facilitate the intersystem crossing (ISC) process to generate triplet excitons in which the molecular conformations become immobilized to effectively suppress radiationless decay. Under the stimuli of mechanical force and solvent vapor, the RTP of SHB2t and SDB2t can be simply turned off and on by breaking and reforming the robust hydrogen bonding, which leads to remarkable and reversible mechanochromism between white and deep-blue emission. Moreover, two different thermochromic processes have been observed for the pristine and ground samples of SDB2t, in which a tricolor switching system between white, deep-blue and blue emission has been successfully achieved through the sequential control of grinding, heating and fuming. From detailed studies we have determined that the mechanism for the thermochromism of SDB2t is correlated with the rearrangement of the white-light emitting molecules to a new packing mode without RTP emission.

Mechanically tunable sub-10 nm metal gap by stretching PDMS substrate.

Manipulating light in sub-10 nm or subnanometer metal nanogaps is crucial to study the strong interaction between electromagnetic waves and matters. However, the fabrication of metallic nanogaps with precisely controlled size and high-throughput still remains a challenge. Here, we developed an approach to actively control the gap distance between adjacent metal nanoparticles from 140 nm to sub-10 nm or even 0 nm via mechanical stretching process. To demonstrate this method, we manufactured the gold disk arrays in a square lattice on the polydimethylsiloxane (PDMS) substrate through interference lithography and gold deposition, and sub-10 nm interparticle gap was achieved as exerting a strain of 100% to the PDMS substrate. Transmission spectra show a remarkable red shift of the dipole resonance with narrowing gap from 140 nm to sub-10 nm. Importantly, a universal scaling law between the gap distance in nanoscale and the stretching amount of PDMS substrate in macroscopic scale were demonstrated experimentally and theoretically. Our method can tune the gap distance continuously and reversibly, suggesting potential applications in surface-enhanced Raman scattering, single photon emitter and quantum tunneling of electric charge.

Slanted gold mushroom array: a switchable bi/tridirectional surface plasmon polariton splitter.

Surface plasmon polaritons (SPPs) show great promise in providing an ultracompact platform for integrated photonic circuits. However, challenges remain in easily and efficiently coupling light into and subsequently routing SPPs. Here, we theoretically propose and experimentally demonstrate a switchable bi/tridirectional beam splitter which can simultaneously perform both tasks. The photonic device consists of a periodic array of slanted gold 'mushrooms' composed of angled dielectric pillars with gold caps extruding from a periodic array of perforations in a gold film. The unidirectional coupling results from the interference of the in-plane guided modes scattered by a pair of dislocated gold gratings, while the output channel is determined by the polarization of the incident beam. This device, in combination with dynamic polarization modulation techniques, has the potential to serve as a router or switch in plasmonic integrated circuits.

Nonreciprocal spin wave elementary excitation in dislocated dimerized Heisenberg chains.

A mechanism for realizing nonreciprocal elementary excitation of spin wave (SW) is proposed. We study a reference model which describes a magnonic crystal (MC) formed by two Heisenberg chains with a lateral displacement (dislocation) and a longitudinal spacer, and derive a criterion to judge whether the elementary excitation spectra are reciprocal in this ferromagnetic lattice. An analytical method based on the spin precession equation is used to solve the elementary excitation spectra. The solution is related to a key factor, the spatio-temporal structure factor [Formula: see text], which can be directly calculated through the structural parameters. When it keeps invariant under the reversions of the external magnetic field [Formula: see text] and the dislocation [Formula: see text], or one of them, the spectra are reciprocal. Otherwise, the SW possesses nonreciprocal spectra with direction-dependent band edges and exhibits a directional magnetoresistance effect. This criterion can be regarded as a necessary and sufficient condition for the (non)reciprocity in the spin lattice. Besides, this novel lattice provides a prototype for spin diodes and spin logic gates.