Cryogenic Electron-Beam Writing for Perovskite Metasurface.

Halide perovskites (HPs) metasurfaces have recently attracted significant interest due to their potential to not only further enhance device performance but also reveal the unprecedented functionalities and novel photophysical properties of HPs. However, nanopatterning on HPs is critically challenging as they are readily destructed by the organic solvents in the standard lithographic processes. Here, we present a novel, subtle, and fully nondestructive HPs metasurface fabrication strategy based on cryogenic electron-beam writing. This technique allows for high-precision patterning and in situ imaging of HPs with excellent compatibility. As a proof-of-concept, broadband absorption enhanced metasurfaces were realized by patterning nanopillar arrays on CH3NH3PbI3 film, which results in photodetectors with approximately 14-times improvement on responsivity and excellent stability. Our findings highlight the great feasibility of cryogenic electron-beam writing for producing perovskite metasurface and unlocking the unprecedented photoelectronic properties of HPs.

Pressure-dependent flow enhancement in carbon nanotubes.

It is a known and experimentally verified fact that the flow of pressure-driven nanoconfined fluids cannot be accurately described by the Navier-Stokes (NS) equations with non-slip boundary conditions, and the measured volumetric flow rates are much higher than those predicted by macroscopical continuum models. In particular, the flow enhancement factors (the ratio between the flow rates directly measured by experiments or simulations and those predicted by the non-slip NS equation) reported by previous studies have more than five orders of magnitude differences. We showcased an anomalous phenomenon in which the flow enhancement exhibits a non-monotonic correlation with fluid pressure within the carbon nanotube with a diameter of 2 nm. Molecular dynamics simulations indicate that the inconsistency of flow behaviors is attributed to the phase transition of nanoconfined fluid induced by fluid pressures. The nanomechanical mechanisms are contributed by complex hydrogen-bonding interactions and regulated water orientations. This study suggests a method for explaining the inconsistency of flow enhancements by considering the pressure-dependent molecular structures.

Surface Engineering of Laser-Induced Graphene Enables Long-Term Monitoring of On-Body Uric Acid and pH Simultaneously.

Laser-induced graphene (LIG) suffers from serious decay in long-term biosensing, which greatly restricts its practical applications. Herein, we report a new strategy to engineer the LIG surface with Au clusters and chitosan sequentially to form a C-Au-LIG electrode with a superhydrophilic and highly conductive 3D graphene surface, which demonstrates superior performance and negligible decay in both long-term storage and practical usage in vitro and in vivo environments. Moreover, the C-Au-LIG electrode can be used for detecting uric acid (UA) and pH simultaneously from a single differential pulse voltammetry curve with low-detection limitation, high accuracy, and negligible interference with other sweat biomarkers. The integrated C-Au-LIG wearable biosensor was employed to continuously monitor the UA content in human sweat, which can well reflect the daily intake of purines for at least 10 days. Therefore, the C-Au-LIG electrode demonstrates significant application potential and provides inspiration for surface engineering of other biosensor materials and electrodes.

Manipulating Dual Bound States in the Continuum for Efficient Spatial Light Modulator.

Spatial light modulators (SLMs) that could control diverse optical properties are highly demanded by many optoelectronic systems. Recently, the integration of nonlinear χ(2) materials and metasurfaces has been recognized as a promising strategy for next-generation SLMs. However, their modulation efficiency still encounters challenges due to low quality factor and weak light-matter interaction. Here, we demonstrate an efficient SLM by manipulating the dual bound state in continuum (BIC) with the assistance of a binary-pore anodic alumina oxide template technique. The coexistence of symmetry-protected BIC and Fabry-Pérot BIC is obtained by a desirable sandwich configuration with a BIC metasurface and EO polymer, which efficiently restrain radiative loss and generate a strong quasi-BIC resonance. The assembled SLM with large absorption and Q-factor delivers a modulation depth of 77% and an f3 dB of nearly 100 MHz. This dual BIC metasurface provides potential for applications including switches, LIDAR, augmented and virtual reality, and so on.

Stable Sodium Metal Anode Enabled by an Interface Protection Layer Rich in Organic Sulfide Salt.

Sodium (Na) metal is considered as a promising anode candidate for large-scale energy storage systems because of its high theoretical capacity and low electrochemical redox potential. However, Na anode suffers from a few challenges, such as the dendrite growth and severe parasitic reactions with electrolytes, which greatly hinder its practical applications. In this work, we demonstrate that an organosulfur compound additive (tetramethylthiuram disulfide) provides a facile and promising approach to overcome the above challenges in carbonate-based electrolytes. This unique organosulfur additive can in situ form a stable interfacial protection layer rich in organic sulfide salts on the sodium metal surface during cycling, leading to a stable stripping/plating cycling. Additionally, a cycling Coulombic efficiency of 94.25% is achieved, and the full battery using Prussian Blue as a cathode delivers a reversible capacity of 86.2 mAh g-1 with a capacity retention of 80% after 600 cycles at 4 C.

Template-Guided Programmable Janus Heteronanostructure Arrays for Efficient Plasmonic Photocatalysis.

Janus heteronanostructures (HNs), as an important class of anisotropic nanomaterials, could facilitate synergistic coupling of diverse functions inherited by their comprised nanocomponents. Nowadays, synthesizing deterministically targeted Janus HNs remains a challenge. Here, a general yet scalable technique is utilized to fabricate an array of programmable Janus HNs based on anodic aluminum oxide binary-pore templates. By designing and employing an overetching process to partially expose four-edges of one set of nanocomponents in a binary-pore template, selective deposition and interfacing of the other set of nanocomponents is successfully achieved along the exposed four-edges to form a densely packed array of Janus HNs on a large scale. In combination with an upgraded two-step anodization, the synthesis provides high degrees of freedom for both nanocomponents of the Janus HNs, including morphologies, compositions, dimensions, and interfacial junctions. Arrays of TiO2-Au and TiO2/Pt NPs-Au Janus HNs are designed, fabricated, and demonstrated about 2.2 times photocurrent density and 4.6 times H2 evolution rate of that obtained from their TiO2 counterparts. The enhancement was mainly determined as a result of localized surface plasmon resonance induced direct hot electron injection and strong plasmon resonance energy transfer near the interfaces of TiO2 nanotubes and Au nanorods. This study may represent a promising step forward to pursue customized Janus HNs, leading to novel physicochemical effects and device applications.

Designing Heterogeneous 1D Nanostructure Arrays Based on AAO Templates for Energy Applications.

In order to fulfill the multiple requirements for energy production, storage, and utilization in the future, the conventional planar configuration of current energy conversion/storage devices has to be reformed, since technological evolution has promoted the efficiency of the corresponding devices to be close to the theoretical values. One promising strategy is to construct multifunctional 1D nanostructure arrays to replace their planar counterparts for device fabrication, ascribing to the significant superiorities of such 1D nanostructure arrays. In the last three decades, technologies based on anodic aluminium oxide (AAO) templates have turned out to be valuable meaning for the realization of 1D nanostructures and have attracted tremendous interest. In this review, recent progress in energy-related devices equipped with heterogeneous 1D nanostructure arrays that fabricated through the assistance of AAO templates is highlighted. Particular emphasis is given on how to develop efficient devices via optimizing the componential and morphological parameters of the 1D nanostructure arrays. Finally, aspects relevant to the further improvement of device performance are discussed.

Cost-effective atomic layer deposition synthesis of Pt nanotube arrays: application for high performance supercapacitor.

Due to the unique advantages of Pt, it plays an important role in fuel cells and microelectronics. Considering the fact that Pt is an expensive metal, a major challenging point nowadays is how to realize efficient utilization of Pt. In this paper, a cost-effective atomic layer deposition (ALD) process with a low N2 filling step is introduced for realizing well-defined Pt nanotube arrays in anodic alumina nano-porous templates. Compared to the conventional ALD growth of Pt, much fewer ALD cycles and a shorter precursor pulsing time are required, which originates from the low N2 filling step. To achieve similar Pt nanotubes, about half cycles and 10% Pt precursor pulsing time is needed using our ALD process. Meanwhile, the Pt nanotube array is explored as a current collector for supercapacitors based on core/shell Pt/MnO2 nanotubes. This nanotube-based electrode exhibits high gravimetric and areal specific capacitance (810 Fg(-1) and 75 mF cm(-2) at a scan rate of 5 mV s(-1) ) as well as an excellent rate capability (68% capacitance retention from 2 to 100 Ag(-1) ). Additionally, a negligible capacitance loss is observed after 8000 cycles of random charging-discharging from 2 to 100 Ag(-1) .

Vectorial diffusion for facile solution-processed self-assembly of insoluble semiconductors: a case study on metal phthalocyanines.

Solution processibility is one of the most intriguing properties of organic semiconductors. However, it is difficult to find a suitable solvent and solution process for most semiconductors. For example, metal phthalocyanines (MPcs) are only soluble in non-volatile solvents, which prevent their applications from solution process. For the first time, vectorial diffusion is utilized for solution processing of MPcs. The obtained large F16CuPc and α-phase CuPc crystals and the efficient phase separation of them suggest the vectorial diffusion process is as slow as a self-assembly process, which is helpful to yield large crystals and purify the semiconductors. This method, which only uses common commercial solvents without any complex and expensive instruments and high-temperature operation, provides a facile approach for purification of organic semiconductors and growth of their crystals in large quantities.

Switchable charge-transfer in the photoelectrochemical energy-conversion process of ferroelectric BiFeO3 photoelectrodes.

Instead of conventional semiconductor photoelectrodes, herein, we focus on BiFeO3 ferroelectric photoelectrodes to break the limits imposed by common semiconductors. As a result of their prominent ferroelectric properties, the photoelectrodes are able to tune the transfer of photo-excited charges generated either in BiFeO3 or the surface modifiers by manipulating the poling conditions of the ferroelectric domains. At 0 V vs Ag/AgCl, the photocurrent could be switched from 0 µA cm(-2) to 10 µA cm(-2) and the open-circuit potential changes from 33 mV to 440 mV, when the poling bias of pretreatment is manipulated from -8 V to +8 V. Additionally, the pronounced photocurrent from charge injection of the excited surface modifiers could be quenched by switching the poling bias from +8 V to -8 V.

Enhanced CO2 Electroreduction to Multi-Carbon Products on Copper via Plasma Fluorination.

The electroreduction of carbon dioxide (CO2) to multi-carbon (C2+) compounds offers a viable approach for the up-conversion of greenhouse gases into valuable fuels and feedstocks. Nevertheless, current industrial applications face limitations due to unsatisfactory conversion efficiency and high overpotential. Herein, a facile and scalable plasma fluorination method is reported. Concurrently, self-evolution during CO2 electroreduction is employed to control the active sites of Cu catalysts. The copper catalyst modified with fluorine exhibits an impressive C2+ Faradaic efficiency (FE) of 81.8% at a low potential of -0.56 V (vs a reversible hydrogen electrode) in an alkaline flow cell. The presence of modified fluorine leads to the exposure and stabilization of high-activity Cu+ species, enhancing the adsorption of *CO intermediates and the generation of *CHO, facilitating the subsequent dimerization. This results in a notably improved conversion efficiency of 13.1% and a significant reduction in the overpotential (≈100 mV) for the C2+ products. Furthermore, a superior C2+ FE of 81.6% at 250 mA cm-2, coupled with an energy efficiency of 31.0%, can be achieved in a two-electrode membrane electrode assembly electrolyzer utilizing the fluorine-modified copper catalyst. The strategy provides novel insights into the controllable electronic modification and surface reconstruction of electrocatalysts with practical potential.

Achieving Reliable and Ultrafast Memristors via Artificial Filaments in Silk Fibroin.

The practical implementation of memristors in neuromorphic computing and biomimetic sensing suffers from unexpected temporal and spatial variations due to the stochastic formation and rupture of conductive filaments (CFs). Here, the biocompatible silk fibroin (SF) is patterned with an on-demand nanocone array by using thermal scanning probe lithography (t-SPL) to guide and confine the growth of CFs in the silver/SF/gold (Ag/SF/Au) memristor. Benefiting from the high fabrication controllability, cycle-to-cycle (temporal) standard deviation of the set voltage for the structured memristor is significantly reduced by ≈95.5% (from 1.535 to 0.0686 V) and the device-to-device (spatial) standard deviation is also reduced to 0.0648 V. Besides, the statistical relationship between the structural nanocone design and the resultant performance is confirmed, optimizing at the small operation voltage (≈0.5 V) and current (100 nA), ultrafast switching speed (sub-100 ns), large on/off ratio (104 ), and the smallest switching slope (SS < 0.01 mV dec-1 ). Finally, the short-term plasticity and leaky integrated-and-fire behavior are emulated, and a reliable thermal nociceptor system is demonstrated for practical neuromorphic applications.

Plasmonic Bound States in the Continuum Metasurface-Semiconductor-Metal Architecture Enables Efficient Hot-Electron-Based Photodetector.

Plasmonic hot-electron-based photodetectors (HEB-PDs) have received widespread attention for their ability to realize effective carrier collection under sub-bandgap illumination. However, due to the low hot electron emission probability, most of the existing HEB-PDs exhibit poor responsivity, which significantly restricts their practical applications. Here, by employing the binary-pore anodic alumina oxide template technique, we proposed a compact plasmonic bound state in continuum metasurface-semiconductor-metal-based (BIC M-S-M) HEB-PD. The symmetry-protected BIC can manipulate a strong gap surface plasmon in the stacked M-S-M structure, which effectively enhances light-matter interactions and improves the photoresponse of the integrated device. Notably, the optimal M-S-M HEB-PD with near-unit absorption (∼90%) around 800 nm delivers a responsivity of 5.18 A/W and an IPCE of 824.23% under 780 nm normal incidence (1 V external bias). Moreover, the ultrathin feature of BIC M-S-M (∼150 nm) on the flexible substrate demonstrates excellent stability under a wide range of illumination angles from -40° to 40° and at the curvature surface from 0.05 to 0.13 mm-1. The proposed plasmonic BIC strategy is very promising for many other hot-electron-related fields, such as photocatalysis, biosensing, imaging, and so on.

Customizing 2.5D Out-of-Plane Architectures for Robust Plasmonic Bound-States-in-the-Continuum Metasurfaces.

Bound states in the continuum (BICs) have a superior ability to confine electromagnetic waves and enhance light-matter interactions. However, the quality-factor of quasi-BIC is extremely sensitive to structural perturbations, thus the BIC metasurfaces usually require a very-high precision nanofabrication technique that greatly restricts their practical applications. Here, distinctive 2.5D out-of-plane architectures based plasmonic symmetry protected (SP)-BIC metasurfaces are proposed, which could deliver robust quality factors even with large structural perturbations. The high-throughput fabrication of such SP-BIC metasurfaces is realized by using the binary-pore anodic aluminum oxide template technique. Moreover, the deep neural network (DNN) is adapted to conduct multiparameter fittings, where the 2.5D hetero-out-of-plane architectures with robust high quality-factors and figures of merit are rapidly predicted and fabricated. Finally, owning to its large second-order surface sensitivity, the desired 2.5D hetero-out-of-plane architecture demonstrates a detection limit of endotoxin as low as 0.01 EU mL-1 , showing a good perspective of biosensors and others.

Manipulating Coupled Field Enhancement in Slot-under-Groove Nanoarrays for Universal Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) is an ultrasensitive spectroscopic technique that can identify materials and chemicals based on their inelastic light-scattering properties. In general, SERS relies on sub-10 nm nanogaps to amplify the Raman signals and achieve ultralow-concentration identification of analytes. However, large-sized analytes, such as proteins and viruses, usually cannot enter these tiny nanogaps, limiting the practical applications of SERS. Herein, we demonstrate a universal SERS platform for the reliable and sensitive identification of a wide range of analytes. The key to this success is the prepared "slot-under-groove" nanoarchitecture arrays, which could realize a strongly coupled field enhancement with a large spatial mode distribution via the hybridization of gap-surface plasmons in the upper V-groove and localized surface plasmon resonance in the lower slot. Therefore, our slot-under-groove platform can simultaneously deliver high sensitivity for small-sized analytes and the identification of large-sized analytes with a large Raman gain.

Erratum to "Single Wire Capacitive Wireless Power Transfer System for Wearable Biomedical Sensors based on Flexible Graphene Film Material".

In [1], this paper was submitted for the Special Issue on Flexible Biomedical Sensors for Healthcare Applications. The paper was instead published in Volume 16, Issue 6, 2022.

A high-throughput fully automatic biosensing platform for efficient COVID-19 detection.

We propose a label-free biosensor based on a porous silicon resonant microcavity and localized surface plasmon resonance. The biosensor detects SARS-CoV-2 antigen based on engineered trimeric angiotensin converting enzyme-2 binding protein, which is conserved across different variants. Robotic arms run the detection process including sample loading, incubation, sensor surface rinsing, and optical measurements using a portable spectrometer. Both the biosensor and the optical measurement system are readily scalable to accommodate testing a wide range of sample numbers. The limit of detection is 100 TCID50/ml. The detection time is 5 min, and the throughput of one single robotic site is up to 384 specimens in 30 min. The measurement interface requires little training, has standard operation, and therefore is suitable for widespread use in rapid and onsite COVID-19 screening or surveillance.

Bidirectional Synaptic Phototransistor Based on Two-Dimensional Ferroelectric Semiconductor for Mixed Color Pattern Recognition.

Optoelectronic synaptic devices capable of processing multiwavelength inputs are critical for neuromorphic vision hardware, which remains an important challenge. Here, we develop a bidirectional synaptic phototransistor based on a two-dimensional ferroelectric semiconductor of α-In2Se3, which exhibits bidirectional potentiated and depressed synaptic weight update under optical pulse stimulation. Importantly, the bidirectional optoelectronic synaptic behavior can be extended to multiwavelengths (blue, green, and red light), which could be used for color recognition. The mechanism underlying the bidirectional synaptic characteristics is attributed to the gate-configurable barrier heights as revealed by the Kelvin probe force microscopy measurement. The α-In2Se3 device exhibits versatile synaptic plasticity such as paired-pulse facilitation, short- and long-term potentiation, and long-term depression. The bidirectional optoelectronic synaptic weight updates under multiwavelength inputs enable a high accuracy of 97% for mixed color pattern recognition.

Label-Free LSPR-Vertical Microcavity Biosensor for On-Site SARS-CoV-2 Detection.

Cost-effective, rapid, and sensitive detection of SARS-CoV-2, in high-throughput, is crucial in controlling the COVID-19 epidemic. In this study, we proposed a vertical microcavity and localized surface plasmon resonance hybrid biosensor for SARS-CoV-2 detection in artificial saliva and assessed its efficacy. The proposed biosensor monitors the valley shifts in the reflectance spectrum, as induced by changes in the refractive index within the proximity of the sensor surface. A low-cost and fast method was developed to form nanoporous gold (NPG) with different surface morphologies on the vertical microcavity wafer, followed by immobilization with the SARS-CoV-2 antibody for capturing the virus. Modeling and simulation were conducted to optimize the microcavity structure and the NPG parameters. Simulation results revealed that NPG-deposited sensors performed better in resonance quality and in sensitivity compared to gold-deposited and pure microcavity sensors. The experiment confirmed the effect of NPG surface morphology on the biosensor sensitivity as demonstrated by simulation. Pre-clinical validation revealed that 40% porosity led to the highest sensitivity for SARS-CoV-2 pseudovirus at 319 copies/mL in artificial saliva. The proposed automatic biosensing system delivered the results of 100 samples within 30 min, demonstrating its potential for on-site coronavirus detection with sufficient sensitivity.

Single Wire Capacitive Wireless Power Transfer System for Wearable Biomedical Sensors Based on Flexible Graphene Film Material.

This paper provides a special flexible graphene film based capacitive wireless power transfer (FGCPT) system for powering biomedical sensors of smart wearable devices. The graphene conductive material is flexible, transparent, highly conductive, and impermeable to most gases and liquids. Generally, the coupling structure of capacitive wireless power transfer (CPT) system is consisted of metal plates. However, it is hard to use for the biomedical sensors as the low power density and big volume. The shape of graphene conductive material could be easily built and changed according to the application requirements. In this paper, the power supply of biomedical sensing system could be accomplished by a single graphene film which is acted as the receiver of FGCPT system. The 200 mW power level is achieved with the maximum 9 V output voltage. The theory and calculation are verified by the simulated and experimental results.