Glass Disorder Modulated Luminescence in Zero-Dimensional Antimony-Chloride Coplanar Dimers for Optical Anti-counterfeiting.

Zero-dimensional metal halides have received wide attention due to their structural diversity, strong quantum confinement, and associated excellent photoluminescence properties. A reversible and tunable luminescence would be desirable for applications such as anti-counterfeiting, information encryption, and artificial intelligence. Yet, these materials are underexplored, with little known about their luminescence tuning mechanisms. Here we report a pyramidal coplanar dimer, (TBA)Sb2Cl7 (TBA = tetrabutylammonium), showing broadband emission wavelength tuning (585-650 nm) by simple thermal treatment. We attribute the broad color change to structural disorder induced by varying the heat treatment temperatures. Increasing the heating temperature transitions the material from long-range ordered crystalline phase to highly disordered glassy phase. The latter exhibits stronger electron-phonon coupling, enhancing the self-trapped exciton emission efficiency. The work provides a new material platform for manifold optical anti-counterfeiting applications and sheds light on the emission color tuning mechanisms for further design of stimuli-responsive materials.

Photoresponsive Biomimetic Functions by Light-Driven Molecular Motors in Three Dimensionally Printed Liquid Crystal Elastomers.

Despite the fascinating developments in design and synthesis of artificial molecular machines operating at the nanoscales, translating molecular motion along multiple length scales and inducing mechanical motion of a three-dimensional macroscopic entity remains an important challenge. The key to addressing this amplification of motion relies on the effective organization of molecular machines in a well-defined environment. By taking advantage of long-range orientational order and hierarchical structures of liquid crystals and unidirectional rotation of light-driven molecular motors, we report here photoresponsive biomimetic functions of liquid crystal elastomers (LCEs) by the repetitive unidirectional rotation of molecular motors using 3D printing. Molecular motors were built in the main chain of liquid crystals oligomers to serve as photoactuators. The oligomers were then used as the ink, and liquid crystal elastomers with different morphologies were printed. The obtained LCEs are able to conduct multiple types of motions including bending, helical coiling, closing of petals, and flipping of wings of a butterfly upon UV illumination, which paves the way for future design of responsive materials with enhanced complex actuating functions.

Supramolecular Polyurethane "Ligaments" Enabling Room-Temperature Self-Healing Flexible Perovskite Solar Cells and Mini-Modules.

Flexible perovskite solar cells (F-PSCs) have emerged as promising alternatives to conventional silicon solar cells for applications in portable and wearable electronics. However, the mechanical stability of inherently brittle perovskite, due to residual lattice stress and ductile fracture formation, poses significant challenges to the long-term photovoltaic performance and device lifetime. In this paper, to address this issue, a dynamic "ligament" composed of supramolecular poly(dimethylsiloxane) polyurethane (DSSP-PPU) is introduced into the grain boundaries of the PSCs, facilitating the release of residual stress and softening of the grain boundaries. Remarkably, this dynamic "ligament" exhibits excellent self-healing properties and enables the healing of cracks in perovskite films at room temperature. The obtained PSCs have achieved power conversion efficiencies of 23.73% and 22.24% for rigid substrates and flexible substrates, respectively, also 17.32% for flexible mini-modules. Notably, the F-PSCs retain nearly 80% of their initial efficiency even after subjecting the F-PSCs to 8000 bending cycles (r = 2 mm), which can further recover to almost 90% of the initial efficiency through the self-healing process. This remarkable improvement in device stability and longevity holds great promise for extending the overall lifetime of F-PSCs.

Self-Powered Colorful Dynamic Electrowetting Display Systems Based on Triboelectricity.

Electrowetting displays (EWDs) based on microfluidics are highly sought after in the fields of electronic devices, smart homes, and information communication. However, the power supply of the EWD systems for visually engaging multi-color displays remains a big challenge. Herein, self-powered colorful dynamic display systems are developed by integrating the triboelectric nanogenerator (TENG) with the EWD device. The TENG is designed with a nanotube-patterned surface and can generate open-circuit voltages ranging from 30 to 295 V by controlling the contact area. The wetting property of the micro-droplet exhibits a response to the applied voltage, enabling the triboelectricity-triggered electrowetting-on-dielectric. Driven by the voltage of 160 V, the monochromatic EWD exhibits bright color switching from magenta to transparent with a pixel aperture ratio of 78%, and the recovery process can be rapidly completed. Furthermore, the self-powered colorful dynamic EWD system can be achieved. By selectively applying the voltage to the pixels in the three monochromatic layers that constitute the colorful EWD, the wetting properties of the fluids can be controlled, allowing for colorful dynamic display. This work contributes to the advancement of color display technology for portable and wearable electronic ink displays, indoor and outdoor sports equipment, and information communication.

Harnessing Smectic Ordering for Electric-Field-Driven Guided-Growth of Surface Topography in a Liquid Crystal Polymer.

The guided-growth strategy has been widely explored and proved its efficacy in fabricating surface micro/nanostructures in a variety of systems. However, soft materials like polymers are much less investigated partly due to the lack of strong internal driving mechanisms. Herein, the possibility of utilizing liquid crystal (LC) ordering of smectic liquid crystal polymers (LCPs) to induce guided growth of surface topography during the formation of electrohydrodynamic (EHD) patterns is demonstrated. In a two-stage growth, regular stripes are first found to selectively emerge from the homogeneously aligned region of an initially flat LCP film, and then extend neatly along the normal direction of the boundary line between homogeneous and homeotropic alignments. The stripes can maintain their directions for quite a distance before deviating. Coupled with the advanced tools for controlling LC alignment, intricate surface topographies can be produced in LCP films starting from relatively simple designs. The regularity of grown pattern is determined by the LC ordering of the polymer material, and influenced by conditions of EHD growth. The proposed approach provides new opportunities to employ LCPs in optical and electrical applications.

A Self-Assembled 3D/0D Quasi-Core-Shell Structure as Internal Encapsulation Layer for Stable and Efficient FAPbI3 Perovskite Solar Cells and Modules.

FAPbI3 perovskites have garnered considerable interest owing to their outstanding thermal stability, along with near-theoretical bandgap and efficiency. However, their inherent phase instability presents a substantial challenge to the long-term stability of devices. Herein, this issue through a dual-strategy of self-assembly 3D/0D quasi-core-shell structure is tackled as an internal encapsulation layer, and in situ introduction of excess PbI2 for surface and grain boundary defects passivating, therefore preventing moisture intrusion into FAPbI3 perovskite films. By utilizing this method alone, not only enhances the stability of the FAPbI3 film but also effectively passivates defects and minimizes non-radiative recombination, ultimately yielding a champion device efficiency of 23.23%. Furthermore, the devices own better moisture resistance, exhibiting a T80 lifetime exceeding 3500 h at 40% relative humidity (RH). Meanwhile, a 19.51% PCE of mini-module (5 × 5 cm2) is demonstrated. This research offers valuable insights and directions for the advancement of stable and highly efficient FAPbI3 perovskite solar cells.

Microwell Confined Electro-Coalescence for Rapid Formation of High-Throughput Droplet Array.

Droplet array is widely applied in single cell analysis, drug screening, protein crystallization, etc. This work proposes and validates a method for rapid formation of uniform droplet array based on microwell confined droplets electro-coalescence of screen-printed emulsion droplets, namely electro-coalescence droplet array (ECDA). The electro-coalescence of droplets is according to the polarization induced electrostatic and dielectrophoretic forces, and the dielectrowetting effect. The photolithographically fabricated microwells are highly regular and reproducible, ensuring identical volume and physical confinement to achieve uniform droplet array, and meanwhile the microwell isolation protects the paired water droplets from further fusion and broadens its feasibility to different fluidic systems. Under optimized conditions, a droplet array with an average diameter of 85 µm and a throughput of 106 in a 10 cm × 10 cm chip can be achieved within 5 s at 120 Vpp and 50 kHz. This ECDA chip is validated for various microwell geometries and functional materials. The optimized ECDA are successfully applied for digital viable bacteria counting, showing comparable results to the plate culture counting. Such an ECDA chip, as a digitizable and high-throughput platform, presents excellent potential for high-throughput screening, analysis, absolute quantification, etc.

Co-Solvent Engineering Contributing to Achieve High-Performance Perovskite Solar Cells and Modules Based on Anti-Solvent Free Technology.

The pinhole-free and defect-less perovskite film is crucial for achieving high efficiency and stable perovskite solar cells (PSCs), which can be prepared by widely used anti-solvent crystallization strategies. However, the involvement of anti-solvent requires precise control and inevitably brings toxicity in fabrication procedures, which limits its large-scale industrial application. In this work, a facile and effective co-solvent engineering strategy is introduced to obtain high- quality perovskite film while avoiding the usage of anti-solvent. The uniform and compact perovskite polycrystalline films have been fabricated through the addition of co-solvent that owns strong coordination capacity with perovskite components , meanwhile possessing the weaker interaction with main solvent . With those strategies, a champion power conversion efficiency (PCE) of 22% has been achieved with the optimal co-solvent, N-methylpyrrolidone (NMP) and without usage of anti-solvent. Subsequently, PSCs based on NMP show high repeatability and good shelf stability (80% PCE remains after storing in ambient condition for 30 days). Finally, the perovskite solar module (5 × 5 cm) with 7 subcells connects in series yielding champion PCE of 16.54%. This strategy provides a general guidance of co-solvent selection for PSCs based on anti-solvent free technology and promotes commercial application of PSCs.

Alternated emotional working memory in individuals with subclinical insomnia disorder: An electrophysiological study.

The deleterious effects of sleep loss on sleep-dependent memory and emotional function have been documented in the current literature. Yet, the effects of insomnia-induced chronic sleep disturbance on emotional short-term memory have been scarcely investigated. Twenty-one participants with subclinical insomnia disorder (SID) and 20 healthy participants (healthy control, HC) performed a delayed recognition task of emotional faces, and event-related potentials (ERPs) involved in memory encoding, retention, and retrieval of faces across different emotional valences were assessed. Behavioral findings revealed that participants in the SID group had a larger response bias, being more likely to perceive negative faces as "old" faces presented in the retrieval phase than those in the HC group. ERP findings revealed that emotional faces in the SID vs. HC group induced significantly smaller P1 and late P3b and larger N170 amplitudes in the encoding phase and smaller negative slow wave (NSW) in the retention phase. In retrieval phase, the interaction between Sleep group and Valence were revealed for P1 and early P3b amplitudes, but no group differences were found after Bonferroni correction. These findings suggested that insomnia induced chronic sleep disturbance would influence performance on emotional working memory and induced processing phase specific regulation of neurophysiology in emotional working memory regardless of valence.

Physics-model-based neural networks for inverse design of binary phase planar diffractive lenses.

The inverse design approach has enabled the customized design of photonic devices with engineered functionalities through adopting various optimization algorithms. However, conventional optimization algorithms for inverse design encounter difficulties in multi-constrained problems due to the substantial time consumed in the random searching process. Here, we report an efficient inverse design method, based on physics-model-based neural networks (PMNNs) and Rayleigh-Sommerfeld diffraction theory, for engineering the focusing behavior of binary phase planar diffractive lenses (BPPDLs). We adopt the proposed PMNN to design BPPDLs with designable functionalities, including realizing a single focal spot, multiple foci, and an optical needle with size approaching the diffraction limit. We show that the time for designing single device is dramatically reduced to several minutes. This study provides an efficient inverse method for designing photonic devices with customized functionalities, overcoming the challenges based on traditional data-driven deep learning.

Spreading Solution Additives Governs the Quality of Polystyrene Particle-Based Two-Dimensional Opals.

Two-dimensional polystyrene sphere opals are important materials for nanotechnology applications and fundamental nanoscience research. They are a facile and inexpensive nanofabrication tool, but the quality factor of these opals has drastic differences between reports. Additives like ethanol, ions, and organic molecules in the aqueous particle spreading solution are known to affect the quality factor and growth efficiency of the produced opals. However, a systematic study on the effect and optimization of some of the most effective additives has not been reported until now. Here, we investigate the influence of additives on the growth efficiency and quality factor of such monolayers formed at the air-water interface without the use of a Langmuir-Blodgett trough. The additives induced large variations in the monolayer quality factor and growth efficiency, and we found that the ideal additive content of the spreading agents is 30 wt % < cethanol < 70 wt %, 0 < cH2SO4 < 30.5 mM, and 0 < csty < 255.0 mM. This study provides a guideline for the rational composition and additive content of the spreading solution to obtain high-quality two-dimensional opals for further applications in nanofabrication and photonics and will enable researchers and application engineers to produce standardized nanofabrication materials.

Accurate and Wide-Voltage-Range Modeling of Electrowetting with a Lattice Boltzmann Approach.

The lattice Boltzmann method (LBM) has been widely used in multi-phase fluid mechanics and is known to be more computationally efficient than the traditional method of numerically solving Navier-Stokes and Cahn-Hilliard equations. Electrowetting is an important component of interfacial sciences, in which the liquid-liquid and solid-liquid interfaces are tuned by electrostatics. Modeling electrowetting using the LBM can be categorized into surface and bulk methods. By modifying the surface tension scalar, the surface method easily reproduces the fundamental Young-Lippmann (YL) equation at low voltages but fails to capture contact angle saturation at high voltages. With fully coupled hydrodynamics and electrostatics in the form of spatially dependent matrices, the bulk method can successfully show contact angle saturation, but it is often unable to reproduce the YL equation due to its intrinsic inaccuracies. The inaccuracies are mainly due to the fact that while the hydrodynamics are all described by continuous physical quantities in the framework of diffusive interfaces, the interfacial electrostatics are governed by discontinuous electric fields caused by sheet charge density. In this paper, we show that accurately modeling electrowetting using the LBM is non-trivial. Additional modeling work, especially the treatment of interfacial electric fields, is needed to recover the fundamental YL equation at low voltages and predict contact angle saturation at high voltages, with a systematic model validation over key parameters and applications.

Hydration Energy-Dependent Ion Intercalation on Graphite and the Asymmetric Electrowetting.

Ion intercalation in graphite is widely used in desalination, batteries, and graphene stripping; it has high value in the fields of industry and research. However, selective ion transport, particularly (de)hydration energy and the hydration shell effect on the intercalation of ions into the graphite interlayer spaces, is still unclear. Here, we report low-voltage ion intercalation as observed by electrowetting on highly oriented pyrolytic graphite of an aqueous drop containing various inorganic salts. The electrowetting response exhibits asymmetric behavior with no contact angle change for the negative polarity and a threshold voltage for the onset of the contact angle change for the positive polarity. To explain the asymmetric electrowetting behavior and quantitatively predict the threshold voltage, we developed a physical model based on the hydration shell energy and size of the ion that undergoes partial breaking/deformation during the co-intercalation into the spaces between graphite layers. Electrowetting experiments using ions with various hydration energies and hydration radii were performed to confirm the prediction of the model. Further, we show a strategy to make the electrowetting response of LiCl drops symmetric via tuning the hydration energy of the Li+ ions using a binary solvent of a glycerol-water mixture. This article will provide an understanding of the hydration (solvation) energy dependence intercalation mechanism in graphite for electrowetting, which underpins various processes such as ion battery applications and the graphene exfoliation process.

Shine light on sleep: Morning bright light improves nocturnal sleep and next morning alertness among college students.

The relationship between daytime light, especially morning light and sleep, has not been well documented. People who work in an office spend most of their time indoors and thus have less access to high-level daylight. The current study employed a field intervention approach to investigate whether exposure to 1.5 h of bright electric light in the early morning for 1 workweek would benefit sleep among students who spent most of their time in an office at the university. Twelve students (24.92 ± 1.78 years) underwent a 2 workday baseline measurement and two inconsecutive 5 workday interventions (with 1 week washout) with morning bright light and regular office light (1000 lx, 6500 K vs. 300 lx, 4000 K, at eye level). The sleep outcomes were recorded with actigraphy and a sleep diary. In addition, self-ratings of daytime sleepiness, mood, mental fatigue, perceived effort, and next morning sleepiness were measured each workday. The results showed that exposure to morning bright light versus regular office light yielded a higher sleep efficiency (83.82% ± 1.60 vs. 80.35% ± 1.57, p = 0.02), a smaller fragmentation index (15.26% ± 1.31 vs. 17.18% ± 1.28, p = 0.05), and a shorter time in bed (7.12 ± 0.13 vs. 7.51 ± 0.12, p = 0.03). Meanwhile, an earlier sleep onset time, shorter sleep latency, and lower morning sleepiness were observed after a 5 workday morning bright light intervention compared with the baseline (ps <0.05), no such benefit was found for self-ratings (ps >0.05). These findings support existing evidence that morning bright light could function as an enhancer of sleep and alertness for office occupants.

Evening prolonged relatively low melanopic equivalent daylight illuminance light exposure increases arousal before and during sleep without altering sleep structure.

Light can influence many psychophysiological functions beyond vision, including alertness, circadian rhythm, and sleep, namely the non-image forming (NIF) effects of light. Melanopic equivalent daylight illuminance (mel-EDI) is currently recommended as the predictor of the NIF effects of light. Although light dose is also critical for entraining and regulating circadian cycle, it is still unknown whether relatively low mel-EDI light exposure for prolonged duration in the evening would affect pre-sleep arousal and subsequent sleep. In all, 18 healthy college students (10 females, mean [standard deviation] age 21.67 [2.03] years) underwent 2 experimental nights with a 1 week interval in a simulated bedroom environment. During experimental nights, participants were either exposed to high or low mel-EDI light (73 versus 38 lx mel-EDI, 90 versus 87 photopic lx at eye level, 150 photopic lx at table level) for 3.5 h before regular bedtime, and their sleep was monitored by polysomnography. Subjective sleepiness, mood, and resting-state electroencephalography during light exposure were also investigated. Results showed no significant differences in sleep structure and sleep quality between the two light conditions, whereas 3.5 h of exposure to high versus low mel-EDI light induced marginally higher physiological arousal in terms of a lower delta but higher beta power density before sleep, as well as a lower delta power density during sleep. Moreover, participants felt happier before sleep under exposure to high versus low mel-EDI light. These findings together with the current literature suggest that evening prolonged relatively low mel-EDI light exposure may mildly increase arousal before and during sleep but affected sleep structure less.

Accelerated Multi-step Sulfur Redox Reactions in Lithium-Sulfur Batteries Enabled by Dual Defects in Metal-Organic Framework-based Catalysts.

The sluggish sulfur redox kinetics and shuttle effect of lithium polysulfides (LiPSs) are recognized as the main obstacles to the practical applications of the lithium-sulfur (Li-S) batteries. Accelerated conversion by catalysis can mitigate these issues, leading to enhanced Li-S performance. However, a catalyst with single active site cannot simultaneously accelerate multiple LiPSs conversion. Herein, we developed a novel dual-defect (missing linker and missing cluster defects) metal-organic framework (MOF) as a new type of catalyst to achieve synergistic catalysis for the multi-step conversion reaction of LiPSs. Electrochemical tests and first-principle density functional theory (DFT) calculations revealed that different defects can realize targeted acceleration of stepwise reaction kinetics for LiPSs. Specifically, the missing linker defects can selectively accelerate the conversion of S8 →Li2 S4 , while the missing cluster defects can catalyze the reaction of Li2 S4 →Li2 S, so as to effectively inhibit the shuttle effect. Hence, the Li-S battery with an electrolyte to sulfur (E/S) ratio of 8.9 mL g-1 delivers a capacity of 1087 mAh g-1 at 0.2 C after 100 cycles. Even at high sulfur loading of 12.9 mg cm-2 and E/S=3.9 mL g-1 , an areal capacity of 10.4 mAh cm-2 for 45 cycles can still be obtained.

Phototriggered Complex Motion by Programmable Construction of Light-Driven Molecular Motors in Liquid Crystal Networks.

Recent developments in artificial molecular machines have enabled precisely controlled molecular motion, which allows several distinct mechanical operations at the nanoscale. However, harnessing and amplifying molecular motion along multiple length scales to induce macroscopic motion are still major challenges and comprise an important next step toward future actuators and soft robotics. The key to addressing this challenge relies on effective integration of synthetic molecular machines in a hierarchically aligned structure so numerous individual molecular motions can be collected in a cooperative way and amplified to higher length scales and eventually lead to macroscopic motion. Here, we report the complex motion of liquid crystal networks embedded with molecular motors triggered by single-wavelength illumination. By design, both racemic and enantiomerically pure molecular motors are programmably integrated into liquid crystal networks with a defined orientation. The motors have multiple functions acting as cross-linkers, actuators, and chiral dopants inside the network. The collective rotary motion of motors resulted in multiple types of motion of the polymeric film, including bending, wavy motion, fast unidirectional movement on surfaces, and synchronized helical motion with different handedness, paving the way for the future design of responsive materials with enhanced complex functions.

CarbonIron Electron Transport Channels in Porphyrin-Graphene Complex for ppb-Level Room Temperature NO Gas Sensing.

It is a great challenge to develop efficient room-temperature sensing materials and sensors for nitric oxide (NO) gas, which is a biomarker molecule used in the monitoring of inflammatory respiratory diseases. Herein, Hemin (Fe (III)-protoporphyrin IX) is introduced into the nitrogen-doped reduced graphene oxide (N-rGO) to obtain a novel sensing material HNG-ethanol. Detailed XPS spectra and DFT calculations confirm the formation of carbon-iron bonds in HNG-ethanol during synthesis process, which act as electron transport channels from graphene to Hemin. Owing to this unique chemical structure, HNG-ethanol exhibits superior gas sensing properties toward NO gas (Ra /Rg  = 3.05, 20 ppm) with a practical limit of detection (LOD) of 500 ppb and reliable repeatability (over 5 cycles). The HNG-ethanol sensor also possesses high selectivity against other exhaled gases, high humidity resistance, and stability (less than 3% decrease over 30 days). In addition, a deep understanding of the gas sensing mechanisms is proposed for the first time in this work, which is instructive to the community for fabricating sensing materials based on graphene-iron derivatives in the future.

Effects of a brief afternoon nap on declarative and procedural memory.

The relationship between sleep and memory consolidation has not been fully revealed. The current study aimed to investigate how a brief afternoon nap contributed to the consolidation of declarative and procedural memory by exploring the relationship between sleep characteristics (i.e., the durations of sleep stages and slow oscillation, slow-wave activity, and spindle activity extracted from sleep) and task performance and the relationship between delta, theta, alpha, and beta bands extracted from wake during task performance and task performance. Twenty-three healthy young adults underwent a paired associates learning task and a sequential finger-tapping task with easy and difficult levels and were tested for memory performance before and after the intervention (i.e., an about 30-min nap or stay awake). Electroencephalogram (EEG) signals were continously recorded during the whole experiment. Results revealed that a short afternoon nap improved movement speed for the procedural memory task, regardless of the task difficulty, but unaffected the performance on the declarative memory task. Besides, the improvement in movement speed for the easy procedural memory task was positively correlated with slow-wave activity (SWA) during non-rapid-eye-movement (NREM) sleep but negatively correlated with slow oscillation and spindle activity during sleep stage 2 and NREM sleep, and the improvement in the difficult procedural memory task correlated positively with SWA during NREM sleep. Moreover, performance on the easy declarative and procedural memory tasks was negatively correlated with the relative power of alpha or theta; whereas the alpha band was positively correlated with the difficult declarative memory performance. These findings suggested that a brief afternoon nap with NREM sleep would benefit procedural memory consolidation but not declarative memory; such contribution of napping to memory consolidation would be either explained by the sleep characteristics or physiological arousal during performing tasks; task difficulty would moderate the relationship between the declarative memory performance and EEGs during task performance.

Controlling the Phase Behavior and Reflection of Main-Chain Cholesteric Oligomers Using a Smectic Monomer.

Cholesteric liquid crystals (CLCs) are a significant class of temperature-responsive photonic materials that have the ability to selectively reflect light of a specific wavelength. However, the fabrication of main-chain CLC oligomers with dramatic reflection band variation upon varying the temperatures remains a challenge. Here, a feasible method for improving and controlling the responsiveness of main-chain cholesteric liquid crystal oligomers by the incorporation of a smectic monomer is reported. The smectic monomer strengthens the smectic character of the oligomers and enhances the magnitude of the change of the pitch as a function of temperature upon approaching the cholesteric-smectic phase transition temperature. The central wavelength of the reflection band can be easily modified by mixing in an additional chiral dopant. This promising method will open the door to the preparation of temperature-responsive photonic devices with excellent responsiveness.