Artificial Optoelectronic Synapse Based on Violet Phosphorus Microfiber Arrays.

Memristor-based artificial synapses are regarded as the most promising candidate to develop brain-like neuromorphic network computers and overcome the bottleneck of Von-Neumann architecture. Violet phosphorus (VP) as a new allotrope of available phosphorus with outstanding electro-optical properties and stability has attracted more and more attention in the past several years. In this study, large-scale, high-yield VP microfiber vertical arrays have been successfully developed on a Sn-coated graphite paper and are used as the memristor functional layers to build reliable, low-power artificial synaptic devices. The VP devices can well mimic the major synaptic functions such as short-term memory (STM), long-term memory (LTM), paired-pulse facilitation (PPF), spike timing-dependent plasticity (STDP), and spike rate-dependent plasticity (SRDP) under both electrical and light stimulation conditions, even the dendritic synapse functions and simple logical operations. By virtue of the excellent performance, the VP artificial synapse devices can be conductive to building high-performance optic-neural synaptic devices simulating the human-like optic nerve system. On this basis, Pavlov's associative memory can be successfully implemented optically. This study provides a promising approach for the design and manufacture of VP-based artificial synaptic devices and outlines a direction with multifunctional neural devices.

SiC@NiO Core-Shell Nanowire Networks-Based Optoelectronic Synapses for Neuromorphic Computing and Visual Systems at High Temperature.

1D nanowire networks, sharing similarities of structure, information transfer, and computation with biological neural networks, have emerged as a promising platform for neuromorphic systems. Based on brain-like structures of 1D nanowire networks, neuromorphic synaptic devices can overcome the von Neumann bottleneck, achieving intelligent high-efficient sensing and computing function with high information processing rates and low power consumption. Here, high-temperature neuromorphic synaptic devices based on SiC@NiO core-shell nanowire networks optoelectronic memristors (NNOMs) are developed. Experimental results demonstrate that NNOMs attain synaptic short/long-term plasticity and modulation plasticity under both electrical and optical stimulation, and exhibit advanced functions such as short/long-term memory and "learning-forgetting-relearning" under optical stimulation at both room temperature and 200 °C. Based on the advanced functions under light stimulus, the constructed 5 × 3 optoelectronic synaptic array devices exhibit a stable visual memory function up to 200 °C, which can be utilized to develop artificial visual systems. Additionally, when exposed to multiple electronic or optical stimuli, the NNOMs effectively replicate the principles of Pavlovian classical conditioning, achieving visual heterologous synaptic functionality and refining neural networks. Overall, with abundant synaptic characteristics and high-temperature thermal stability, these neuromorphic synaptic devices offer a promising route for advancing neuromorphic computing and visual systems.

In Situ Growth of Iron Sulfide on Fast Charge Transfer V2 C-MXene for Superior Sodium Storage Anodes.

Due to the upstream pressure of lithium resources, low-cost sodium-ion batteries (SIBs) have become the most potential candidates for energy storage systems in the new era. However, anode materials of SIBs have always been a major problem in their development. To address this, V2 C/Fe7 S8 @C composites with hierarchical structures prepared via an in situ synthesis method are proposed here. The 2D V2 C-MXene as the growth substrate for Fe7 S8  greatly improves the rate capability of SIBs, and the carbon layer on the surface provides a guarantee for charge-discharge stability. Unexpectedly, the V2 C/Fe7 S8 @C anode achieves satisfactory sodium storage capacity and exceptional rate performance (389.7 mAh g-1  at 5 A g-1 ). The sodium storage mechanism and origin of composites are thoroughly studied via ex situ characterization techniques and first-principles calculations. Furthermore, the constructed sodium-ion capacitor assembled with N-doped porous carbon delivers excellent energy density (135 Wh kg-1 ) and power density (11 kW kg-1 ), showing certain practical value. This work provides an advanced system of sodium storage anode materials and broadens the possibility of MXene-based materials in the energy storage.

Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro-Phototronic Effects.

The bottom-up preparation of two-dimensional material micro-nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom-up micro-nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom-up preparation of fibrous phosphorus micropillar (FP-MP) arrays via a low-pressure gas-phase transport (LP-CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self-powered photodetectors (PD) of FP-MP arrays with pyro-phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom-up preparation of other crystalline allotropes of phosphorus.

Stabilizing Solid-state Lithium Metal Batteries through In Situ Generated Janus-heterarchical LiF-rich SEI in Ionic Liquid Confined 3D MOF/Polymer Membranes.

Pursuing high power density lithium metal battery with high safety is essential for developing next-generation energy-storage devices, but uncontrollable electrolyte degradation and the consequence formed unstable solid-electrolyte interface (SEI) make the task really challenging. Herein, an ionic liquid (IL) confined MOF/Polymer 3D-porous membrane was constructed for boosting in situ electrochemical transformations of Janus-heterarchical LiF/Li3 N-rich SEI films on the nanofibers. Such a 3D-Janus SEI-incorporated into the separator offers fast Li+ transport routes, showing superior room-temperature ionic conductivity of 8.17×10-4  S cm-1 and Li+ transfer number of 0.82. The cryo-TEM was employed to visually monitor the in situ formed LiF and Li3 N nanocrystals in SEI and the deposition of Li dendrites, which is greatly benefit to the theoretical simulation and kinetic analysis of the structural evolution during the battery charge and discharge process. In particular, this membrane with high thermal stability and mechanical strength used in solid-state Li||LiFePO4 and Li||NCM-811 full cells and even in pouch cells showed enhanced rate-performance and ultra-long life spans.

Cluster Nanozymes with Optimized Reactivity and Utilization of Active Sites for Effective Peroxidase (and Oxidase) Mimicking.

Single-atom catalysts have attracted attention in the past decade since they maximize the utilization of active sites and facilitate the understanding of product distribution in some catalytic reactions. Recently, this idea has been extended to single-atom nanozymes (SAzymes) for the mimicking of natural enzymes such as horseradish peroxidase (HRP) often used in bioanalytical applications. Herein, it is demonstrated that those SAzymes without constructing the reaction pocket of HRP still undergo the OH radical-mediated pathway like most of the reported nanozymes. Their positively charged single-atom centers resulting from support electronegative oxygen/nitrogen hinder the reductive conversion of H2 O2 to OH radicals and hence display low activity per site. In contrast, it is found that this step can be facilitated over their metallic counterparts on cluster nanozymes with much higher site activity and atom efficiency (cf. SAzymes with 100% atom utilization). Besides the mimicking of HRP in glucose detection, cluster nanozymes are also demonstrated as a better oxidase mimetic for glutathione detection.

Chemical Energy-Driven Lithiation Preparation of Defect-Rich Transition Metal Nanostructures for Electrocatalytic Hydrogen Evolution.

Transition metal nanostructures are widely regarded as important catalysts to replace the precious metal Pt for hydrogen evolution reaction (HER) in water splitting. However, it is difficult to obtain uniform-sized and ultrafine metal nanograins through general high-temperature reduction and sintering processes. Herein, a novel method of chemical energy-driven lithiation is introduced to synthesize transition metal nanostructures. By taking advantage of the slow crystallization kinetics at room temperature, more surface and boundary defects can be generated and remained, which reduce the atomic coordination number and tune the electronic structure and adsorption free energy of the metals. The obtained Ni nanostructures therein exhibit excellent HER performance. In addition, the bimetal of Co and Ni shows better electrocatalytic kinetics than individual Ni and Co nanostructures, reaching 100 mA cm-2 at a low overpotential of 127 mV. The high HER performance originates from well-formed synergistic effect between Ni and Co by tuning the electronic structures. Density functional theory simulations confirm that the bimetallic NiCo possesses a low Gibbs free energy of hydrogen adsorption, which are conducive to enhance its intrinsic activity. This work provides a general strategy that enables simultaneous defect engineering and electronic modulation of transition metal catalysts to achieve an enhancement in HER performance.

Optimization of PEC and photocathodic protection performance of TiO2/CuInS2heterojunction photoanodes.

The establishment of heterojunction is a powerful strategy to enhance the photoresponse performance of photoanode. Here, TiO2/CuInS2(T/CIS) composites were prepared via a two-step hydrothermal method, and their morphologies were controlled by adjusting the reaction time. The absorption spectra show that CuInS2can significantly improve the absorption of visible light. The T/CIS2 (2 h reaction time) photoanode exhibited the most outstanding photoelectrochemical (PEC) performance, with a photocurrent density of 168% that of the pure TiO2photoanode. Under simulated sunlight, this photoanode can supply a protective photocurrent of 0.49 mA cm-2and a protective voltage of 0.36 V to stainless steel (304ss), which are about 4 and 2 times those of the TiO2sample. The enhancement in the photocathodic protection performance is attributed to enlarged visible light absorbance and higher charge separation rate. This study demonstrates that the TiO2/CuInS2photoanode is a promising candidate for application in photoinduced cathodic protection of metallic materials.

Promotion of Melanoma Cell Proliferation by Cyclic Straining through Regulatory Morphogenesis.

The genotype and phenotype of acral melanoma are obviously different from UV-radiation-induced melanoma. Based on the clinical data, mechanical stimulation is believed to be a potential cause of acral melanoma. In this case, it is desirable to clarify the role of mechanical stimulation in the progression of acral melanoma. However, the pathological process of cyclic straining that stimulates acral melanoma is still unclear. In this study, the influence of cyclic straining on melanoma cell proliferation was analyzed by using a specifically designed cell culture system. In the results, cyclic straining could promote melanoma cell proliferation but was inefficient after the disruption of cytoskeleton organization. Therefore, the mechanotransduction mechanism of promoted proliferation was explored. Both myosin and actin polymerization were demonstrated to be related to cyclic straining and further influenced the morphogenesis of melanoma cells. Additionally, the activation of mechanosensing transcription factor YAP was related to regulatory morphogenesis. Furthermore, expression levels of melanoma-involved genes were regulated by cyclic straining and, finally, accelerated DNA synthesis. The results of this study will provide supplementary information for the understanding of acral melanoma.

Electronic Structure Tuning of 2D Metal (Hydr)oxides Nanosheets for Electrocatalysis.

2D metal (hydr)oxide nanosheets have captured increasing interest in electrocatalytic applications aroused by their high specific surface areas, enriched chemically active sites, tunable physiochemical properties, etc. In particular, the electrocatalytic reactivities of materials greatly rely on their surface electronic structures. Generally speaking, the electronic structures of catalysts can be well adjusted via controlling their morphologies, defects, and heterostructures. In this Review, the latest advances in 2D metal (hydr)oxide nanosheets are first reviewed, including the applications in electrocatalysis for the hydrogen evolution reaction, oxygen reduction reaction, and oxygen evolution reaction. Then, the electronic structure-property relationships of 2D metal (hydr)oxide nanosheets are discussed to draw a picture of enhancing the electrocatalysis performances through a series of electronic structure tuning strategies. Finally, perspectives on the current challenges and the trends for the future design of 2D metal (hydr)oxide electrocatalysts with prominent catalytic activity are outlined. It is expected that this Review can shed some light on the design of next generation electrocatalysts.

Tunable white light emission of an anti-ultraviolet rare-earth polysiloxane phosphors based on near UV chips.

A novel white-light copolymer matched with 365 nm chips is prepared by bonding the vinyl-functionalized complexes Eu(TTA)2(Phen)(MAA), Tb(p-BBA)3(UA) and Zn(BTZ)(UA) to polysiloxaneprepolymer(synthesized by polycondensation of vinyltrimethoxysilane and diphenylsilanediol) through a technical route of polymerization after coordination. Its structure was characterized by infrared and ultraviolet. Under the excitation of 365 nm, when the ratio of the tricolor complexes is controlled to be 0.5: 3: 1.5, white light copolymer with CIE color coordinates of (0.327, 0.321) was obtained and packaged to get white light LED devices. After aging, the CIE color coordinates of the device change from (0.325, 0.329) to (0.341, 0.348), the color rendering index changes from 91 to 88, and the correlated color temperature changes from 5967 K to 5612 K. The loss of brightness is only 10.4%, which shows good resistance to UV aging. Moreover, the initial decomposition temperature of the copolymer is 235°C. The above results show that the bonding-type anti-ultraviolet copolymer phosphor has potential application in near ultraviolet LEDs.

Interface-engineered Co3S4/CoMo2S4nanosheets as efficient bifunctional electrocatalysts for alkaline overall water splitting.

Exploring bifunctional electrocatalysts with high efficiency, inexpensive, and easy integration is still the daunt challenge for the production of hydrogen on a large scale by means of water electrolysis. In this work, a novel free-standing Co3S4/CoMo2S4heterostructure on nickel foam by a facial hydrothermal method is demonstrated to be an effective bifunctional electrocatalyst for overall water splitting (OWS). The synthesized Co3S4/CoMo2S4electrocatalyst achieves ultralow overpotentials of 143 mV@10 mA cm-2for hydrogen evolution reaction (HER) and 221 mV@25 mA cm-2for oxygen evolution reaction (OER), respectively, in 1 M KOH. Moreover, it presents a greatly improved durability and stability under operando electrochemical conditions. When used as catalysts for OWS, the Co3S4/CoMo2S4-3//Co3S4/CoMo2S4-3 electrodes just need 1.514 V to make it to the current density of 10 mA cm-2. It is supposed that the introduction of heterogeneous interface between Co3S4and CoMo2S4could give rise to plentiful active sites and enhanced conductivity, and thus boost excellent catalytic performances. Moreover, the porous feature of free-standing nanosheets on nickel foam could benefits catalytic performances by accelerating charge transport and releasing bubbles rapidly. This work proposes a bifunctional catalyst system with the heterogeneous interface, which could be used in a sustainable green energy system.

Charge compensation weakening ionized impurity scattering and assessing the minority carrier contribution to the Seebeck coefficient in Pb-doped Mg3Sb2 compounds.

This work reports the electrical and thermal transport processes in p-type Pb-doped Mg3(1+x)Sb2-yPby (0.02 ≤ x ≤ 0.08; 0 ≤ y ≤ 0.02) compounds. Low-energy electron acceptor defects Mg vacancies are easy to form, which can provide holes and make p-type transport in the Mg3Sb2 matrix. However, with an increase in excess Mg, the transport behavior changes from p type to n type as manifested synergistically by both the Hall coefficient and Seebeck coefficient. This indicates the effective role of Mg in tuning carrier type and concentration for a pristine Mg3Sb2 compound. Upon substitution of Sb by Pb, the hole concentration slightly increases, and mobility is greatly improved by 133% at room temperature. The significant increase in mobility is attributed to the weakening ionized impurity scattering, stemming from the decreasing concentration induced by Pb doping. Thus, the power factor is enhanced with a 146% improvement at room temperature. Consequently, the figure of merit ZT of the Pb-doped sample is 1.8 times larger than the pristine one at around 300 K. Moreover, the non-degenerate transport behavior revealed by electrical properties is simply analyzed regarding the effects of minority carriers on the overall Seebeck coefficient. This study proposes a new strategy of charge compensation for improving mobility and a simple way to guide the prediction about the onset of bipolar conduction for Mg3Sb2-based compounds and other potential thermoelectric materials.

High-Performance Organic Electroluminescence: Design from Organic Light-Emitting Materials to Devices.

Organic electroluminescence is considered as the most competitive alternative for the future solid-state displays and lighting techniques owing to many advantages such as self-luminescence, high efficiency, high contrast, high color rendering index, ultra-thin thickness, transparency, flat and flexibility, etc. The development of high-performance organic electroluminescence has become the continuing focus of research. In this personal account, a brief overview of representative achievements in our study on the design of highly efficient novel organic light-emitting materials (including fluorescent materials, phosphorescent iridium(III) complexes and conjugated polymers bearing phosphorescent iridium(III) complex) and high-performance device structures together with working principles are given. At last, we will give some perspectives on this fascinating field, and also try to provide some potential directions of research on the basis of the current stage of organic electroluminescence.

Direct imaging of a single Ni atom cutting graphene to form a graphene nanomesh.

A large area graphene nanomesh (GNM) etched by Ni is synthesized by a facile one-step liquid arc discharge in a Ni-containing solution. Atomic-resolution scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS) is applied to identify the atomic structures of the product. The results show that the GNM with a pore size of about 10-50 nm comprises single- or few layer graphene, and there are some small pores of size 1 nm and defects of five membered rings or seven membered rings in the positions of the skeletons. Also Ni atoms or nanoparticles are uniformly distributed in graphene or at the edges of the GNM. A dynamic study using a microscope shows that the Ni atom at the edge of graphene is active and can move along the edge, which facilitates the fracture of C-C bonds and the diffusion of carbon atoms greatly. DFT calculation results show that the diffusion of carbon atoms along the edge in the GNM containing Ni is easier than that in pristine graphene. The Ni atoms or particles act as an "atomic knife" to cut the graphene sheet to feed the formation of the GNM. These results represent a significant advancement in the growth mechanism study of GNMs and thus the precise structure control of graphene.

Direct imaging of construction of carbon onions by curling few-layer graphene flakes.

The violent reaction processing and required high-temperature environment involved in growing carbon onions make it difficult to obtain an insight into their evolution mechanism. By using deionized water as the medium of arc discharge, we successfully froze the synthetic reaction at intermediary stages and observed detailed structures of the obtained intermediates of carbon onions. Here we present the atomic-scale scanning transmission electron microscopy investigation of carbon onions produced by arc discharge in water. We directly observed that carbon onions at intermediary growth stage are characterized by unclosed few-layer graphene shells. Meanwhile, a kind of graphene flakes composed of 3 layers or less were also observed in the sample. The kindred evolution linkage was induced to exist among these few-layer graphene flakes and carbon onions in the arc discharge synthetic process. On the basis of microscopy observations, we propose that carbon onions are constructed by curling few-layer graphene flakes, which is beneficial for structural designs and controls of related carbon materials used in different fields.

Morphologies and optical and electrical properties of InGaN/GaN micro-square array light-emitting diode chips.

InGaN/GaN micro-square array light-emitting diode (LED) chips (micro-chips) have been prepared via the focused ion beam (FIB) etching technique, which can not only reduce ohmic contact degradation but also control the aspect ratio precisely in three-dimensional (3D) structure LED (3D-LED) device fabrication. The effects of FIB beam current and micro-square array depth on morphologies and optical and electrical properties of the micro-chips have been studied. Our results show that sidewall surface morphology and optical and electrical properties of the micro-chips degrade with increased beam current. After potassium hydroxide etching with different times, an optimal current-voltage and luminescence performance can be obtained. Combining the results of cathodoluminescence mappings and light output-current characteristics, the light extraction efficiency of the micro-chips is reduced as FIB etch depth increases. The mechanisms of micro-square depth on light extraction have been revealed by 3D finite difference time domain.

Effect of potential barrier height on the carrier transport in InGaAs/GaAsP multi-quantum wells and photoelectric properties of laser diode.

The growth and strain-compensation behaviour of InGaAs/GaAsP multi-quantum wells, which were fabricated by metal-organic chemical vapor deposition, have been studied towards the application of these quantum wells in high-power laser diodes. The effect of the height of the potential barrier on the confined level of carrier transport was studied by incorporating different levels of phosphorus content into the GaAsP barrier. The crystal quality and interface roughness of the InGaAs/GaAsP multi-quantum wells with different phosphorus contents were evaluated by high resolution X-ray diffraction and in situ optical surface reflectivity measurements during the growth. The surface morphology and roughness were characterized by atomic force microscopy, which indicates the variation law of surface roughness, terrace width and uniformity with increasing phosphorus content, owing to strain accumulation. Moreover, the defect generation and structural disorder of the multi-quantum wells were investigated by Raman spectroscopy. The optical properties of the multi-quantum wells were characterized by photoluminescence, which shows that the spectral intensity increases as the phosphorus content increases. The results suggest that more electrons are well bound in InGaAs because of the high potential barrier. Finally, the mechanism of the effect of the height of the potential barrier on laser performance was proposed on the basis of simulation calculations and experimental results.

Metallofullerenes encaging mixed-metal clusters: synthesis and structural studies of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80.

Metallofullerenes of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 encapsulating mixed-metal nitride clusters were synthesized. Spectroscopic characterization of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 was employed to reveal their structural and vibrational properties. The structural properties of these species were analyzed by using theoretical calculations. The studies of Gdx Ho3-x N@C80 and Gdx Lu3-x N@C80 laid the foundations for these species to be used as multifunctional molecules.

Blackening of magnesium alloy using femtosecond laser.

Magnesium alloy, a potential structural and biodegradable material, has been increasingly attracting attention. In this paper, two structures with enhanced light absorption on an AZ31B magnesium surface are fabricated by femtosecond laser texturing. Laser power and the number of laser pulses are mainly investigated for darkening effect. After irradiation, surface characteristics are analyzed by a scanning electron microscope equipped with an energy dispersive spectrometer and laser scanning confocal microscope. The darkening effect is investigated by a spectrophotometer with an integrating sphere. Microgroove and stripe structures are obtained, which are covered with homogeneous nanoprotrusions and nanoparticles. The main surface chemical composition after laser ablation is MgO. The optimal light absorption in the visible range (wavelength of 400-800 nm) reaches about 98%, which is significantly improved compared with the untreated surface. The enhanced light absorption is mainly attributed to surface structure. Femtosecond laser surface texturing technology offers potential in the application of stealth technology, airborne devices, and biomedicine.