Optoelectronic Synapses Based on MXene/Violet Phosphorus van der Waals Heterojunctions for Visual‑Olfactory Crossmodal Perception

The crossmodal interaction of different senses,which is an important basis for learning and memory in the human brain,is highly desired to be mimicked at the device level for developing neuromorphic crossmodal perception,but related researches are scarce.Here,we demonstrate an optoelectronic synapse for vision-olfactory crossmodal perception based on MXene/violet phosphorus(VP)van der Waals heterojunctions.Benefiting from the efficient separation and transport of photogenerated carriers facilitated by conductive MXene,the photoelectric responsivity of VP is dramatically enhanced by 7 orders of magnitude,reaching up to 7.7 A W^(−1).Excited by ultraviolet light,multiple synaptic functions,including excitatory postsynaptic currents,pairedpulse facilitation,short/long-term plasticity and“learning-experience”behavior,were demonstrated with a low power consumption.Furthermore,the proposed optoelectronic synapse exhibits distinct synaptic behaviors in different gas environments,enabling it to simulate the interaction of visual and olfactory information for crossmodal perception.This work demonstrates the great potential of VP in optoelectronics and provides a promising platform for applications such as virtual reality and neurorobotics.

Two-Dimensional Black Phosphorus: An Emerging Anode Material for Lithium-Ion Batteries

Two-dimensional black phosphorus(2D BP),an emerging material,has aroused tremendous interest once discovered.This is due to the fact that it integrates unprecedented properties of other 2D materials,such as tunable bandgap structures,outstanding electrochemical properties,anisotropic mechanical,thermodynamic,and photoelectric properties,making it of great research value in many fields.The emergence of 2D BP has greatly promoted the development of electrochemical energy storage devices,especially lithium-ion batteries.However,in the application of 2D BP,there are still some problems to be solved urgently,such as the difficulty in the synthesis of large-scale high-quality phosphorene,poor environmental stability,and the volume expansion as electrode materials.Herein,according to the latest research progress of 2D BP in the field of energy storage,we systematically summarize and compare the preparation methods of phosphorene and discuss the basic structure and properties of BP,especially the environmental instability and passivation techniques.In particular,the practical application and challenges of 2D BP as anode material for lithium-ion batteries are analyzed in detail.Finally,some personal perspectives on the future development and challenges of BP are presented.

Strategies to improve electrocatalytic and photocatalytic performance of two-dimensional materials for hydrogen evolution reaction

Two-dimensional materials(2D)with unique physicochemical properties have been widely studied for their use in many applications,including as hydrogen evolution catalysts to improve the efficiency of water splitting.Recently,typical 2D materials MoS2,graphene,MXenes,and black phosphorus have been widely investigated for their application in the hydrogen evolution reaction(HER).In this review,we summarize three efficient strategies—defect engineering,heterostructure formation,and heteroatom doping—for improving the HER performance of 2D catalysts.The d-band theory,density of states,and Fermi energy level are discussed to provide guidance for the design and construction of novel 2D materials.The challenges and prospects of 2D materials in the HER are also considered.

Recent Progress of Two-Dimensional Thermoelectric Materials

Thermoelectric generators have attracted a wide research interest owing to their ability to directly convert heat into electrical power.Moreover,the thermoelectric properties of traditional inorganic and organic materials have been significantly improved over the past few decades.Among these compounds,layered two-dimensional(2D)materials,such as graphene,black phosphorus,transition metal dichalcogenides,IVA–VIA compounds,and MXenes,have generated a large research attention as a group of potentially high-performance thermoelectric materials.Due to their unique electronic,mechanical,thermal,and optoelectronic properties,thermoelectric devices based on such materials can be applied in a variety of applications.Herein,a comprehensive review on the development of 2D materials for thermoelectric applications,as well as theoretical simulations and experimental preparation,is presented.In addition,nanodevice and new applications of 2D thermoelectric materials are also introduced.At last,current challenges are discussed and several prospects in this field are proposed.

Electronic, optical property and carrier mobility of graphene, black phosphorus, and molybdenum disulfide based on the first principles

The band structure, density of states, optical properties, carrier mobility, and loss function of graphene, black phosphorus（BP）, and molybdenum disulfide（MoS_2） were investigated by the first-principles method with the generalized-gradient approximation. The graphene was a zero-band-gap semiconductor. The band gaps of BP and MoS_2 were strongly dependent on the number of layers. The relationships between layers and band gap were built to predict the band gap of few-layer BP and MoS_2. The absorption showed an explicit anisotropy for light polarized in（1 0 0） and（0 0 1） directions of graphene, BP,and MoS_2. This behavior may be readily detected in spectroscopic measurements and exploited for optoelectronic applications. Moreover, graphene（5.27 × 10~4 cm^2·V^（-1）·s^（-1））, BP（1.5 × 10~4 cm^2·V^（-1）·s^（-1））, and MoS_2（2.57×102 cm2·V-1·s-1）have high carrier mobility. These results show that graphene, BP, and MoS_2 are promising candidates for future electronic applications.

Revealing of the ultrafast third-order nonlinear optical response and enabled photonic application in two-dimensional tin sulfide

Black phosphorus(BP), a typical mono-elemental and two-dimensional(2D) material, has gathered significant attention owing to its distinct optoelectronic properties and promising applications, despite its main obstacle of long-term stability. Consequently, BP-analog materials with long-term chemical stability show additional potential. In this contribution, tin sulfide(SnS), a novel two-elemental and 2D structural BP-analog monochalcogenide, has been demonstrated to show enhanced stability under ambient conditions. The broadband nonlinear optical properties and carrier dynamics have been systematically investigated via Z-scan and transient absorption approaches. The excellent nonlinear absorption coefficient of 50.5 × 10^-3 cm∕GW, 1 order of magnitude larger than that of BP, endows the promising application of SnS in ultrafast laser generation. Two different decay times of τ1~873 fs and τ2~96.9 ps allow the alteration between pure Q switching and continuous-wave(CW) mode locking in an identical laser resonator. Both mode-locked and Q-switched operations have been experimentally demonstrated using an SnS saturable absorber at the telecommunication window. Femtosecond laser pulses with tunable wavelength and high stability are easily obtained, suggesting the promising potential of SnS as an efficient optical modulator for ultrafast photonics. This primary investigation may be considered an important step towards stable and high-performance BP-analog material-based photonic devices.

Recent advances in anisotropic two-dimensional materials and device applications

Two-dimensional(2D)materials,such as transition metal dichalcogenides(TMDs),black phosphorus(BP),MXene and borophene,have aroused extensive attention since the discovery of graphene in 2004.They have wide range of applications in many research fields,such as optoelectronic devices,energy storage,catalysis,owing to their striking physical and chemical properties.Among them,anisotropic 2D material is one kind of 2D materials that possess different properties along different directions caused by the intrinsic anisotropic atoms5 arrangement of the 2D materials,mainly including BP,borophene,low-symmetry TMDs(ReSe2 and ReSa)and group IV monochalcogenides(SnS,SnSe,GeS,and GeSe).Recently,a series of new devices has been fabricated based on these anisotropic 2D materials.In this review,we start from a brief introduction of the classifications,crystal structures,preparation techniques,stability,as well as the strategy to discriminate the anisotropic characteristics of 2D materials.Then,the recent advanced applications including electronic devices,optoelectronic devices,thermoelectric devices and nanomechanical devices based on the anisotropic 2D materials both in experiment and theory have been summarized.Finally,the current challenges and prospects in device designs,integration,mechanical analysis,and micro-/nano-fabrication techniques related to anisotropic 2D materials have been discussed.This review is aimed to give a generalized knowledge of anisotropic 2D materials and their current devices applications,and thus inspiring the exploration and development of other kinds of new anisotropic 2D materials and various novel device applications.

Solvent-stabilized few-layer violet phosphorus and its ultrafast nonlinear optics

Featured with high thermal decomposition temperature and layered structure,violet phosphorus(VP)offers an unparalleled stable allotrope of phosphorus to demonstrate the optoelectronic device and photonics elements with high performance at the nanoscale.Here,we report few-layer and hundreds of nanometer-sized VP with robust stability in different solvents and ambient conditions by ultrasound-assisted liquid phase exfoliation approach.For the first time,the ultrafast carrier dynamics and thirdorder nonlinear optical response of VP were investigated.Sub-picosecond timescale ultrafast carrier dynamic and ultrafast nonlinear saturable absorption of VP were demonstrated.Our findings demonstrated that VP possessed a promising potential for use in ultrafast nonlinear photonic applications such as saturable absorbers and optical switches.

Two-dimensional square transition metal dichalcogenides with lateral heterostructures

Fabrication of lateral heterostructures （LHS） is promising for a wide range of next-generation devices and could sufficiently unlock the potential of two-dimensional materials.Herein,we demonstrate the design of lateral heterostructures based on new building materials,namely 1S-MX2 LHS,using first-principles calculations.1S-MX2 LHS exhibits excellent stability,demonstrating high feasibility in the experiment.The desired bandgap opening can endure application at room temperature and was confirmed in 1S-MX2 LHS with spin-orbit coupling （SOC）.A strain strategy further resulted in efficient bandgap engineering and an intriguing phase transition.We also found that black phosphorus can serve as a competent substrate to support 1S-MX2 LHS with a coveted type-Ⅱ band alignment,allowing versatile functionalized bidirectional heterostructures with built-in device functions.Furthermore,the robust electronic features could be maintained in the 1S-MX2 LHS with larger components.Our findings will not only renew interest in LHS studies by enriching their categories and properties,but also highlight the promise of these lateral heterostructures as appealing materials for future integrated devices.

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

Environmental catalysis has drawn a great deal ofattention due to its clean ways to produce useful chemicals or carry out some chemical processes.Photocatalysis and electrocatalysis play important roles in these fields.They can decompose and remove organic pollutants from the aqueous environment,and prepare some fine chemicals.Moreover,they also can carry out some important reactions,such as 02 reduction reaction(ORR),O2 evolution reaction(OER),H2 evolution reaction(HER),CO2 reduction reaction(C02 RR),and N2 fixation(NRR).For catalytic reactions,it is the key to develop high-performance catalysts to meet the demand fortargeted reactions.In recentyears,two-dimensional(2 D) materials have attracted great interest in environmental catalysis due to their unique layered structures,which offer us to make use of their electronic and structural characteristics.Great progress has been made so far,including graphene,black phosphorus,oxides,layered double hydroxides(LDHs),chalcogenides,bismuth-based layered compounds,MXenes,metal organic frameworks(MOFs),covalent organic frameworks(COFs),and others.This content drives us to invite many famous groups in these fields to write the roadmap on two-dimensional nanomaterials for environmental catalysis.We hope that this roadmap can give the useful guidance to researchers in future researches,and provide the research directions.

Laser-ablated violet phosphorus/graphene heterojunction as ultrasensitive ppb-level room-temperature NO sensor

Two dimensional(2D)materials are promising gas sensing materials,but the most of them need to be heated to show promising sensing performance.Sensing structures with high sensing performance at room-temperature are urgent.Here,another 2D material,violet phosphorus(VP)nanoflake is investigated as gas sensing material.The VP nanoflakes have been effectively ablated to have layers of 1–5 layers by laser ablation in glycol.The VP nanoflakes are combined with graphene to form VP/G heterostructuresbased NO sensor.An ultra-high gauge factor of 3×10^(7)for ppb-level sensing and high resistance response of 59.21%with ultra-short recovery time of 6s for ppm-level sensing have been obtained.The sensing mechanism is also analysed by density functional theory(DFT)calculations.The adsorption energy of VP/G is calculated to be-0.788 e V,resulting in electrons migration from P to N to form a P-N bond in the gap between VP and graphene sheet.This work provides a facile approach to ablate VP for mass production.The as-produced structures have also provided potential gas sensors with ultrasensitive performance as ppb-level room-temperature sensors.

Liquid-phase exfoliation of violet phosphorus for electronic applications

Large-scale production of two-dimensional(2D)materials still is a crucial point toward its practical applications.Violet phosphorus(VP)with a wide bandgap accelerates and broadens the potential applications of elemental phosphorus in optoelectronics.Here,we demonstrate the scalable production of solution-processable violet phosphorus flakes stably dispersed in several solvents.The exfoliated VP flakes exhibit thickness-dependent visible photoluminescence characteristics,which covers the shortcoming of black phosphorus.Meanwhile,the VP-based field-effect transistor reveals relatively competitive electrical properties to other liquid-phase exfoliated 2D materials.Our study paves the way for a wide range of applications of optical devices,energy storage,catalysis,and sodium batteries based on large-scale VP flakes.

High-performance violet phosphorus photodetectors with van der Waals-assisted contacts

Black phosphorus(BP) as a narrow-bandgap two-dimensional semiconductor material has been extensively studied. And the allotrope violet phosphorus(VP) exhibits wide bandgap properties extending the application in the visible light band. However,due to the Schottky barrier of metal/semiconductor contacts(M/S), further device application of VP is limited. Here, VP-based photodetectors with van der Waals-assisted contact were demonstrated, achieving quasi-Ohmic M/S contacts. The output characteristics in dark conditions show ultralow current at the pA level. And the device exhibits a high current on-off ratio of 10~5and a fast response speed of 8.4 ms. Furthermore, we constructed the first allotropic photodetector based on BP and VP heterojunction. The device maintains ultralow dark current(~ pA) while exhibiting faster carrier transport, with 945 μs response time and polarization detection capability. These results offer an effective way to study the optoelectronic properties of VP and promote the study of allotropic heterojunction devices.

Control of crystal growth to obtain needle-shaped violet phosphorus with excellent photocatalytic degradation performance

The control of crystal growth is important but challenging for multi-disciplinary research.Violet phosphorus,the most stable phosphorus allotrope,has recently been produced as a unique semiconducting layered structure.The crystal orientation and morphology bring extra performance due to its unique structure and anisotropy.Herein,the layered violet phosphorus has been controlled to grow along the c-axis to give tunable length up to centimeters with the assistance of tin,while the reported flat bulk ones with thickness are limited to micrometers.The as-produced needle-shaped violet phosphorus has also been demonstrated to significantly enhance the photocatalytic degradation of methyl orange pollutants due to its special crystallographic orientation.About 98.6%of methyl orange pollutants with a concentration of 50 ppm were degraded within 80 min under visible light conditions by needle-shaped violet phosphorus,which is much more effective than that of amorphous red phosphorus with only 14.1%degradation.

A brief review of tribological properties for black phosphorus

Black phosphorus (BP) is a new class of two-dimensional (2D) layered material, which shows the unanticipated characteristics in many aspects including electronics, transistors, sensors, energy storage, batteries, photocatalysis, and other applications due to its high charge carrier mobility, tunable direct bandgap, and unique in-plane anisotropic structure. In addition, BP has drawn tremendous attention in the field of tribology due to the low shear strength, the layered structure, and the weak connected force between the layers by van der Waals interaction. In recent years, many significant progresses have been made in experimental studies on BP materials as solid lubricants or lubrication additives. This work offers a review of researching regarding the tribological properties of BP. Moreover, the lubrication mechanisms of BP as the lubrication additive including the formation of the tribo-film, micro-bearing effect, and self-repair performance are also summarized. Finally, the current challenges and prospects of BP material as lubricant are proposed.

Investigation of black phosphorus as a nano-optical polarization element by polarized Raman spectroscopy

Manipulating the polarization of light at the nanoscale is essential for the development of nano-optical devices. Owing to its corrugated honeycomb structure, two-dimensional （2D） layered black phosphorus （BP） exhibits outstanding in-plane optical anisotropy with distinct linear dichroism and optical birefringence in the visible region, which are superior characteristics for ultrathin polarizing optics. Herein, taking advantage of polarized Raman spectroscopy, we demonstrate that layered BP with a nanometer thickness can remarkably alter the polarization state of a linearly-polarized laser and behave as an ultrathin optical polarization element in a BP-Bi2Se3 stacking structure by inducing the exceptionally polarized Raman scattering of isotropic Bi2Se3. Our findings provide a promising alternative for designing novel polarization optics based on 2D anisotropic materials, which can be easily integrated in micro- sized all-optical and optoelectronic devices.

Nanoscopy reveals surface-metallic black phosphorus

Black phosphorus(BP)is an emerging two-dimensional material with intriguing physical properties.It is highly anisotropic and highly tunable by means of both the number of monolayers and surface doping.Here,we experimentally investigate and theoretically interpret the near-field properties of a-few-atomic-monolayer nanoflakes of BP.We discover near-field patterns of bright outside fringes and a high surface polarizability of nanofilm BP consistent with its surface-metallic,plasmonic behavior at mid-infrared frequencies o1176 cm−1.We conclude that these fringes are caused by the formation of a highly polarizable layer at the BP surface.This layer has a thickness of~1 nm and exhibits plasmonic behavior.We estimate that it contains free carriers in a concentration of n≈1.1×10^(20) cm^(−3).Surface plasmonic behavior is observed for 10–40 nm BP thicknesses but absent for a 4-nm BP thickness.This discovery opens up a new field of research and potential applications in nanoelectronics,plasmonics and optoelectronics.

Interstitial copper-doped edge contact for n-type carrier transport in black phosphorus

Black phosphorus(BP)has been shown as a promising two-dimensional(2D)material for electronic devices owing to its high carrier mobility.To realize complementary electronic circuits with 2D materials,it is important to fabricate both n-type and p-type transistors with the same channel material.By engineering the contact region with copper(Cu)-doped BP,here we demonstrate an n-type carrier transport in BP field-effect transistors(FETs),which usually exhibit strongly p-type characteristics.Cu metal atoms are found to severely penetrate into the BP flakes,which forms interstitial Cu(Cuint)-doped edge contact and facilitates the electron transport in BP.Our BP FETs in backgated configuration exhibit n-type dominant characteristics with a high electron mobility of^138 cm^2 V^−1 s^−1 at room temperature.The Schottky barrier height for electrons is relatively low because of the edge contact between Cuint-doped BP and pristine BP channel.The contact doping of BP by highly mobile Cu atoms gives rise to n-type transport property of BP FETs.Furthermore,we demonstrate a p-n junction on the same BP flake with asymmetric contact.This strategy on contact engineering can be further extended to other 2D materials.

Tri-functional lanthanum-based biochar for efficient phosphorus recovery,bacterial inhibition,and soil fertility enhancement

Excess phosphorus(P)in water can lead to eutrophication and upset ecological balance.In this study,biochar with ultrathin two-dimensional nanosheets from the natural mesocarp of shaddock was chosen as the carrier.The highly dispersed and small particle size of La(OH)_(3) on the surface of the nanosheets(MSBL3)was successfully achieved using chemical impregnation for the adsorption of P in aqueous solution,and the maximum adsorption capacity was 260.0 mg P g^(−1)[La].The differences in surface crystallization of La(OH)_(3) on biochar at different La loadings were analyzed using the high-precision characterization methods.After six adsorption-desorption cycles,MSBL3 retained 76.7%of its initial performance in terms of the P adsorption capacity.The preparation of 1 g of MSBL3 costs about RMB 1,and it could reduce the P concentration in 2.6 ton of Laoyu River water to below the eutrophication threshold;and the inhibitory effect of MSBL3 on the eutrophication of water bodies was confirmed by the growth state of water hyacinth.Furthermore,0.1 M MSBL3 could inhibit Escherichia coli and Staphylococcus aureus up to 98.7%and 85.0%,respectively,which indicates that MSBL3 can be used to recover P from water and also to improve water quality.In addition,the growth of the maize seedlings verified that the P-absorbed MSBL3 waste is a good soil fertilizer and can solve the problem of post-treatment of the adsorbent.In conclusion,MSBL3 prepared in this study is a promising P sorbent for application.

Covalent carbene modification of 2D black phosphorus

Black phosphorus(BP)has attracted an ever-growing interest due to its unique anisotropic two-dimensional structure,impressive photoelectronic properties and attractive application potential.However,the tools for bandgap engineering and passivation via covalent modification of BP nanosheets remain limited to diazonium salt and nucleophilic addition methods,so that developing new modification strategies for BP nanosheets is crucial to explore its physical and chemical properties and enrich the toolbox for functionalization.Herein,we report the covalent modification of liquid-phase exfoliated BP nanosheets based on a rational analysis of BP structure.The modification of BP is achieved via carbene,a highly reactive organic mediate.The carbene modification improves the solubility and stability of BP nanosheets.Detailed microscopic and spectroscopic characterizations including infrared spectra,Raman spectra,X-ray photoelectron spectra,SEM and TEM were conducted to provide insights for the reaction.The proof of the existence of covalent bonds between BP nanosheets and organic moieties confirms the successful modification.Moreover,theoretical calculations were conducted to unveil the reaction mechanism of the two different types of bonds and the chemical property of two-dimensional BP.