Synthesis of two-dimensional/one-dimensional heterostructures with tunable width

Two-dimensional/one-dimensional(2D/1D)heterostructures as a new type of heterostructure have been studied for their unusual properties and promising applications in electronic and optoelectronic devices.However,the studies of 2D/1D heterostructures are mainly focused on vertical heterostructures,such as MoS_(2) nanosheet-carbon nanotubes.The research on lateral 2D/1D heterostructures with a tunable width of 1D material is still scarce.In this study,bidirectional flow chemical vapor deposition(CVD)was used to accurately control the width of the WS_(2)/WSe2(WS_(2)/MoS_(2))heterostructures by controlling reacting time.WSe2 and MoS_(2) with different widths were epitaxially grown at the edge of WS_(2),respectively.Optical microscope,atomic force microscope(AFM),and scanning electron microscope(SEM)images show the morphology and width of the heterostructures.These results show that the width of the heterostructures can be as low as 10 nm by using this method.The interface of the heterostructure is clear and smooth,which is suitable for application.This report offers a new method for the growth of 1D nanowires,and lays the foundation for the future study of the physical and chemical properties of 2D/1D lateral heterostructures.

Intercalation of Two-dimensional Layered Materials

Two-dimensional(2D)layered materials have attracted great attention due to their unique electrical,optical,thermal and mechanical properties.2D layered materials have miique van der Waals gaps,thus the foreign substance,such as atoms,molecules and ions,can be inserted into the gaps to change the physical and chemical properties of 2D layered materials,which is conducive to realize their multi-fimctional application.Herein,we present a critical review of recent research progress of 2D intercalated materials,including the synthesizing metliods,theoretical calculation,characterization and multifunctional application.Finally,we will summarize llie current challenges and future opportunities in the development of 2D intercalated materials.

Patterning two-dimensional semiconductors with thermal etching

The controllable synthesis of complicated nanostructures in advanced two-dimensional(2D)semiconductors,such as periodic regular hole arrays,is essential and remains immature.Here,we report a green,facile,highly controlled synthetic method to efficiently pattern 2D semiconductors,such as periodic regular hexagonal-shaped hole arrays(HHA),in 2D-TMDs.Combining the production of artificial defect arrays through laser irradiation with anisotropic annealing etching,we created HHA with different arrangements,controlled hole sizes,and densities in bilayer WS_(2).Atomic force microscopy(AFM),Raman,photoluminescence(PL),and scanning transmission electron microscopy(STEM)characterization show that the 2D semiconductors have high quality with atomical clean and sharp edges as well as undamaged crystals in the unetched region.Furthermore,other nanostructures,such as nanoribbons and periodic regular triangular-shaped 2D-TMD arrays,can be fabricated.This kind of 2D semiconductors fabrication strategy is general and can be extended to a series of 2D materials.Density functional theory(DFT)calculations show that one WS_(2)molecule from the edges of the laser-irradiated holed region exhibits a robust etching activation,making selective etching at the artificial defects and the fabrication of regular 2D semiconductors possible.

Hierarchically porous Cu current collector with lithiophilic CuxO interphase towards high-performance lithium metal batteries

Lithium metal is one of the most promising anode materials for next-generation electrochemical energy storage due to low electrochemical potential and high specific capacity.However,large volume change and uncontrollable formation of lithium dendrite during cycling severely hinder the practical application of rechargeable Li metal batteries.Herein,we report a hierarchically porous Cu covered with lithiophilic CuxO(HPCu-CuxO) via femtosecond laser strategy in about 2 min as current collector for highperformance Li metal batteries.With precisely tunable pore volume and depth as well as lithiophilic CuxO interphase,the HPCu-CuxO not only guides homogeneous Li nucleation,resulting in a smooth and dendrite-free lithium surface,but also provides space to alleviate the volume expansion of Li metal anode,achieving excellent structure stability.Consequently,highly stable Coulombic efficiency and ultralow overpotential of 15 mV even up to 1000 h were achieved at the current density of 1 mA cm^(-2).Moreover,the resultant Li@HPCu-CuxO//LiFePO_(4) full battery delivered outstanding cycle stability and rate capability.These results offer a pathway toward high-energy-density and safe rechargeable Li metal batteries.

Black phosphorus-based field effect transistor devices for Ag ions detection

Black phosphorus （BP）, an attractive two-dimensional （2D） semiconductor, is widely used in the fields of optoelec- tronic devices, biomedicine, and chemical sensing. Silver ion （Ag＋）, a commonly used additive in food industry, can sterilize and keep food fresh. But excessive intake of Ag＋ will harm human health. Therefore, high sensitive, fast and simple Ag＋ detection method is significant. Here, a high-performance BP field effect transistor （FET） sensor is fabricated for Ag＋ detection with high sensitivity, rapid detection speed, and wide detection concentration range. The detection limit for Ag＋ is 10 l0 mol/L. Testing time for each sample by this method is 60 s. Besides, the mechanism of BP-FET sensor for Ag＋ detection is investigated systematically. The simple BP-FET sensor may inspire some relevant research and potential applications, such as providing an effective method for the actual detection of Ag＋, especially in wimessed inspections field of food.

Vapor phase growth of two-dimensional PdSe2 nanosheets for high-photoresponsivity near-infrared photodetectors

Palladium diselenide(PdSe2),a stable layered material with pentagonal structure,has attracted extensive interest due to its excellent electrical and optoelectronic performance.Here,we report a reliable process to synthesize PdSe2 via chemical vapor deposition(CVD)method.Through systematic regulation of temperature in the growth process,we can tune the thickness,size,nucleation density and morphology of PdSe2 nanosheets.Field-effect transistors based on PdSe2 nanosheets exhibit n-type behavior and present a high electron mobility of 105 cm^2·V^−1·s^−1.The electrical property of the devices after 6 months keeping in the air show little change,implying outstanding air-stability of PdSe2.In addition,PdSe2 near-infrared photodetector shows a photoresponsivity of 660 A·W^−1 under 914 nm laser.These performances are better than those of most CVD-grown 2D materials,making ultrathin PdSe2 a highly qualified candidate material for next-generation optoelectronic applications.

Narrow-bandgap materials for optoelectronics applications

Narrow-bandgap materials possess the intriguing optical-electric properties and unique structures,which can be widely applied in the field of photonics,energy optoelectronic sensing and biomedicine,etc.Nowadays,the researches on nonlinear optical properties of narrow-bandgap materials have attracted extensive attention worldwide.In this paper,we review the progress of narrow-bandgap materials from many aspects,such as background,nonlinear optical properties,energy band structure,methods of preparation,and applications.These materials have obvious nonlinear optical characteristics and the interaction with the short pulse laser excitation shows the extremely strong nonlinear absorption characteristics,which leads to the optical limiting or saturable absorption related to Pauli blocking and excited state absorption.Especially,some of these novel narrow-bandgap materials have been utilized for the generation of ultrashort pulse that covers the range from the visible to mid-infrared wavelength regions.Hence,the study on these materials paves a new way for the advancement of optoelctronics devices.

In situ formation of lithiophilic Li_(22)Sn_(5) alloy and high Li-ion conductive Li_(2)S/Li_(2)Se via metal chalcogenide SnSSe for dendrite-free Li metal anodes

Lithium metal has gained extensive attention as the most ideal candidate for next-generation battery anode owing to the ultrahigh specific capacity and the lowest electrochemical potential.However,uncontrollable dendrite growth and huge volume variation extremely restrict the future deployment of lithium metal batteries.Herein,we report metal chalcogenide SnSSe with unique nanoplate stacking structure as a robust substrate for stable Li metal anode.During the initial Li plating process,lithiophilic Li_(22)Sn_(5) alloy and Li_(2)S/Li_(2)Se sites are obtained via in-situ electrochemical reaction of Li metal and SnSSe.Density functional theory(DFT)calculation demonstrates that the formed Li_(2)S/Li_(2)Se achieves low Li diffusion energy barrier,ensuring rapid Li~+migration.Li_(22)Sn_(5) alloy provides strong nucleation sites,promoting uniform Li nucleation.Furthermore,in-situ optical microscopy analysis suggests that the synthesized effect fundamentally inhibits lithium dendrite growth.Consequently,SnSSe modified Cu foil delivered an ultralow nucleation overpotential,superior cycling stability with 450 cycles(Coulombic efficiency,>98%),and excellent plating/stripping behavior over 2200 h at 0.5 mA cm^(-2).Moreover,the brilliant reversible cycles and rate capability were also realized in Li@SnSSe//LiFePO_(4)(LFP)full cell,shedding light on the feasibility of SnSSe for stable and dendrite-free lithium metal anode.

Controlled vapor growth of 2D magnetic Cr_(2)Se_(3)and its magnetic proximity effect in heterostructures

Two-dimensional(2D)magnetic materials have aroused tremendous interest due to the 2D confinement of magnetism and potential applications in spintronic and valleytronic devices.However,most of the currently 2D magnetic materials are achieved by the exfoliation from their bulks,of which the thickness and domain size are difficult to control,limiting the practical device applications.Here,we demonstrate the realization of thickness-tunable rhombohedral Cr_(2)Se_(3)nanosheets on different substrates via the chemical vapor deposition route.The magnetic transition temperature at about 75 K is observed.Furthermore,van der Waals heterostructures consisting of Cr_(2)Se_(3)nanosheets and monolayer WS2 are constructed.We observe the magnetic proximity effect in the heterostructures,which manifests the manipulation of the valley polarization in monolayer WS2.Our work contributes to the vapor growth and applications of 2D magnetic materials.

Controlled Growth of Two-Dimensional Heterostructures:In-Plane Epitaxy or Vertical Stack

CONSPECTUS:Two-dimensional(2D)heterostructures have created many novel properties and triggered a variety of promising applications,thus setting off a boom in the modern semiconductor industry.As the first road to step into adequately exploring the properties and real applications,the material preparation process matters a lot.Adhering to the concept of epitaxial growth,chemical vapor deposition(CVD)shows great potential for the preparation of heterostructures for commercialization.

Large unsaturated magnetoresistance of 2D magnetic semiconductor Fe-SnS_(2) homojunction

A magnetic semiconductor whose electronic charge and spin can be regulated together will be an important compon-ent of future spintronic devices.Here,we construct a two-dimensional(2D)Fe doped SnS_(2)(Fe-SnS_(2))homogeneous junction and investigate its electromagnetic transport feature.The Fe-SnS_(2) homojunction device showed large positive and unsatur-ated magnetoresistance(MR)of 1800%in the parallel magnetic field and 600%in the vertical magnetic field,indicating an obvi-ous anisotropic MR feature.In contrast,The MR of Fe-SnS_(2) homojunction is much larger than the pure diamagnetic SnS_(2) and most 2D materials.The application of a gate voltage can regulate the MR effect of Fe-SnS_(2) homojunction devices.Moreover,the stability of Fe-SnS_(2) in air has great application potential.Our Fe-SnS_(2) homojunction has a significant potential in future mag-netic memory applications.

Advanced Potassium-Ion Batteries with High Areal Capacity

High areal capacity is one of the critically important points for potassium-ion batteries(PIBs)for practical applications,which relies on high areal-massloading electrodes operating at high reversible capacity.However,it is remarkably restricted by the mechanical instability and sluggish charge transfer induced by the increased mass loading.To overcome such challenge,we report the rationally designed bimetallic selenides CoSe2/SnSe2 heterostructures confined in hierarchical carbon nanofibers(CSSe@CNFs),which enables the electrodes robust mechanical stability,enhanced electron transport,and reduced ion-diffusion energy barrier for facilitating reaction kinetics.Accordingly,an impressive areal mass loading up to 25.3 mg cm^(−2)was achieved,which endowed a high areal capacity of 7.58 mAh cm^(−2)for such a free-standing electrode.This is stateof-the-art among the PIBs,exceeding that of today’s industry standard(∼3 mAh cm^(−2)for LIBs).Furthermore,it delivered long-term stability over 3700 cycles at high current density(∼2 mA cm^(−2),vs 1 mA cm^(−2)in LIBs).Moreover,the as-constructed full battery achieved a high energy density of 172.8 Wh kg-1 at 0.05 A g^(−1)with a satisfied cycle stability over 2000 cycles at 2 A g^(−1)and high reversibility with Coulombic efficiency of 100%;thus,signifying its bright future toward commercial application for advanced PIBs.

Recent Advances in Spin-coating Precursor Mediated Chemical Vapor Deposition of Two-Dimensional Transition Metal Dichalcogenides

Two-dimensional(2D)transition metal dichalcogenides(TMDs)have garnered widespread interest in the scientific community and industry for their exceptional physical and chemistry properties,and great potential for applications in diverse fields including(opto)electronics,electrocatalysis,and energy storage.Chemical vapor deposition(CVD)is one of the most compelling growth methods for the scalable growth of high-quality 2D TMDs.However,the conventional CVD process for synthesis of 2D TMDs still encounters significant challenges,primarily attributed to the high melting point of precursor powders,and achieving a uniform distribution of precursor atmosphere on the substrate to obtain controllable smaple domains is difficult.The spin-coating precursor mediated chemical vapor deposition(SCVD)strategy provides refinement over traditional methods by eliminating the use of solid precursors and ensuring a more clean and uniform distribution of the growth material on the substrate.Additionally,the SCVD process allows fine-tuning of material thickness and purity by manipulating solution composition,concentration,and the spin coating process.This Review presents a comprehensive summary of recent advances in controllable growth of 2D TMDs with a SCVD strategy.First,a series of various liquid precursors,additives,source supply methods,and substrate engineering strategies for preparing atomically thin TMDs by SCVD are introduced.Then,2D TMDs heterostructures and novel doped TMDs fabricated through the SCVD method are discussed.Finally,the current challenges and perspectives to synthesize 2D TMDs using SCVD are discussed.

Chemical vapor deposition synthesis and Raman scattering investigation of quasi-one-dimensional ZrS_(3)nanoflakes

Quasi-one-dimensional ZrS_(3)nanoflakes attract intense interest attributed to their superior electrical and optical anisotropy,stemming from the low symmetry in the crystal structure.However,the conventional chemical vapor transport method for synthesizing bulk ZrS_(3)is limited by morphology and size controllability.It is highly desirable to propose a facile way to precisely synthesize ZrS_(3)nanoflakes.In this work,the chemical vapor deposition method is proposed as a feasible way to synthesize ZrS_(3)nanoflakes.The effects of various substrates and temperatures on ZrS_(3)synthesis have been investigated.For the as-grown ZrS_(3),good crystallinity is confirmed with X-ray diffraction and transmission electron microscopy.The structure and interlayer coupling are investigated with Raman scattering spectroscopy.The strong in-plane anisotropy and interlayer coupling of the ZrS_(3)nanoflakes are illustrated with angle-resolved Raman spectroscopy and temperature-dependent Raman characterization,respectively.This study demonstrates a feasible way for the synthesis of transition metal trisulfides,which may shed new light on the research of other two-dimensional anisotropic transition metal materials.

Lithiophilic montmorillonite as a robust substrate toward high-stable lithium metal anodes

Lithium metal is considered a desirable anode for the nextgeneration high-energy-density rechargeable energy storage devices.Unfortunately,poor lifespan and safety issues caused by unexpected dendrites growth have prevented the commercialization of Li metal anode.

van der Waals epitaxial growth of ultrathin metallic NiSe nanosheets on WSe2 as high performance contacts for WSe2 transistors

A prerequisite for widespread applications of atomically thin transition metal dichalcogenides in future electronics is to achieve reliable electrical contacts,which is of considerable challenge due to the difficulties in selectively doping and inevitable physical damages of these atomically thin materials during typical metal integration process.Here,we report the in situ growth of ultrathin metallic NiSe single crystals on WSe2 in which the metallic NiSe nanosheets function as the contact electrodes to WSe2,creating an interface that is essentially free from chemical disorder.The NiSe/WSe2 heterostructures also exhibit well-aligned lattice orientation between the two layers,forming a periodic Moire pattern.Electrical transport studies demonstrate that the NiSe nanosheets exhibit an excellent metallic feature,as evidenced by the extra-high electrical conductivity of up to 1.6×10^6 S-nf1.The WSe2 transistors with the NiSe contact show field-effect mobilities (/vFe) more than double that with Cr/Au electrodes.This study demonstrates an effective pathway to achieve reliable electrical contacts to the atomically thin 2D materials,and maybe readily extended for fabricating 2D/2D low-resistance contacts for a variety of transition metal dichalcogenides.

Controllable synthesis of NiS and NiS2 nanoplates by chemical vapor deposition

Mulitipe stoichiometric ratio of two-dimensional(2D)transition metal dichalcogenides(TMDCs)attracted considerable interest for their unique chemical and physical properties.Here we developed a chemical vapor deposition(CVD)method to controllably synthesize ultrathin NiS and NiS2 nanoplates.By tuning the growth temperature and the amounts of the sulfur powder,2D nonlayered NiS and NiS2 nanoplates can be selectively prepared with the thickness of 2.0 and 7.0 nm,respectively.X-ray diffraction(XRD)and transmission electron microscopy(TEM)characterization reveal that the 2D NiS and N1S2 nanoplates are high-quality single crystals in the hexagonal and cubic phase,respectively.Electrical transport studies show that electrical conductivities of the 2D NiS and N1S2 nanoplates are as high as 4.6 x 10^5 and 6.3 x 10^5 S·m^-1,respectively.The electrical results demonstrate that the synthesized metallic NiS and NiS2 could serve as good electrodes in 2D electronics.

Trimetallic oxyhydroxides as active sites for large-current-density alkaline oxygen evolution and overall water splitting

Earth-abundant electrocatalysts for large-current-density water splitting under alkaline condition are desirable.Oxygen evolution reaction,which is a bottleneck of the overall water splitting,faces the problems of complicated reconstruction and deficiency in rational design of active sites.Herein,we report a series of transition metal chalcogenides for alkaline OER.Among them,FeCoNi(S)displayed a low overpotential of 293 m V to deliver a current density of 500 m A cm^(-2),which is in the top level of non-precious metal based OER electrocatalysts.A combination of(ex)in situ characterizations and DFT calculation shows that Ni(Fe,Co)trimetallic oxyhydroxides were the active sites for highly-efficient OER.Furthermore,for FeCoNi(S),when used as a bifunctional catalyst for water splitting,it only required a cell voltage of 1.84 V to deliver~500 m A cm^(-2) with extraordinary long-term stability over 2000 h.This work provides the comprehension of high-efficiency,robust catalysts for OER and overall water splitting at large current densities in alkaline media.

Direct van der Waals epitaxial growth of 1D/2D Sb2Se3/WS2 mixed-dimensional p-n heterojunctions

The mixed-dimensional integration of two-dimensional (2D) materials with non-2D materials can give rise to prominent advances in performance or function.To date,the mixed-dimensional one-dimensional (1D)/2D heterostructures have been fabricated using various physical assembly approaches.However,direct epitaxial growth method which has notable advantages in preparing large-scale products and obtaining perfect interfaces is rarely investigated.Herein,we demonstrate for the first time the direct synthesis of the 1D/2D mixed-dimensional heterostructures by sequential vapor-phase growth of Sb2Se3 nanowires on WS2 monolayers.X-ray diffraction (XRD) pattern and Raman spectrum confirm the composition of the Sb2Se3/NS2 heterostructures.Transmission electron microscope (TEM) measurement demonstrates high quality of the heterostructures.Electrical transport characterization reveals that Sb2Se3 nanowire exhibits p-type characteristic and that WS2 monolayer exhibits n-type behavior,and that the p-n diode from 1D/2D mixed-dimensional Sb2Se3/WS2 heterostructure possesses obvious current rectification behavior.Optoelectronic measurements of the heterostructures show apparent photovoltaic response with an open-circuit voltage of 0.19 V,photoresponsivity of 1.51 A/W (Vds =5 V) and fast response time of less than 8 ms.The van der Waals epitaxial growth mode of Sb2Se3 nanowires on WS2 monolayers is verified by stripping the Sb2Se3 nanowire from the heterostructures using tape.Together,the direct van der Waals epitaxy opens a facile pathway to 1D/2D mixed-dimensional heterostructures for functional electronic and optoelectronic devices.

Bimetallic chalcogenides for electrocatalytic CO_(2)reduction

Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)converts CO_(2)into valuable chemical fuels,which can effectively alleviate global warming and energy crisis.However,limited by its slow reaction rate and low product selectivity,it is urgent to design efficient,cheap,safe,and highly selective CO_(2)RR electrocatalysts.Owing to the advantages of adjustable electronic structure,abundant active sites,low cost,environmental friendliness and excellent electrochemical performance,bimetallic chalcogenides have aroused great interest.Here,we briefly summarized different bimetallic oxides and sulfides for electrocatalytic CO_(2)RR in the past five years.In addition,different hybridizations formed between metal atoms,including intermetallic compounds,heterostructures and metal doping,were generalized.Their positive effects on CO_(2)RR catalytic selectivity and activity were deeply uncovered.Besides,we also put forward some views about the future research directions and perspectives in CO_(2)RR field.This review aims to provide a reference for the rational design of bimetallic chalcogenides towards electrocatalytic CO_(2)reduction.