Lewis acid-doped transition metal dichalcogenides for ultraviolet–visible photodetectors

Ultraviolet photodetectors(UV PDs)are widely used in civilian,scientific,and military fields due to their high sensitivity and low false alarm rates.We present a temperature-dependent Lewis acid p-type doping method for transition metal dichalcogenides(TMDs),which can effectively be used to extend the optical response range.The p-type doping based on surface charge transfer involves the chemical adsorption of the Lewis acid SnCl_(4)as a light absorption layer on the surface of WS_(2),significantly enhancing its UV photodetection performance.Under 365 nm laser irradiation,WS_(2)PDs exhibit response speed of 24 ms/20 ms,responsivity of 660 mA/W,detectivity of 3.3×10^(11)Jones,and external quantum efficiency of 226%.Moreover,we successfully apply this doping method to other TMDs materials(such as MoS_(2),MoSe_(2),and WSe_(2))and fabricate WS_(2) lateral p–n heterojunction PDs.

Defect-engineered two-dimensional transition metal dichalcogenides towards electrocatalytic hydrogen evolution reaction

Recently,two-dimensional transition metal dichalcogenides(TMDs)demonstrated their great potential as cost-effective catalysts in hydrogen evolution reaction.Herein,we systematically summarize the existing defect engineering strategies,including intrinsic defects(atomic vacancy and active edges)and extrinsic defects(metal doping,nonmetal doping,and hybrid doping),which have been utilized to obtain advanced TMD-based electrocatalysts.Based on theoretical simulations and experimental results,the electronic structure,intermediate adsorption/desorption energies and possible catalytic mechanisms are thoroughly discussed.Particular emphasis is given to the intrinsic relationship between various types of defects and electrocatalytic properties.Furthermore,current opportunities and challenges for mechanical investigations and applications of defective TMD-based catalysts are presented.The aim herein is to reveal the respective properties of various defective TMD catalysts and provide valuable insights for fabricating high-efficiency TMD-based electrocatalysts.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Current advances of transition metal dichalcogenides in electromagnetic wave absorption:A brief review

Transition metal dichalcogenides(TMDs)show great advantages in electromagnetic wave(EMW)absorption due to their unique structure and electrical properties.Tremendous research works on TMD-based EMW absorbers have been conducted in the last three years,and the comprehensive and systematical summary is still a rarity.Therefore,it is of great significance to elaborate on the interaction among the morphologies,structures,phases,components,and EMW absorption performances of TMD-based absorbers.This review is devoted to analyzing TMD-based absorbers from the following perspectives:the EMW absorption regulation strategies of TMDs and the latest progress of TMD-based hybrids as EMW absorbers.The absorption mechanisms and component-performance dependency of these achievements are also summarized.Finally,a straightforward insight into industrial revolution upgrading in this promising field is proposed.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

MoiréDirac fermions in transition metal dichalcogenides heterobilayers

Monolayer group-VIB transition metal dichalcogenides(TMDs)feature low-energy massive Dirac fermions,which have valley contrasting Berry curvature.This nontrivial local band topology gives rise to valley Hall transport and optical selection rules for interband transitions that open up new possibilities for valleytronics.However,the large bandgap in TMDs results in relatively small Berry curvature,leading to weak valley contrasting physics in practical experiments.Here,we show that Dirac fermions with tunable large Berry curvature can be engineered in moirésuperlattice of TMD heterobilayers.These moiréDirac fermions are created in a magnified honeycomb lattice with its sublattice degree of freedom formed by two local moirépotential minima.We show that applying an on-site potential can tune the moiréflat bands into helical ones.In short-period moirésuperlattice,we find that the two moirévalleys become asymmetric,which results in a net spin Hall current.More interestingly,a circularly polarized light drives these moiréDirac fermions into quantum anomalous Hall phase with chiral edge states.Our results open a new possibility to design the moiré-scale spin and valley physics using TMD moiréstructures.

Hydrogenic donor impurity states and intersubband optical absorption spectra of monolayer transition metal dichalcogenides in dielectric environments

The hydrogenic donor impurity states and intersubband optical absorption spectra in monolayer transition metal dichalcogenides(ML TMDs) under dielectric environments are theoretically investigated based on a two-dimensional(2D)nonorthogonal associated Laguerre basis set. The 2D quantum confinement effect together with the strongly reduced dielectric screening results in the strong attractive Coulomb potential between electron and donor ion, with exceptionally large impurity binding energy and huge intersubband oscillator strength. These lead to the strong interaction of the electron with light in a 2D regime. The intersubband optical absorption spectra exhibit strong absorption lines of the non-hydrogenic Rydberg series in the mid-infrared range of light. The strength of the Coulomb potential can be controlled by changing the dielectric environment. The electron affinity difference leads to charge transfer between ML TMD and the dielectric environment, generating the polarization-electric field in ML TMD accompanied by weakening the Coulomb interaction strength. The larger the dielectric constant of the dielectric environment, the more the charge transfer is, accompanied by the larger polarization-electric field and the stronger dielectric screening. The dielectric environment is shown to provide an efficient tool to tune the wavelength and output of the mid-infrared intersubband devices based on ML TMDs.

Growing Biomorphic Transition Metal Dichalcogenides and Their Alloys Toward High Permeable Membranes and Efficient Electrocatalysts Applications

3D architecratured transition metal dichalcogenides constructed by atomically thin layers are appealing building blocks in various applications,such as catalysts,energy storage,conversions,sensors,and so on.However,the direct growth of 3D transition metal dichalcogenides architectures with high crystal quality and well-controlled size/thickness remains a huge challenge.Herein,we report a facile,highly-repeatable,and versatile chemical vapor deposition strategy,for the mass production of high-quality 3D-architecratured transition metal dichalcogenides(e.g.,MoS_(2),WS_(2),and ReS_(2))and their alloys(e.g.,W_(x)Mo(1–x)S_(2)and Rex Mo_((1–x))S_(2))nanosheets on naturally abundant and low-cost diatomite templates.Particularly,the purified transition metal dichalcogenides products exhibit unique and designable 3D biomorphic hierarchical microstructures,controllable layer thicknesses,tailorable chemical compositions,and good crystallinities.The weak interlayer interactions endow them with good dispersity in solutions to form stable additive-free inks for solution-processing-based applications,for example,high-permeable and high-stable separation membranes for water purification,and efficient electrocatalysts for hydrogen evolution reactions.This work paves ways for the low-cost,mass production of versatile transition metal dichalcogenides powder-like materials with designable structures and properties,toward energy/environmental-related applications and beyond.

Electronic structures and elastic properties of monolayer and bilayer transition metal dichalcogenides MX_2(M= Mo,W;X= O,S,Se,Te):A comparative first-principles study

First-principle calculations with different exchange-correlation functionals, including LDA, PBE, and vd W-DF functional in the form of opt B88-vd W, have been performed to investigate the electronic and elastic properties of twodimensional transition metal dichalcogenides（TMDCs） with the formula of MX2（M = Mo, W; X = O, S, Se, Te） in both monolayer and bilayer structures. The calculated band structures show a direct band gap for monolayer TMDCs at the K point except for MoO2 and WO2. When the monolayers are stacked into a bilayer, the reduced indirect band gaps are found except for bilayer WTe2, in which the direct gap is still present at the K point. The calculated in-plane Young moduli are comparable to that of graphene, which promises possible application of TMDCs in future flexible and stretchable electronic devices. We also evaluated the performance of different functionals including LDA, PBE, and opt B88-vd W in describing elastic moduli of TMDCs and found that LDA seems to be the most qualified method. Moreover, our calculations suggest that the Young moduli for bilayers are insensitive to stacking orders and the mechanical coupling between monolayers seems to be negligible.

Photodetectors based on junctions of two-dimensional transition metal dichalcogenides

Transition metal dichalcogenides （TMDCs） have gained considerable attention because of their novel properties and great potential applications. The flakes of TMDCs not only have great light absorption from visible to near infrared, but also can be stacked together regardless of lattice mismatch like other two-dimensional （2D） materials. Along with the studies on intrinsic properties of TMDCs, the junctions based on TMDCs become more and more important in applications of photodetection. The junctions have shown many exciting possibilities to fully combine the advantages of TMDCs, other 2D materials, conventional and organic semiconductors together. Early studies have greatly enriched the application of TMDCs in photodetection. In this review, we investigate the efforts in photodetectors based on the junctions of TMDCs and analyze the properties of those photodetectors. Homojunctions based on TMDCs can be made by surface chemical doping, elemental doping and electrostatic gating. Heterojunction formed between TMDCs/2D materials, TMDCs/conventional semiconductors and TMDCs/organic semiconductor also deserve more attentions. We also compare the advantages and disadvantages of different junctions, and then give the prospects for the development of junctions based on TMDCs.

Catalyst activation: Surface doping effects of group Ⅵ transition metal dichalcogenides towards hydrogen evolution reaction in acidic media

Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.

Pressure-induced phase transition and electronic structure evolution in layered semimetal HfTe_(2)

Motivated by the recent experimental work,the pressure-induced structural transition of well-known two-dimensional(2D)1T-Hf Te_(2)was investigated up to 50 GPa through the advanced CALYPSO structure search technique combined with the first-principles calculations.Our calculations suggested that the 1T-Hf Te_(2)will first transform to C2/m phase at 3.6 GPa with a volume reduction of 7.6%and then to P62m phase at 9.6 GPa with a volume collapse of 4.6%.The occurrences of 3D C2/m and P62m phases mainly originated from the enhanced Te-Te interlayer coupling and the drastic distortions of Hf-Te polyhedrons in P3m1 phase under compression.Concomitantly,the coordination number of Hf atoms increased from six in P3m1 to eight in C2/m and eventually to nine in P62m at elevated pressure.The metallic and semimetallic nature of C2/m and P62m phases were characterized,and the evidence of the reinforced covalent interactions of Te-Hf and Te-Te orbitals in these two novel high-pressure phases were manifested by the atom-projected electronic DOS and Bader charge.

Rubidium-induced phase transitions among metallic,band-insulating,Mott-insulating phases in 1T-TaS_(2)

Realizing phase transitions via non-thermal sample manipulations is important not only for applications,but also for uncovering the underlying physics.Here,we report on the discovery of two distinct metal–insulator transitions in 1T-TaS_(2) via angle-resolved photoemission spectroscopy and in-situ rubidium deposition.At 205 K,the rubidium deposition drives a normal metal–insulator transition via filling electrons into the conduction band.While at 225 K,however,the rubidium deposition drives a bandwidth-controlled Mott transition as characterized by a rapid collapsing of Mott gap and a loss of spectral weight of the lower Hubbard band.Our result,from a doping-controlled perspective,succeeds in distinguishing the metallic,band-insulating,and Mott-insulating phases of 1T-TaS_(2),manifesting a delicate balance among the electronitineracy,interlayer-coupling and Coulomb repulsion.We also establish an effective method to tune the balance between these interactions,which is useful in seeking exotic electronic phases and designing functional phase-changing devices.

Valley polarization in transition metal dichalcogenide layered semiconductors:Generation,relaxation,manipulation and transport

In recent years,valleytronics researches based on 2D semiconducting transition metal dichalcogenides have attracted considerable attention.On the one hand,strong spin–orbit interaction allows the presence of spin–valley coupling in this system,which provides spin addressable valley degrees of freedom for information storage and processing.On the other hand,large exciton binding energy up to hundreds of me V enables excitons to be stable carriers of valley information.Valley polarization,marked by an imbalanced exciton population in two inequivalent valleys(+K and-K),is the core of valleytronics as it can be utilized to store binary information.Motivated by the potential applications,we present a thorough overview of the recent advancements in the generation,relaxation,manipulation,and transport of the valley polarization in nonmagnetic transition metal dichalcogenide layered semiconductors.We also discuss the development of valleytronic devices and future challenges in this field.

Flat band in hole-doped transition metal dichalcogenide observed by angle-resolved photoemission spectroscopy

Layered transition metal dichalcogenides(TMDCs)gained widespread attention because of their electron-correlationrelated physics,such as charge density wave(CDW),superconductivity,etc.In this paper,we report the high-resolution angle-resolved photoemission spectroscopy(ARPES)studies on the electronic structure of Ti-doped 1T-Ti_(x)Ta_(1-x)S_(2) with different doping levels.We observe a flat band that originates from the formation of the star of David super-cell at the x=5%sample at the low temperature.With the increasing Ti doping levels,the flat band vanishes in the x=8%sample due to the extra hole carrier.We also find the band shift and variation of the CDW gap caused by the Ti-doping.Meanwhile,the band folding positions and the CDW vector g_(CDW)intact.Our ARPES results suggest that the localized flat band and the correlation effect in the 1T-TMDCs could be tuned by changing the filling factor through the doping electron or hole carriers.The Ti-doped 1T-Ti_(x)Ta_(1-x)S_(2) provides a platform to fine-tune the electronic structure evolution and a new insight into the strongly correlated physics in the TMDC materials.

Electronic structure of transition metal dichalcogenides PdTe_2 and Cu_(0.05)PdTe_2 superconductors obtained by angle-resolved photoemission spectroscopy

The layered transition metal chalcogenides have been a fertile land in solid state physics for many decades. Various MX2-type transition metal dichalcogenides, such as WTe2, IrTe2, and MoS2, have triggered great attention recently, either for the discovery of novel phenomena or some extreme or exotic physical properties, or for their potential applications. PdTe2 is a superconductor in the class of transition metal dichalcogenides, and superconductivity is enhanced in its Cu- intercalated form, Cuo.05PdTe2. It is important to study the electronic structures of PdTe2 and its intercalated form in order to explore for new phenomena and physical properties and understand the related superconductivity enhancement mecha- nism. Here we report systematic high resolution angle-resolved photoemission （ARPES） studies on PdTe2 and Cuo.05PdTe2 single crystals, combined with the band structure calculations. We present in detail for the first time the complex multi-band Fermi surface topology and densely-arranged band structure of these compounds. By carefully examining the electronic structures of the two systems, we find that Cu-intercalation in PdTe2 results in electron-doping, which causes the band structure to shift downwards by nearly 16 meV in Cuo.05PdTe2. Our results lay a foundation for further exploration and investigation on PdTe2 and related superconductors.

Dual bound states in the continuum enhanced second harmonic generation with transition metal dichalcogenides monolayer

The emergence of two dimensional(2D)materials has opened new possibilities for exhibiting second harmonic genera-tion(SHG)at the nanoscale,due to their remarkable optical response related to stable excitons at room temperature.However,the ultimate atomic-scale interaction length with light makes the SHG of Transition Metal Dichalcogenides(TM-Ds)monolayers naturally weak.Here,we propose coupling a monolayer of TMDs with a photonic grating slab that works with doubly resonant bound states in the continuum(BIC).The BIC slabs are designed to exhibit a pair of BICs,reson-ant with both the fundamental wave(FW)and the second harmonic wave(SHW).Firstly,the spatial mode matching can be fulfilled by tilting FW's incident angle.We theoretically demonstrate that this strategy leads to more than four orders of magnitude enhancement of SHG efficiency than a sole monolayer of TMDs,under a pump light intensity of 0.1 GW/cm^(2).Moreover,we demonstrate that patterning the TMDs monolayer can further enhance the spatial overlap coefficient,which leads to an extra three orders of magnitude enhancement of SHG efficiency.These results demonstrate remarkable pos-sibilities for enhancing SHG with nonlinear 2D materials,opening many opportunities for chip-based light sources,nano-lasers,imaging,and biochemical sensing.

Two-dimensional transition metal dichalcogenides for lead halide perovskites-based photodetectors: band alignment investigation for the case of CsPbBr3/MoSe2

The distinguished electronic and optical properties of lead halide perovskites(LHPs)make them good candidates for active layer in optoelectronic devices.Integrating LHPs and two-dimensional(2 D)transition metal dichalcogenides(TMDs)provides opportunities for achieving increased performance in heterostructured LHPs/TMDs based optoelectronic devices.The electronic structures of LHPs/TMDs heterostructures,such as the band offsets and interfacial interaction,are of fundamental and technological interest.Here CsPbBr3 and MoSe2 are taken as prototypes of LHPs and 2 D TMDs to investigate the band alignment and interfacial coupling between them.Our GGA-PBE and HSE06 calculations reveal an intrinsic type-II band alignment between CsPbBr3 and MoSe2.This type-II band alignment suggests that the performance of CsPbBr3-based photodetectors can be improved by incorporating MoSe2 monolayer.Furthermore,the absence of deep defect states at CsPbBr3/MoSe2 interfaces is also beneficial to the better performance of photodetectors based on CsPbBr3/MoSe2 heterostructure.This work not only offers insights into the improved performance of photodetectors based on LHPs/TMDs heterostructures but it also provides guidelines for designing high-efficiency optoelectronic devices based on LHPs/TMDs heterostructures.

In situ TEM revealing the effects of dislocations on lithium-ion migration in transition metal dichalcogenides

The two-dimensional (2D) structure of layered transition metal dichalcogenides (TMDs) provides unusual physical properties [1,2]and chemical reactivity [3,4], which can be influenced by defects such as dislocations [5,6]. For example, dislocations can act as nucleation sites for the onset of deformation when subjected to stress [7].

Transition Metal Dichalcogenides(WS2 and MoS2)Saturable Absorbers for Mode-Locked Erbium-Doped Fiber Lasers

We demonstrate an ultrafast fiber laser based on transition metal dichalcogenide materials which are tungsten disulfide (WS2) and molybdenum disulfide (MoS2) as saturable absorber (SA). These materials are fabricated via a simple drop-casting method. By employing WS2, we obtain a stable harmonic mode-locking at the threshold pump power of 184 mW, and the generated soliton pulse has 3.48 MHz of repetition rate. At the maximum pump power of 250 mW, we also obtain a small value of pulse duration, 2.43 ps with signal-to-noise ratio (SNR) of 57 dB. For MoS2 SA, the pulse is generated at 105 mW pump power with repetition rate of 1.16 MHz. However, the pulse duration cannot be detected by the autocorrelator device as the pulse duration recorded is 468 ns, with the SNR value of 35 dB.