Search

Transition metal dichalcogenide (TMD) monolayers, such as MoS2, possess a direct optical bandgap and are useful for emerging ultrathin optoelectronics in the visible light range, whereas their thickness limits light absorption and emission properties. To address this drawback, one promising approach is to hybridize plasmonic nanostructures with monolayer TMDs to utilize local field enhancement effects owing to localized surface plasmon resonance (LSPR). Herein, we propose a strong enhancement of the local light–matter interaction in MoS2 monolayers on naturally generated nanoscale grooves. The nanogrooves are formed at grain boundaries (GBs) of template-stripped metal film substrates that are fabricated by mechanically stripping Ag films deposited on an ultra-flat Si substrate, wherein the nanogroove densities are systematically modulated by the Ag film thickness. We observe an effective photoluminescence enhancement factor of 758 and a Raman spectroscopy intensity enhancement of approximately 5 times in MoS2 on the subwavelength-scale nanogrooves, compared with that on grain planes, which is attributed to a strong local field enhancement of the LSPR effect. Moreover, this plasmonic enhancement effect is elucidated by dark-field scattering spectroscopy and optical simulations. Our results can facilitate the utilization of density-controllable plasmonic nanogrooves synthesized without nanopatterning techniques for plasmonic hybrids on 2D semiconductors.

Atomically thin monolayer transition-metal dochalcogenides (1L-TMDs) are optically active direct band gap semiconducting materials with interesting properties; they are appropriate platform to study and investigate the modulated optoelectronic properties due to locally induced charge transfer phenomenon using various approaches. Herein, 1L-TMDs (MoS2, WS2 and WSe2) grown using chemical vapor deposition (CVD) were transferred above 10-nm-thick patterned platinum (Pt) stripes deposited on SiO2/Si substrate to fabricate a local vertical heterostructure of 1L-TMDs with Pt. The optical characterization showed that the PL intensities of n (p)-type 1L-TMDs, namely MoS2 and WS2 (WSe2), deposited above Pt were reduced with peak positions blue (red)-shifted by 40 (16) meV compared to the samples on SiO2/Si substrates. This was attributed to the transfer of electrons from the 1L-TMDs to the Pt due to a charge transfer process at the interface. At the same time, an enhanced photocurrent, in comparison to 1L-MoS2 alone was observed under a negative gate voltage of − 40 V from the homojunctions of 1L-MoS2 and 1L-MoS2/Pt formed within the same grain structure due to a Pt-induced local p-doping effect. The charge modulation of the opto-electrical properties of 1L-TMDs due to charge transfer caused using patterned metal provides a simple lateral homojunction for enhanced photovoltaic applications.

The extreme elastic strain of monolayer transition metal dichalcogenides provides an ideal platform to achieve efficient exciton funneling via local strain modulation; however, studies conducted thus far have focused on the use of substrates with fixed strain profiles. We prepared 1L-WS2 on a flexible substrate such that the formation of topographic wrinkles could be switched on or off, and the depth or the direction of the wrinkle could be modified by external strain, thereby providing full control of the periodic undulation of the band gap profile of 1L-WS2 in the range 0-57 meV. Nanoscale photoluminescence (PL) imaging unambiguously evinced that the photoexcited excitons of 1L-WS2 were accumulated at the top regions of the wrinkles with less band gap than the valley region. Our results of broad tunability of the two-dimensional (2D) exciton funneling suggest a promising route to control exciton drift for enhanced optoelectronic performances and future 2D exciton devices.

Domain morphology plays a pivotal role not only for the synthesis of high-quality 2D transition metal dichalcogenides (TMDs) but also for the further unveiling of related physical and chemical properties, yet little has been divulged to date, especially for metallic TMDs. In addition, solid precursor as a transition metal source has been conventionally introduced for the synthesis of TMDs, which leads to an inhomogeneous distribution of local domains with the substrate position, making it difficult to obtain a reliable film. Here, we tailor the domain morphologies of metallic NbSe2 and NbSe2/WSe2 heterostructures using liquid-precursor chemical vapor deposition (CVD). We find that triangular, hexagonal, tripod-like, and herringbone-like NbSe2 flakes are constructed through control of growth temperature and promoter and precursor concentration. Liquid-precursor CVD ensures domain morphologies that are highly reproducible over repeated growth and uniform along the gas-flow direction. A domain coverage of ∼80% is achieved at a high precursor concentration, starting with tripod-like NbSe2 domain and evolving to the herringbone fractal. Furthermore, mixing liquid W and Nb precursors results in sea-urchin-like heterostructure domains with long-branch-shaped NbSe2 at low temperature, whereas protruded hexagonal heterostructure domains grow at high temperature. Our liquid precursor approach provides a shortcut for tailoring the domain morphologies of metallic TMDs as well as metal/semiconductor heterostructures.

The contact properties of van der Waals layered semiconducting materials are not adequately understood, particularly for edge contact. Edge contact is extremely helpful in the case of graphene, for...

Transition metal dichalcogenides (TMDCs) are promising two-dimensional (2D) materials for realizing next-generation electronics and optoelectronics with attractive physical properties. However, mon...

International audience; Monolayers of transition metal dichalcogenides are semiconducting materials which offer many prospects in optoelectronics. A monolayer of molybdenum disulfide (MoS2) has a direct bandgap of 1.88 eV. Hence, when excited with optical photon energies below its bandgap, no photocarriers are generated and a monolayer of MoS2 is not ofmuch use in either photovoltaics or photodetection.Here, we demonstrate that large size MoS2 monolayer sandwiched between two graphene layers makes this heterostructure optically active well below the band gap of MoS2. An ultrafast optical pump-THz probe experiment reveals in real-time, transfer of carriers between graphene and MoS2 monolayer upon photoexcitation with photon energies down to 0.5 eV. It also helps to unravel an unprecedented enhancement in the broadband transient THz response of this tri-layer material system. We propose possible mechanism which can account for this phenomenon. Such specially designed heterostructures, which can be easily built around different transition metal dichalcogenide monolayers, will considerably broaden the scope for modern optoelectronic applications at THz bandwidth.

Atomic dopants and defects play a crucial role in creating new functionalities in 2D transition metal dichalcogenides (2D TMDs). Therefore, atomic‐scale identification and their quantification warrant precise engineering that widens their application to many fields, ranging from development of optoelectronic devices to magnetic semiconductors. Scanning transmission electron microscopy with a sub‐Å probe has provided a facile way to observe local dopants and defects in 2D TMDs. However, manual data analytics of experimental images is a time‐consuming task, and often requires subjective decisions to interpret observed signals. Therefore, an approach is required to automate the detection and classification of dopants and defects. In this study, based on a deep learning algorithm, fully convolutional neural network that shows a superior ability of image segmentation, an efficient and automated method for reliable quantification of dopants and defects in TMDs is proposed with single‐atom precision. The approach demonstrates that atomic dopants and defects are precisely mapped with a detection limit of ≈1 × 1012 cm−2, and with a measurement accuracy of ≈98% for most atomic sites. Furthermore, this methodology is applicable to large volume of image data to extract atomic site‐specific information, thus providing insights into the formation mechanisms of various defects under stimuli., The deep learning‐assisted quantification algorithm reduces heavy load of data processing for researchers, which has hindered the pace of design and development of 2D transition metal dichalcogenides (2D TMDs). Furthermore, an integrated understanding of the atomic‐scale behavior of point defects in 2D TMDs under environmental stimuli is now available without data reduction or sampling.

One primary concern in diluted magnetic semiconductors (DMSs) is how to establish a long-range magnetic order with a low magnetic doping concentration to maintain the gate tunability of the host semiconductor, as well as to increase Curie temperature. Two-dimensional van der Waals semiconductors have been recently investigated to demonstrate the magnetic order in DMSs; however, a comprehensive understanding of the mechanism responsible for the gate-tunable long-range magnetic order in DMSs has not been achieved yet. Here, we introduce a monolayer tungsten diselenide (WSe2) semiconductor with V dopants to demonstrate the long-range magnetic order through itinerant spin-polarized holes. The V atoms are sparsely located in the host lattice by substituting W atoms, which is confirmed by scanning tunneling microscopy and high-resolution transmission electron microscopy. The V impurity states and the valence band edge states are overlapped, which is congruent with density functional theory calculations. The field-effect transistor characteristics reveal the itinerant holes within the hybridized band; this clearly resembles the Zener model. Our study gives an insight into the mechanism of the long-range magnetic order in V-doped WSe2, which can also be used for other magnetically doped semiconducting transition metal dichalcogenides., 19 pages, 4 figures

The THz conductivity of MoS 2 , MoSe 2 monolayers and their heterostructure is compared and reported here. We also measured the hot carrier relaxation upon optical excitation in these samples below and above the bandgap of the monolayers. While in the heterostructure the recovery kinetics of the carriers resembles that of monolayers, the conductivity change is enhanced by one order of magnitude. A simple model accounts for this phenomenon.

The steady state AC terahertz (THz) conductivity and photo-induced carrier dynamics in a single layer of MoS 2 sandwiched in between graphene layers have been studied using sub-200 fs THz pulses. The THz conductivity of the heterostructure resembles that of the graphene. When excited with photon energy of ~1.55 eV, it is shown that about 70% of energetic carriers generated in graphene are rapidly and efficiently transferred back and forth from graphene towards MoS 2 . A mechanism accounting for this phenomenon is proposed.

Diluted magnetic semiconductors including Mn‐doped GaAs are attractive for gate‐controlled spintronics but Curie transition at room temperature with long‐range ferromagnetic order is still debatable to date. Here, the room‐temperature ferromagnetic domains with long‐range order in semiconducting V‐doped WSe2 monolayer synthesized by chemical vapor deposition are reported. Ferromagnetic order is manifested using magnetic force microscopy up to 360 K, while retaining high on/off current ratio of ≈105 at 0.1% V‐doping concentration. The V‐substitution to W sites keeps a V–V separation distance of 5 nm without V–V aggregation, scrutinized by high‐resolution scanning transmission electron microscopy. More importantly, the ferromagnetic order is clearly modulated by applying a back‐gate bias. The findings open new opportunities for using 2D transition metal dichalcogenides for future spintronics.

By understanding how the environmental composition impacts the optoelectronic properties of transition metal dichalcogenide monolayers, we demonstrate that simple photoluminescence (PL) measurements of tungsten disulfide (WS2) monolayers can differentiate relative humidity environments. In this paper, we examine the PL and photoconductivity of chemical vapor deposition grown WS2 monolayers under three carefully controlled environments: inert gas (N2), dry air (O2 in N2), and humid nitrogen (H2O vapor in N2). The WS2 PL is measured as a function of 532 nm laser power and exposure time and can be decomposed into the exciton, trion, and lower energy state(s) contributions. Under continuous illumination in either O2 or H2O vapor environment, we find dramatic (and reversible) increases in PL intensity relative to the PL in an inert environment. The PL bathochromically shifts in an O2 environment and is dominated by increased trion emission and diminished exciton emission. In contrast, the WS2 PL increase in a H2O environment results from an overall increase in emission from all spectral components where the exciton contribution dominates. The drastic increases in PL are anticorrelated with corresponding decreases in photoconductivity, as measured by time-resolved microwave conductivity. The results suggest that both O2 and H2O react photochemically with the WS2 monolayer surface, modifying the optoelectronic properties, but do so via distinct pathways. Thus, we use these optoelectronic differences to differentiate the amount of humidity in the air, which we show with 0%, 40%, and 80% relative humidity environments. This deeper understanding of how ambient conditions impact WS2 monolayers enables novel humidity sensors as well as a better understanding of the correlation between TMDC surface chemistry, light emission, and photoconductivity. Moreover, these WS2 measurements highlight the importance of considering the impact of the local environment on reported results.

Two-dimensional (2D) van der Waals (vdW) heterostructures exhibit novel physical and chemical properties, allowing the development of unprecedented electronic, optical, and electrochemical devices. However, the construction of wafer-scale vdW heterostructures for practical applications is still limited due to the lack of well-established growth and transfer techniques. Herein, we report a method for the fabrication of wafer-scale 2D vdW heterostructures with an ultraclean interface between layers via the aid of a freestanding viscoelastic polymer support layer (VEPSL). The low glass transition temperature ( Tg) and viscoelastic nature of the VEPSL ensure absolute conformal contact between 2D layers, enabling the easy pick-up of layers and attaching to other 2D layers. This eventually leads to the construction of random sequence 2D vdW heterostructures such as molybdenum disulfide/tungsten disulfide/molybdenum diselenide/tungsten diselenide/hexagonal boron nitride. Furthermore, the VEPSL allows the conformal transfer of 2D vdW heterostructures onto arbitrary substrates, irrespective of surface roughness. To demonstrate the significance of the ultraclean interface, the fabricated molybdenum disulfide/graphene heterostructure employed as an electrocatalyst yielded excellent results of 73.1 mV·dec-1 for the Tafel slope and 0.12 kΩ of charge transfer resistance, which are almost twice as low as that of the impurity-trapped heterostructure.

Monolayer tungsten disulfide (WS2) has emerged as an active material for optoelectronic devices due to its quantum yield of photoluminescence. Despite the enormous research about physical characteristics of monolayer WS2, the defect-related Raman scattering has been rarely studied. Here, we report the correlation of topography and Raman scattering in monolayer WS2 by using tip-enhanced resonance Raman spectroscopy and reveal defect-related Raman modes denoted as D and D′ modes. We found that the sulfur vacancies introduce not only the red-shifted A1g mode but also the D and D′ modes by the density functional theory calculations. The observed defect-related Raman modes can be utilized to evaluate the quality of monolayer WS2 and will be helpful to improve the performance of WS2 optoelectronic devices.

Chemical treatment using bis(trifluoromethane) sulfonimide (TFSI) was shown to be particularly effective for increasing the photoluminescence (PL) of monolayer (1L) MoS2, suggesting a convenient method for overcoming the intrinsically low quantum yield of this material. However, the underlying atomic mechanism of the PL enhancement has remained elusive. Here, we report the microscopic origin of the defect healing observed in TFSI-treated 1L-MoS2 through a correlative combination of optical characterization and atomic-scale scanning transmission electron microscopy, which showed that most of the sulfur vacancies were directly repaired by the extrinsic sulfur atoms produced from the dissociation of TFSI, concurrently resulting in a significant PL enhancement. Density functional theory calculations confirmed that the reactive sulfur dioxide molecules that dissociated from TFSI can be reduced to sulfur and oxygen gas at the vacancy site to form strongly bound S—Mo. Our results reveal how defect-mediated nonra...

Although many studies have been carried out on the doping of transition metal dichalcogenides (TMDCs), introducing controllable amounts of dopants into a TMD lattice is still insufficient. Here we demonstrate doping controlled TMDC growth by the replacement of selenium with phosphorus during the synthesis of the monolayer WSe2. The phosphorus doping density was precisely controlled by fine adjustment of the amount of P2O5 dopant powder along the pre-annealing time. Raman spectroscopy, photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), and high-angle annular bright field scanning tunneling electron microscopy (HAADF STEM) provide evidence that P doping occurs within the WSe2 crystal with P occupying the substitutional Se sites. With regard to its electrical characteristics, the hole majority current of P-doped WSe2 is 100-times higher than that of the intrinsic WSe2. The measured doping concentration ranged from ∼8.16 × 1010 to ∼1.20 × 1012 depending on the amount of P2O5 dopant powder by pre-annealing.

The conversion of chalcogen atoms to other types in transition metal dichalcogenides has significant advantages for tuning bandgaps and constructing in-plane heterojunctions; however, difficulty arises from the conversion of sulfur or selenium to tellurium atoms owing to the low decomposition temperature of tellurides. Here, we propose the use of sodium for converting monolayer molybdenum disulfide (MoS2) to molybdenum ditelluride (MoTe2) under Te-rich vapors. Sodium easily anchors tellurium and reduces the exchange barrier energy by scooting the tellurium to replace sulfur. The conversion was initiated at the edges and grain boundaries of MoS2, followed by complete conversion in the entire region. By controlling sodium concentration and reaction temperature of monolayer MoS2, we tailored various phases such as semiconducting 2H-MoTe2, metallic 1T′-MoTe2, and 2H-MoS2−xTex alloys. This concept was further extended to WS2. A high valley polarization of ~37% in circularly polarized photoluminescence was obtained in the monolayer WS2−xTex alloy at room temperature., Two dimensional monolayer transition metal ditellurides and their alloys are interesting but their growth has been difficult. Herein, Yun et al. demonstrate the use of sodium salts to convert transition metal disulfide to ditelluride and alloys in tellurium vapor at low temperature.

The optical and electrical properties of monolayer transition-metal dichalcogenides (1L-TMDs) are critically influenced by two dimensionally confined exciton complexes. Although, extensive studies on controlling the optical properties of 1L-TIVIDs through external doping or defect engineering have been carried out, the effects of excess charges, defects, and the populations of exciton complexes on the light emission of 1L-TMDs are not yet fully understood. Here, we present a simple chemical treatment method for n dope 1L-TMDs, which also enhances their optical and electrical properties. We show that dipping lLs of MoS2 WS2, and WSe2, whether exfoliated or grown'y chemical vapor deposition, into methanol for several hours can increase the electron density and also can reduce the defects, resulting in the enhancement of their photoluminescence, light absorption, and the carrier mobility:. This methanol treatment was effective for both n- and p-type 1L-TMDs, suggesting that the surface restructuring around structural defects by methanol is responsible for the enhancement of optical and electrical characteristics. Our results have revealed a simple process for external doping.that can enhance both the optical and electrical properties of 1L-TMDs and help us understand how the exciton emission in 1L-TMDs can be modulated by chemical treatments.

Photoinduced generation of mobile charge carriers is the fundamental process underlying many applications, such as solar energy harvesting, solar fuel production, and efficient photodetectors. Monolayer transition-metal dichalcogenides (TMDCs) are an attractive model system for studying photoinduced carrier generation mechanisms in low-dimensional materials because they possess strong direct band gap absorption, large exciton binding energies, and are only a few atoms thick. While a number of studies have observed charge generation in neat TMDCs for photoexcitation at, above, or even below the optical band gap, the role of nonlinear processes (resulting from high photon fluences), defect states, excess charges, and layer interactions remains unclear. In this study, we introduce steady-state microwave conductivity (SSMC) spectroscopy for measuring charge generation action spectra in a model WS

Monolayer MoS 2 with a direct and suitable bandgap and high flexibility make them fascinating building blocks for constructing novel nanostructures via a self-assembly process [1], [2]. In this work, we exploit liquid intercalation to activate the self-assembly of MoS 2 nanoscroll (NS) architectures from the monolayer flakes. Both metallic and semiconducting MoS 2 NSs can be identified by field-effect IV characterizations, and further linked to their Raman spectra in a statistical analysis. The self-assembled NS architecture bridges and inherits the unique properties of 1D and 2D nanomaterials, rendering great potential in various applications such as electronic/optoelectronic devices and energy storage.

Transition Metal Dichalcogenides In article number 2003709, Young Hee Lee, Young‐Kyu Han, Ki Kang Kim, and co‐workers demonstrate the unique basal plane activation of 2D MoS(2) via substituted V atom near chalcogen vacancy (VS(n) unit) in the lattice. The VS(n) units act as active sites and charge transfer pathways for efficient hydrogen evolution. This study adds insight into ways to engineer active sites in transition metal dichalcogenides electrocatalyst at the atomic level. [Image: see text]

Among transition metal dichalcogenides (TMdCs) as alternatives for Pt‐based catalysts, metallic‐TMdCs catalysts have highly reactive basal‐plane but are unstable. Meanwhile, chemically stable semiconducting‐TMdCs show limiting catalytic activity due to their inactive basal‐plane. Here, metallic vanadium sulfide (VSn) nanodispersed in a semiconducting MoS2 film (V–MoS2) is proposed as an efficient catalyst. During synthesis, vanadium atoms are substituted into hexagonal monolayer MoS2 to form randomly distributed VSn units. The V–MoS2 film on a Cu electrode exhibits Pt‐scalable catalytic performance; current density of 1000 mA cm−2 at 0.6 V and overpotential of −0.08 V at a current density of 10 mA cm−2 with excellent cycle stability for hydrogen‐evolution‐reaction (HER). The high intrinsic HER performance of V–MoS2 is explained by the efficient electron transfer from the Cu electrode to chalcogen vacancies near vanadium sites with optimal Gibbs free energy (−0.02 eV). This study provides insight into ways to engineer TMdCs at the atomic‐level to boost intrinsic catalytic activity for hydrogen evolution., The nanodispersed vanadium sulfide (VSn) in the MoS2 lattice is key for efficient hydrogen evolution by increasing the electrical conductivity and basal plane activity of V–MoS2 catalyst. The engineering advantage is that the stability of VS2 is ensured by the embedded VSn in MoS2 and the copper substrate tunes the Gibbs free energy and facilitates electron injection to active sites.

Growth of 2D van der Waals layered single-crystal (SC) films is highly desired not only to manifest the intrinsic physical and chemical properties of materials, but also to enable the development of unprecedented devices for industrial applications. While wafer-scale SC hexagonal boron nitride film has been successfully grown, an ideal growth platform for diatomic transition metal dichalcogenide (TMdC) films has not been established to date. Here, the SC growth of TMdC monolayers on a centimeter scale via the atomic sawtooth gold surface as a universal growth template is reported. The atomic tooth-gullet surface is constructed by the one-step solidification of liquid gold, evidenced by transmission electron microscopy. The anisotropic adsorption energy of the TMdC cluster, confirmed by density-functional calculations, prevails at the periodic atomic-step edge to yield unidirectional epitaxial growth of triangular TMdC grains, eventually forming the SC film, regardless of the Miller indices. Growth using the atomic sawtooth gold surface as a universal growth template is demonstrated for several TMdC monolayer films, including WS2 , WSe2 , MoS2 , the MoSe2 /WSe2 heterostructure, and W1- x Mox S2 alloys. This strategy provides a general avenue for the SC growth of diatomic van der Waals heterostructures on a wafer scale, to further facilitate the applications of TMdCs in post-silicon technology.

Monolayer transition metal dichalcogenides (TMDs) are atomically thin semiconductor films that are ideal platforms for the study and engineering of quantum heterostructures for optoelectronic applications. We present a simple method for the fabrication of TMD heterostructures containing MoSe2 quantum dots (QDs) and a MoS2 or WSe2 monolayer. The strong modification of photoluminescence and Raman spectra that includes the quenching of MoSe2 QDs and the varied spectral weights of trions for the MoS2 and WSe2 monolayers were observed, suggesting the charge transfer occurring in these TMD heterostructures. Such optically active heterostructures, which can be conveniently fabricated by dispersing TMD QDs onto TMD monolayers, are likely to have various nanophotonic applications because of their versatile and controllable properties.

Exciton transitions are mostly responsible for the optical properties of transition metal dichalcogenide monolayers (1L-TMDs). Extensive studies of optical and structural characterization indicated that the presence of local structural defects and charge population critically influence the exciton emissions of 1L-TMDs. However, due to large variations of sample and experimental conditions, the exact mechanism of the exciton emission influenced by local structural defects and charge population is not clearly understood. In this work by using near-field scanning optical imaging and spectroscopy, we directly visualized spatially- and spectrally-resolved emission profiles of excitons, trions and defect bound excitons in CVD-grown monolayer tungsten disulfide (1L-WS2) with ∼70 nm spatial resolution. We found that exciton emission is spatially uniform while emission of trions and defect bound excitons was strongly modulated by the presence of structural features such as defects and wrinkles. We also visually observe a strong correlation between local charge accumulation and the trion formation upon increased photo-excitation.

An unusually large bandgap modulation of 1.23-2.65 eV in monolayer MoS2 on a SiO2 /Si substrate is found due to the inherent local bending strain induced by the surface roughness of the substrate, reaching the direct-to-indirect bandgap transition. Approximately 80% of the surface area reveals an indirect bandgap, which is confirmed further by the degraded photoluminescence compared to that from suspended MoS2 .

We report a systematic study of the synthesis of large-area monolayer WSe 2 on gold foil by controlling the growth temperature and the partial pressure of hydrogen during chemical vapor deposition. The gold surface causes surface-mediated growth to form monolayer WSe 2 films. The amount of the tungsten source is controlled by adjusting the partial pressure of hydrogen, which plays a role in the reduction of WO 3 (solid phase) into WO 3−x (vapor phase). The coverage of monolayer WSe 2 can be effectively controlled by changing either the partial pressure of hydrogen or the growth temperature at a fixed growth time under an Se-rich atmosphere, resulting in 100% coverage of the WSe 2 film. The crystallinity and thickness uniformity are characterized by Raman spectroscopy, photoluminescence, and transmission electron microscopy. This characterization reveals that the quality of the WSe 2 film is comparable to mechanically-exfoliated monolayer WSe 2 and possesses good thickness uniformity.

Two-dimensional (2D) semiconductors are promising candidates for quantum-well devices with the inherent quantum confinement of the subnanometer thickness along the out-of-plane direction. Coulomb/quantum oscillation phenomena have been demonstrated in 2D semiconductors devices, including artificial quantum dots with local electrostatic gating and stacked heterostructure quantum wells. However, the exact quantized energy states, let alone the complexity of the device structures and low observation temperature, have not been clearly revealed. Here, we report a rational fabrication platform of 2D semiconductor nanotransistors to directly construct a Schottky-barrier quantum well (SB-QW) for quantized energy states engineering. The feature size of the quantum well is tailored by a vertical nanochannel of monolayer transition metal dichalcogenides (TMDCs) via an insulating spacer. Meanwhile, the potential barrier is constructed by the Schottky barrier. Quantum oscillations are clearly observed and the quantized energy states are extracted from the source-drain current modulated with the gate bias. Such quantum oscillations are preserved up to ~100 K with a channel length of approximately 16 nm. With an evaluated Schottky barrier height of approximately 27 meV, the quantized energy states are estimated from 2 to 24 meV near the conduction band edge, consistent with corresponding explicit principal quantum numbers. Our work demonstrates the feasibility of moving 2D van der Waals semiconductor nanotransistors towards quantum transistors.

While a hexagonal WS2 monolayer, grown by chemical vapor deposition, exhibits distinctive patterns in photoluminescence mapping, segmented with alternating S-vacancy (SV) and W-vacancy (WV) domains in a single crystal, the formation mechanism for native alternating defect domains remains unresolved to date. Here, the formation mechanism of alternating defect domains in hexagonal WS2 via the precursor accumulation model is experimentally elucidated. A triangular WS2 seed is initially formed, followed by a hexagonal flake. Alternating W-rich (SV) and W-deficient (WV) domains are constructed in hexagonal WS2 flake, which is confirmed by confocal photoluminescence mapping and secondary ion mass spectroscopy. This is explained by the accumulation or scarcity of W-precursors at the edge of the WS2 flake. The W-precursors accumulate near the edges of the initial triangular WS2 seed over time, while they are deficient near the corners of the triangular WS2 , eventually forming WV domains in the truncated hexagonal domains. The heterogeneous accumulation becomes more prominent in the presence of H2 gas through desorption of the W-precursors.

Layered van der Waals materials have recently attracted attention owing to their exceptional electrical and optical properties in thin layer form. One way to extend their utility is to form a heterostructure which combines various properties of layered materials to reveal intriguing behavior. Conventional heterostructure synthesis methods are difficult to develop and the heterostructure formed can be limited to a small area. Here, we investigate the phase transformation of SnS2 to SnS by removing sulfur atoms at the top surface using Ar plasma. By varying the plasma power and exposure time, we observed that SnS is subsequently formed on top of the mogul-like structure of SnS2. Since SnS is a p-type semiconductor and SnS2 is an n-type semiconductor, we naturally formed a vertical p-n junction. By using graphene at the top and bottom as transparent electrodes, a vertical p-n diode device is constructed. The device demonstrates good rectifying behavior and large photocurrent generation under white light. This method can be applied to large-area heterostructure synthesis using plasma via phase transformation of various metal dichalcogenides to metal monochalcogenides.

Wafer-scale hBN crystalline films Although wafer-scale polycrystalline films of insulating hexagonal boron nitride (hBN) can be grown, the grain boundaries can cause both scattering or pinning of charge carriers in adjacent conducting layers that impair device performance. Lee et al. grew wafer-scale single-crystal films of hBN by feeding the precursors into molten gold films on tungsten substrates. The low solubility of boron and nitrogen in gold caused micrometer-scale grains of hBN to form that coalesced into single crystals. These films in turn supported the growth of epitaxial wafer-scale films of graphene and tungsten disulfide. Science , this issue p. 817

Monolayer (1L) transition metal dichalcogenides (TMDCs) are promising materials for nanoscale optoelectronic devices because of their direct band gap and wide absorption range (ultraviolet to infrared). However, 1L-TMDCs cannot be easily utilized for practical optoelectronic device applications (e.g., photodetectors, solar cells, and light-emitting diodes) because of their extremely low optical quantum yields (QYs). In this investigation, a high-gain 1L-MoS2 photodetector was successfully realized, based on the surface plasmon (SP) of the Ag nanowire (NW) network. Through systematic optical characterization of the hybrid structure consisting of a 1L-MoS2 and the Ag NW network, it was determined that a strong SP and strain relaxation effect influenced a greatly enhanced optical QY. The photoluminescence (PL) emission was drastically increased by a factor of 560, and the main peak was shifted to the neutral exciton of 1L-MoS2. Consequently, the overall photocurrent of the hybrid 1L-MoS2 photodetector was ob...

We report the synthesis of centimeter-scale monolayer WS2 on gold foil by chemical vapor deposition. The limited tungsten and sulfur solubility in gold foil allows monolayer WS2 film growth on gold surface. To ensure the coverage uniformity of monolayer WS2 film, the tungsten source-coated substrate was placed in parallel with Au foil under hydrogen sulfide atmosphere. The high growth temperature near 935 °C helps to increase a domain size up to 420 μm. Gold foil is reused for the repeatable growth after bubbling transfer. The WS2-based field effect transistor reveals an electron mobility of 20 cm(2) V(-1) s(-1) with high on-off ratio of ∼10(8) at room temperature, which is the highest reported value from previous reports of CVD-grown WS2 samples. The on-off ratio of integrated multiple FETs on the large area WS2 film on SiO2 (300 nm)/Si substrate shows within the same order, implying reasonable uniformity of WS2 FET device characteristics over a large area of 3 × 1.5 cm(2).

The polar edges of two-dimensional monolayer transition metal dichalcogenides (TMD) and their alloys are examined by combined theoretical (density functional theory) and experimental approaches. For these polar edges, the growth reaction energies between different edge terminations are considered instead of the surface free energies. Due to different energy evolutions during growth on the zigzag edges between MoS2 and WS2, the S-ZZ edges in the WS2 monolayer flakes more easily decompose into sawtooth-like edges in M-ZZ type as compared to the MoS2 monolayer; thus, the hexagonal morphology can be seen more often in WS2. Moreover, the observed anisotropic short-range order in the MoS2/WS2 alloys is originated from the freezed edge configurations during growth, explainable by the growth kinetics and thermodynamics of the Mo-ZZ-edges. The determination of the growing edge terminations is of great importance for the controllable synthesis of the emergent two-dimensional TMD materials.

International audience; his paper reports on the integration of freestanding transition metal dichalcogenides (TMDs). Monolayer (1‐L) MoS2, WS2, and WSe2 as representative TMDs are transferred on ZnO nanorods (NRs), used here as nanostructured substrates. The photoluminescence (PL) spectra of 1‐L TMDs on NRs show a giant PL intensity enhancement, compared with those of 1‐L TMDs on SiO2. The strong increases in Raman and PL intensities, along with the characteristic peak shifts, confirm the absence of stress in the TMDs on NRs. In depth analysis of the PL emission also reveals that the ratio between the exciton and trion peak intensity is almost not modified after transfer. The latter shows that the effect of charge transfer between the 1‐L TMDs and ZnO NRs is here negligible. Furthermore, confocal PL and Raman spectroscopy reveal a fairly consistent distribution of PL and Raman intensities. These observations are in agreement with a very limited points contact between the support and the 1‐L TMDs. The entire process reported here is scalable and may pave the way for the development of very efficient ultrathin optoelectronics.

Hexagonal boron nitride (h-BN) has recently been in the spotlight due to its numerous applications including its being an ideal substrate for two-dimensional electronics, a tunneling material for vertical tunneling devices, and a growth template for heterostructures. However, to obtain a large area of h-BN film while maintaining uniform thickness is still challenging and has not been realized. Here, we report the systematical study of h-BN growth on Pt foil by using low pressure chemical vapor deposition with a borazine source. The monolayer h-BN film was obtained over the whole Pt foil (2 × 5 cm(2)) under100 mTorr, where the size is limited only by the Pt foil size. A borazine source was catalytically decomposed on the Pt surface, leading to the self-limiting growth of the monolayer without the associating precipitation, which is very similar to the growth of graphene on Cu. The orientation of the h-BN domains was largely confined by the Pt domain, which is confirmed by polarizing optical microscopy (POM) assisted by the nematic liquid crystal (LC) film. The total pressure and orientation of the Pt lattice plane are crucial parameters for thickness control. At high pressure (∼0.5 Torr), thick film was grown on Pt (111), and in contrast, thin film was grown on Pt (001). Our advances in monolayer h-BN growth will play an important role to further develop a high quality h-BN film that can be used for vertical tunneling, optoelectronic devices and growth templates for a variety of heterostructures.

We report long-range ferromagnetic ordering in a vanadium-doped monolayer WSe2 semiconductor using spin-polarized density functional calculations. We found that the vanadium dopant is located in the fully occupied state inside the valence band, inherent from spin–orbit coupling, leading to the presence of free holes in the valence band. As a consequence, the spin-polarized hole carriers are delocalized not only in the vanadium site but also persistently in the tungsten sites distant from vanadium to facilitate the long-range ferromagnetic ordering in the vanadium-doped monolayer WSe2. Our findings of this study pave the way for the future exploration of carrier-mediated room-temperature two-dimensional ferromagnetic semiconductors via magnetic dopants.

2D van der Waals layered heterostructures allow for a variety of energy band offsets, which help in developing valuable multifunctional devices. However, p–n diodes, which are typical and versatile, are still limited by the material choice due to the fixed band structures. Here, the vanadium dopant concentration is modulated in monolayer WSe2 via chemical vapor deposition to demonstrate tunable multifunctional quantum tunneling diodes by vertically stacking SnSe2 layers at room temperature. This is implemented by substituting tungsten atoms with vanadium atoms in WSe2 to provoke the p‐type doping effect in order to efficiently modulate the Fermi level. The precise control of the vanadium doping concentration is the key to achieving the desired quantum tunneling diode behaviors by tuning the proper band alignment for charge transfer across the heterostructure. By constructing a p–n diode for p‐type V‐doped WSe2 and heavily degenerate n‐type SnSe2, the type‐II band alignment at low V‐doping concentration is clearly shown, which evolves into the type‐III broken‐gap alignment at heavy V‐doping concentration to reveal a variety of diode behaviors such as forward diode, backward diode, negative differential resistance, and ohmic resistance.

Lateral heterojunction (HJ) of two-dimensional transition metal dichalcogenides has various optoelectronic applications that utilize in-plane charge separation. However, it has been difficult to identify charge transfer characteristics at HJ due to the limited spatial resolution of optical spectroscopy. In this study, near-field scanning optical microscopy is used to directly image the exciton separation occurring at the lateral MoSe2/WSe2 HJ, which was found to be ∼370 nm in spatial width. Efficient charge separation at HJ was confirmed by inspecting local variations of trion and exciton emissions of MoSe2 and WSe2.

We successfully achieve the tip-enhanced nano Raman scattering images of a tungsten disulfide monolayer with optimizing a fabrication method of gold nanotip by controlling the concentration of etchant in an electrochemical etching process. By applying a square-wave voltage supplied from an arbitrary waveform generator to a gold wire, which is immersed in a hydrochloric acid solution diluted with ethanol at various ratios, we find that both the conical angle and radius of curvature of the tip apex can be varied by changing the ratio of hydrochloric acid and ethanol. We also suggest a model to explain the origin of these variations in the tip shape. From the systematic study, we find an optimal condition for achieving the yield of similar to 60% with the radius of similar to 34 nm and the cone angle of similar to 35 degrees. Using representative tips fabricated under the optimal etching condition, we demonstrate the tip-enhanced Raman scattering experiment of tungsten disulfide monolayer grown by a chemical vapor deposition method with a spatial resolution of similar to 40 nm and a Raman enhancement factor of similar to 4,760.

Delamination of thin films from the supportive substrates is critical issues in thin film industry and technology. The emergent two-dimensional materials, atomic layered materials, such as transition metal dichalcogenides are highly flexible thus the buckles and wrinkles can be easily generated and play vital effects on the physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, mainly due to the thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with strains, whereas the transmission electron microscopy revealed the special sawtooth shaped edge structures which break the geometrical symmetry of the buckling behavior of hexagonal samples. The condition of this edge delamination is in accordance with the fracture theory. This edge delamination process and buckling upon synthesis is universal for most of the ultrathin two dimensional materials, and it is definitely noteworthy in their future applications., Comment: 18 pages, 6 figures

Two-dimensional (2D) transition-metal dichalcogenide (TMD) monolayers of versatile material library are spotlighted for numerous unexplored research fields. While monolayer TMDs exhibit an efficient excitonic emission, the weak light absorption arising from their low dimensionality limits potential applications. To enhance the light-matter interactions of TMDs, while various plasmonic hybridization methods have been intensively studied, controlling plasmonic nanostructures via self-assembly processes remains challenging. Herein, strong light-matter interactions are reported in plasmonic Ag nanoparticles (NPs) hybridized on TMDs via an aging-based self-assembly process at room temperature. This hybridization is implemented by transferring MoS2 monolayers grown via chemical vapor deposition onto thin-spacer-covered Ag films. After a few weeks of aging in a vacuum desiccator, the Ag atoms in the heterolayered film diffuse to the MoS2 layers through a SiO2 spacer and self-cluster onto MoS2 point defects, resulting in the formation of Ag-NPs with an estimated diameter of ≈50 nm. The photoluminescence intensities for the Ag-NP/MoS2 hybrids are enhanced up to 35-fold compared with bare MoS2 owing to the local field enhancement near the plasmonic Ag-NPs. The localized surface plasmon resonances modes of this hybrid are systematically investigated via numerical simulations and dark-field scattering microscopy.

While transmission electron microscopy and scanning tunneling microscopy reveal atomic structures of point defect and grain boundary in monolayer transition-metal dichalcogenides (TMDs), information on point defect distribution in macroscale is still not available. Herein, we visualize the point defect distribution of monolayer TMDs using dark-field optical microscopy. This was realized by anchoring silver nanoparticles on defect sites of MoS2 under light illumination. The optical images clearly revealed that the point defect distribution varies with light power and exposure time. The number of silver nanoparticles increased initially and reached a plateau in response to light power or exposure time. The size of silver nanoparticles was a few hundred nanometers in the plateau region as observed using optical microscopy. The measured defect density in macroscale was ∼2 × 10(10) cm(-2), slightly lower than the observed value (4 × 10(11) cm(-2)) from scanning tunneling microscopy.

Although hexagonal boron nitride (h-BN) is a good candidate for gate-insulating materials by minimizing interaction from substrate, further applications to electronic devices with available two-dimensional semiconductors continue to be limited by flake size. While monolayer h-BN has been synthesized on Pt and Cu foil using chemical vapour deposition (CVD), multilayer h-BN is still absent. Here we use Fe foil and synthesize large-area multilayer h-BN film by CVD with a borazine precursor. These films reveal strong cathodoluminescence and high mechanical strength (Young’s modulus: 1.16±0.1 TPa), reminiscent of formation of high-quality h-BN. The CVD-grown graphene on multilayer h-BN film yields a high carrier mobility of ~24,000 cm[superscript 2] V[superscript −1] s[superscript −1] at room temperature, higher than that (~13,000 [superscript 2] V[superscript −1] s[superscript −1]) with exfoliated h-BN. By placing additional h-BN on a SiO[subscript 2]/Si substrate for a MoS[subscript 2] (WSe[subscript 2]) field-effect transistor, the doping effect from gate oxide is minimized and furthermore the mobility is improved by four (150) times., Korea Institute of Science and Technology. Institutional Program, National Science Foundation (U.S.) (STC Center for Integrated Quantum Materials Grant DMR-1231319), Massachusetts Institute of Technology. Institute for Soldier Nanotechnologies

We investigated the physical properties of molybdenum disulfide (MoS2) atomic crystals with a sulfur vacancy passivation after treatment with alkanethiol molecules including their electrical, Raman, and photoluminescence (PL) characteristics. MoS2, one of the transition metal dichalcogenide materials, is a promising two-dimensional semiconductor material with good physical properties. It is known that sulfur vacancies exist in MoS2, resulting in the n-type behavior of MoS2. The sulfur vacancies on the MoS2 surface tend to form covalent bonds with sulfur-containing groups. In this study, we deposited alkanethiol molecules on MoS2 field effect transistors (FETs) and then characterized the electrical properties of the devices before and after the alkanethiol treatment. We observed that the electrical characteristics of MoS2 FETs dramatically changed after the alkanethiol treatment. We also observed that the Raman and PL spectra of MoS2 films changed after the alkanethiol treatment. These effects are attributed to the thiol (-SH) end groups in alkanethiols bonding at sulfur vacancy sites, thus altering the physical properties of the MoS2. This study will help us better understand the electrical and optical properties of MoS2 and suggest a way of tailoring the properties of MoS2 by passivating a sulfur vacancy with thiol molecules.

We report the synthesis of centimeter-scale, uniform 1T′- and 2H-MoTe2 thin films via the tellurization of Mo thin films. 1T′-MoTe2 was initially grown and converted gradually to 2H-MoTe2 over a prolonged growth time under a Te atmosphere. Maintaining excessive Te was essential for obtaining the stable stoichiometric 2H-MoTe2 phase. Further annealing under a lower partial pressure of Te at the same temperature, followed by a rapid quenching, led to the reverse phase transition from 2H-MoTe2 to 1T′-MoTe2. The orientation of the 2H-MoTe2 film was determined by the tellurization rate. Slow tellurization was the key for obtaining a highly oriented 2H-MoTe2 film over the entire area, while fast tellurization led to a 2H-MoTe2 film with a randomly oriented c-axis.