Transition Metal Dichalcogenides Flakes Research Articles

Van der Waals Heterostructures With Built-In Mie Resonances For Polarization-Sensitive Photodetection.

Few-layer transition metal dichalcogenides (TMDs) and their combination as van der Waals heterostructures provide a promising platform for high-performance optoelectronic devices. However, the ultrathin thickness of TMD flakes limits efficient light trapping and absorption, which triggers the hybrid construction with optical resonant cavities for enhanced light absorption. The optical structure enriched photodetectors can also be wavelength- and polarization-sensitive but require complicated fabrication. Herein, a new-type TMD-based photodetector embedded with nanoslits is proposed to enhance light trapping. Taking ReS2 as an example, strong anisotropic Mie-type optical responses arising from the intrinsic in-plane anisotropy and nanoslit-enhanced anisotropy are discovered. Owing to the nanoslit-enhanced optical resonances and band engineering, excellent photodetection performances are demonstrated with high responsivity of 27 A W-1 and short rise/decay times of 3.7/3.7ms. More importantly, through controlling the angle between the nanoslit orientation and the polarization direction to excite different resonant modes, polarization-sensitive photodetectors with anisotropy ratios from 5.9 to 12.6 can be achieved, representing one of the most polarization-sensitive TMD-based photodetectors. The depth and orientation of nanoslits are demonstrated crucial for optimizing the anisotropy ratio. The findings bring an effective scheme to construct high-performance and polarization-sensitive photodetectors.

Optical propagation of exciton polaritons in ultrathin van der Waals microcrystals down to few monolayers

The exciton polariton is a kind of quasiparticles and provides a promising opportunity to explore fundamental quantum phenomena for photonic applications. Transition-metal dichalcogenide (TMD) materials provide the platform of nanophotonics that supports the propagative exciton polaritons even at room-temperature. Previously, real space studies on thin flakes of TMDs by scattering-type scanning nearfield optical microscopy (s-SNOM) were limited to waveguide thickness down to 30 nm. In this work, we present the nano-optical imaging of ordinary transverse electric modes of exciton polaritons in MoS2 and WSe2 down to a few atomic layers, measured by atomic force microscope-based s-SNOM. Surprisingly, the interference fringe patterns can be observed clearly at the prepared ultrathin TMD flakes with thickness down to ~3 nm (4 ML) and ~8 nm (12 ML) for MoS2 and WSe2, respectively, which breaks greatly the previous measurement limitation. The wavevectors stay around 1.6k0−1.7k0 constantly when the thickness approaching to a few MLs, instead of 1k0 according to the theory. These modes are supported by the nearly-freestanding TMD microflakes in the form of three-layer symmetric waveguide to confine the exciton polaritons. Our results provide in-depth understanding and open new avenues to explore the polaritonic devices operating at the near infrared region based on ultrathin TMD materials.

In Situ Active Switching of Bipolar Current Rectification in 2D Semiconductor Vertical Diodes.

Two-dimensional semiconducting transition-metal dichalcogenides (TMDCs) have attracted extensive attention as building blocks of miniaturized electronic and optical devices. However, as the characteristics of TMDC devices are predominately determined by their device structures, the function of TMDC devices is fixed once fabricated, leaving the reconfigurable active device and circuit a challenge. Here, we have demonstrated the current rectification switching in TMDC vertical diodes using a liquid metal (EGaIn) top electrode with a reconfigurable contact area. The rectification switching is closely related to the ultrathin gallium oxide layer on the surface of EGaIn. Under the small contact, with the existence of gallium oxide, photocurrent dominates the electrical transport showing a negative rectification, while as the contact increases, the broken gallium oxide leads to rectification switching to the positive bias direction. Such rectification switching applies to thin TMDC flakes down to 3 nm, benefitting from the soft electrical contact between the TMDC and the EGaIn electrode. Our work shows the new possibility of actively reconfigurable TMDC vertical diodes enabled by the liquid metal electrode and will promote promising applications of flexible and tunable TMDC-based nanoelectronic devices.

Microwave Facilitated Covalent Organic Framework/Transition Metal Dichalcogenide Heterostructures.

Organic/inorganic heterostructures present a versatile platform for creating materials with new functionalities and hybrid properties. In particular, junctions between two dimensional materials have demonstrated utility in next generation electronic, optical, and optoelectronic devices. This work pioneers a microwave facilitated synthesis process to readily incorporate few-layer covalent organic framework (COF) films onto monolayer transition metal dichalcogenides (TMDC). Preferential microwave excitation of the monolayer TMDC flakes result in selective attachment of COFs onto the van der Waals surface with film thicknesses between 1 and 4 nm. The flexible process is extended to multiple TMDCs (MoS2, MoSe2, MoSSe) and several well-known COFs (TAPA-PDA COF, TPT-TFA-COF, and COF-5). Photoluminescence studies reveal a power-dependent defect formation in the TMDC layer, which facilitates electronic coupling between the materials at higher TMDC defect densities. This coupling results in a shift in the A-exciton peak location of MoSe2, with a red or blue shift of 50 or 19 meV, respectively, depending upon the electron donating character of the few-layer COF films. Moreover, optoelectronic devices fabricated from the COF-5/TMDC heterostructure present an opportunity to tune the PL intensity and control the interaction dynamics within inorganic/organic heterostructures.

Transition metal dichalcogenide metaphotonic and self-coupled polaritonic platform grown by chemical vapor deposition

Transition metal dichalcogenides (TMDCs) have recently attracted growing attention in the fields of dielectric nanophotonics because of their high refractive index and excitonic resonances. Despite the recent realizations of Mie resonances by patterning exfoliated TMDC flakes, it is still challenging to achieve large-scale TMDC-based photonic structures with a controllable thickness. Here, we report a bulk MoS2 metaphotonic platform realized by a chemical vapor deposition (CVD) bottom-up method, supporting both pronounced dielectric optical modes and self-coupled polaritons. Magnetic surface lattice resonances (M-SLRs) and their energy-momentum dispersions are demonstrated in 1D MoS2 gratings. Anticrossing behaviors with Rabi splitting up to 170 meV are observed when the M-SLRs are hybridized with the excitons in multilayer MoS2. In addition, distinct Mie modes and anapole-exciton polaritons are also experimentally demonstrated in 2D MoS2 disk arrays. We believe that the CVD bottom-up method would open up many possibilities to achieve large-scale TMDC-based photonic devices and enrich the toolbox of engineering exciton-photon interactions in TMDCs.

Layer-Number Engineered Momentum-Indirect Interlayer Excitons with Large Spectral Tunability.

Interlayer excitons (IXs) in type II van der Waals (vdW) heterostructures are equipped with an oriented permanent dipole moment and long lifetime and thus would allow promising applications in excitonic and optoelectronic devices. However, based on the widely studied heterostructures of transition-metal dichalcogenides (TMDs), IX emission is greatly influenced by the lattice mismatch and geometric misalignment between the constituent layers, increasing the complexity of the device fabrication. Here, we report on the robust momentum-indirect IX emission in TMD/two-dimensional (2D) perovskite vdW heterostructures, which were fabricated without considering the orientation arrangement or momentum mismatch. The IXs show a large diffusion coefficient of ∼10 cm2 s-1, and importantly the IX emission energy can be widely tuned from 1.3 to 1.6 eV via changing the layer number of the 2D perovskite or the thickness of TMD flakes, shedding light on the applications of vdW interface engineering to broad-spectrum optoelectronics.

Dynamic growth/etching model for the synthesis of two-dimensional transition metal dichalcogenides via chemical vapour deposition

The preparation of two-dimensional transition metal dichalcogenides on an industrially relevant scale will rely heavily on bottom-up methods such as chemical vapour deposition. In order to obtain sufficiently large quantities of high-quality material, a knowledge-based optimization strategy for the synthesis process must be developed. A major problem that has not yet been considered is the degradation of materials by etching during synthesis due to the high growth temperatures. To address this problem, we introduce a mathematical model that accounts for both growth and, for the first time, etching to describe the synthesis of two-dimensional transition metal dichalcogenides. We consider several experimental observations that lead to a differential equation based on several terms corresponding to different supply mechanisms, describing the time-dependent change in flake size. By solving this equation and fitting two independently obtained experimental data sets, we find that the flake area is the leading term in our model. We show that the differential equation can be solved analytically when only this term is considered, and that this solution provides a general description of complex growth and shrinkage phenomena. Physically, the dominance suggests that the supply of material via the flake itself contributes most to its net growth. This finding also implies a predominant interplay between insertion and release of atoms and their motion in the form of a highly dynamic process within the flake. In contrast to previous assumptions, we show that the flake edges do not play an important role in the actual size change of the two-dimensional transition metal dichalcogenide flakes during chemical vapour deposition.

Self-Limiting Opto-Electrochemical Thinning of Transition-Metal Dichalcogenides.

Two-dimensional monolayer and few-layer transition-metal dichalcogenides (TMDs) are promising for advanced electronic and photonic applications due to their extraordinary optoelectronic and mechanical properties. However, it has remained challenging to produce high-quality TMD thin films with controlled thickness and desired micropatterns, which are essential for their practical implementation in functional devices. In this work, a self-limiting opto-electrochemical thinning (sOET) technique is developed for on-demand thinning and patterning of TMD flakes at high efficiency. Benefiting from optically enhanced electrochemical reactions, sOET features a low operational optical power density of down to 70 μW μm-2 to avoid photodamage and thermal damage to the thinned TMD flakes. Through selective optical excitation with different laser wavelengths based on the thickness-dependent band gaps of TMD materials, sOET enables precise control over the final thickness of TMD flakes. With the capability of thickness control and site-specific patterning, our sOET offers an effective route to fabricating high-quality TMD materials for a broad range of applications in nanoelectronics, nanomechanics, and nanophotonics.

Charting the Exciton–Polariton Landscape of WSe2 Thin Flakes by Cathodoluminescence Spectroscopy

Semiconducting transition‐metal dichalcogenides (TMDCs) provide a fascinating discovery platform for strong light–matter interaction effects in the visible spectrum at ambient conditions. While most of the works have focused on hybridizing excitons with resonant photonic modes of external mirrors, cavities, or nanostructures, intriguingly, TMDC flakes of subwavelength thickness can themselves act as nanocavities. Herein, the optical response of such freestanding planar waveguides of WSe2 by means of cathodoluminescence spectroscopy is determined. Strong exciton–photon interaction effects that foster long‐range propagating exciton–polaritons and enable direct imaging of the energy transfer dynamics originating from cavity‐like Fabry–Pérot resonances are revealed. Furthermore, confinement effects due to discontinuities in the flakes are demonstrated as an efficient means to tailor mode energies, spin–momentum couplings, and the exciton–photon coupling strength, as well as to promote photon‐mediated exciton–exciton interactions. The combined experimental and theoretical results provide a deeper understanding of exciton–photon self‐hybridization in semiconducting TMDCs and may pave the way to optoelectronic nanocircuits exploiting exciton–photon interaction beyond the routinely employed two‐oscillator coupling effects.

Photoluminescence enhancement in multilayered MoSe2 nanostructures obtained by local anodic oxidation

Monolayers of transition metal dichalcogenides (TMDCs) exhibit attractive properties and are promising for fabricating photonic and optoelectronic devices, while bulk multilayered structures based on the same materials only recently has revealed many properties useful for nanophotonics. In this regard, the combination of monolayer and multilayer properties in one device (on a single flake) is an important and fruitful task that needs to be solved. In this work, we demonstrate the use of local anodic oxidation to improve the optical properties of multilayer MoSe2 flakes on a gold-covered substrate. Using this method, we fabricated nanostructures demonstrating extraordinarily enhanced photoluminescence (PL), with an intensity up to three orders of magnitude compared to that of the original structure. Low-frequency Raman spectroscopy showed that the nature of this PL enhancement is that the bindings between the layers inside the nanostructures are severely disrupted. This means that the nanostructures consist of quasi-monolayers, which is in good agreement with the intensity and the position of PL peak. Here, we also propose a mechanism of forming these quasi-monolayers. Therefore, this method allows using multilayer TMDC flakes on a conductive substrate to fabricate areas with quasi-monolayer optical properties, exhibiting an enhanced PL intensity.

Nanotribology of transition metal dichalcogenide flakes deposited by chemical vapour deposition: The influence of chemical composition and sliding speed on nanoscale friction of monolayers

We present nanoscale frictional analysis of three commonly used transition metal dichalcogenide (TMD) monolayers, WS2, MoSe2 and WSe2, deposited by chemical vapour deposition (CVD). The monolayers were characterised by Raman spectroscopy, photoluminescence spectroscopy (PL), and X-ray spectroscopy (XPS), to determine the composition of the coating and confirm monolayer structure. Nanoscale frictional analysis was performed by atomic force microscopy (AFM). Load-dependent frictional behaviour was measured at different sliding speeds to quantitatively assess friction on each sample. All samples experienced low nanoscale friction, with the lowest friction observed on WSe2. The friction was independent of sliding speed within the analysed range. Furthermore, monolayer TMDs significantly increase the operational load range by at least one order of magnitude when compared to SiO2 substrate.

Covalent Cross-Linking of 2H-MoS2 Nanosheets.

The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS2 -MoS2 homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS2 sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials.

Strain Induced Phase Transition of WS2 by Local Dewetting of Au/Mica Film upon Annealing

Here, we present a proof-of-concept experiment where phase engineering at the nanoscale of 2D transition metal dichalcogenides (TMDC) flakes (from semiconducting 2H phase to metallic 1T phase) can be achieved by thermal annealing of a TMDC/Au/mica system. The local dewetting of Au particles and resulting tensile strain produced on the TMDC flakes, strongly bound to the Au surface through effective S-Au bonds, can induce a local structural phase transition. An important role is also played by the defects induced by the thermal annealing: when vacancies are present, the threshold strain needed to trigger the phase transition is significantly reduced. Scanning photoelectron microscopy (SPEM) was revealed to be the perfect tool to monitor the described phenomena.

Magnetic Moments Induced by Atomic Vacancies in Transition Metal Dichalcogenide Flakes.

2D magnetism plays a key role in both fundamental physics and potential device applications. However, the instability of the discovered 2D magnetic materials has been one main obstacle in deep research and potential application of 2D magnetism. Here, a localized magnetic moment induced by Pt vacancies in air-stable type-II Dirac semimetal PtSe2 flakes is reported. The localized magnetic moments give rise to the Kondo effect, evidenced by logarithmic increment of resistance with decreasing temperature and isotropic negative longitudinal magnetoresistance. Additionally, the induced magnetic moment and Kondo temperature appear to depend on thickness in the thinner samples (<10nm). The small magnetocrystalline anisotropy revealed by first-principles calculation indicates that the magnetic moments are randomly localized instead of long-range ordered. The findings demonstrate a new means to induce magnetism in 2D non-magnetic materials.

ALD-Based Synthesis of Wafer-Scale Transition Metal Dichalcogenides Towards Nanoelectronics and Optoelectronics Applications

Two-dimensional (2D) transition metal dichalcogenides (TMDs), such as MoS2 and WS2 have been widely studied due to their unique physical and electronic properties even at one atomic layer thickness. Since the first report on the MoS2 field-effect transistor (FET) device [1], great efforts have been made in the past decade to extend the intriguing features of TMDs to practical applications. However, such integration has been severely bottlenecked by the lack of effective approaches to achieve wafer-scale, uniform, crystalline and stoichiometric TMD films.Till now, it is still prevalent to fabricate TMD-based electronic devices using mechanical exfoliation methods. Although single-crystal flakes with least defects can be obtained, the size, thickness and location of the exfoliated TMD flakes are largely uncontrollable, making it unsuitable for large-scale device integration and massive production. So far, various synthetic approaches have been proposed to grow large-area TMD thin films. Chemical vapor deposition (CVD)-based method is one of the major routines to synthesize high-quality monolayer and few-layer TMD flakes [2-4]. For example, in typical CVD processes to grow MoS2, the films can be achieved either by the reduction reaction between the S and MoO3 source powders or by sulfurizing the Mo (or MoOx) films pre-deposited by using physical vapor deposition. However, the nucleation sites in the CVD process are uncontrollable which may lead to the vertical stacking of the MoS2 flakes in triangle shape deteriorating the crystalline properties of the film. On the other hand, the pre-deposited Mo or MoOx film by using e-beam evaporation or sputtering usually suffer from rough surface morphology and unsatisfactory film uniformity which further limit the homogeneity of the large-scale film and device integration.Atomic layer deposition (ALD) is a surface-controlled film fabrication and can provide a possible route towards the synthesis of TMD thin films since the ALD approach follows the layer-by-layer deposition mechanism [5,6]. As compared to the conventional CVD method, ALD can enable precise thickness control on atomic scale and excellent film uniformity as well as good stoichiometry and crystallinity with proper annealing steps. In this work, we employed the ALD-based synthesis method to grow wafer-scale MoS2 and WS2 thin films. Non-toxic MoCl5, WCl5 and hexamethyldisilathiane (HMDST) precursors have been used which are different and superior to those used in previous work. Film characterizations have confirmed the wafer-level uniformity, crystallinity and stoichiometry of the synthesized films. Homogeneous electrical behaviors have also been obtained from the fabricated FET device arrays. In addition, optoelectronic devices such as photodetectors and simple logic gates such as n-type inverter arrays have been demonstrated using the wafer-scale MoS2 FET arrays. Furthermore, we have used the substitutional doping in the ALD process to achieve controllable p-type doping of MoS2 films, which can provide solid basis for the complimentary metal-oxide-semiconductor (CMOS) integrated circuit applications. This work shows that the ALD-based synthesis of the 2D TMD thin films is an attractive approach and has provided a promising platform to further push forward the circuit and system level applications of the TMD materials.

Low‐Damaged Layer‐by‐Layer Etching of Large‐Area Molybdenum Disulfide Films via Mild Plasma Treatment

AbstractControlling the number of layers of 2D transition metal dichalcogenide (TMDC) film is indispensable for optoelectronic applications because of their layer‐dependent optical features. However, most of methodologies on controlling TMDC layers induce undesirable defect formation and are performed on TMDC flakes, obtained from mechanical exfoliation. These limitations make practical TMDC‐based optoelectronic applications more difficult. Herein, layer‐by‐layer etching methodology of molybdenum disulfide (MoS2) films is developed using mild sulfur hexafluoride (SF6) plasma treatment. It is confirmed that the number of layers is successfully controlled from trilayer to monolayer by increasing plasma treatment time, while preserving overall film quality. Such low‐damaged layer‐by‐layer etching is attributed to this mild plasma etching system to only introduce the chemical reaction between ionized fluorine and MoS2, without physical damage to MoS2. Electrical properties of layer‐controlled MoS2 devices are also investigated, achieving comparatively high field‐effect mobilities of 16.2, 8.84, and 2.87 cm2 V−1 s−1 for tri‐, bi‐, and monolayer MoS2, respectively. This finding provides the possibility of realizing layer‐by‐layer engineering of 2D TMDCs.

Gold-vapor-assisted chemical vapor deposition of aligned monolayer WSe2 with large domain size and fast growth rate

Orientation-controlled growth of two-dimensional (2D) transition metal dichalcogenides (TMDCs) may enable many new electronic and optical applications. However, previous studies reporting aligned growth of WSe2 usually yielded very small domain sizes. Herein, we introduced gold vapor into the chemical vapor deposition (CVD) process as a catalyst to assist the growth of WSe2 and successfully achieved highly aligned monolayer WSe2 triangular flakes grown on c-plane sapphire with large domain sizes (130 µm) and fast growth rate (4.3 µm·s−1). When the aligned WSe2 domains merged together, a continuous monolayer WSe2 was formed with good uniformity. After transferring to Si/SiO2 substrates, field effect transistors were fabricated on the continuous monolayer WSe2, and an average mobility of 12 cm2·V−1·s−1 was achieved, demonstrating the good quality of the material. This report paves the way to study the effect of catalytic metal vapor in the CVD process of TMDCs and contributes a novel approach to realize the growth of aligned TMDC flakes.

Field emission from nanotubes and flakes of transition metal dichalcogenides

Transition metal dichalcogenides such as MoS2 and WS2 are low-dimensional semiconductor materials. MoS2 and WS2 nanotubes and flakes were grown by a chemical transport reaction under a temperature gradient. I2 was used as a transport agent for previously synthesized MoS2 and WS2, respectively. These multilayered nanotubes are indirect bandgap semiconductors with a bandgap depending on their diameter. WS2 flakes were prepared by the sulfurization of thin WOx flakes. To increase the field enhancement of such low-dimensional structures by a higher aspect ratio, two approaches were examined: (a) the MoS2 and WS2 nanotubes were attached individually by a focused ion beam with Pt on dry etched n-type Si pillars and (b) the WS2 flakes were grown directly on the surface of the (n-type and p-type) Si pillars. Integral field emission measurements were performed in a diode configuration with a 50 μm mica spacer in a vacuum chamber at pressures of about 10−9 mbar. At a voltage of 900 V (18 MV/m), the integral emission current from the nanotubes is up to 11 μA for the lateral mounted MoS2 and about 1.3 μA (1.0 μA) for the upright mounted WS2 (MoS2). The onset voltage for a current of 1 nA is about 550 V for MoS2 and 500 V for WS2, respectively. The voltage conversion factor is in the range of 6 × 104–8 × 104 cm−1 for the nanotubes. The mounted MoS2 flakes show a field emission current of about 6 μA at 18 MV/m in contrast to the directly grown WS2 flakes, which show a pronounced saturation regime and, therefore, a lower emission current of about 0.5 μA is reached at 1500 V (25 MV/m). The WS2 flakes show a two times higher (1 × 105 cm−1) voltage conversion factor in comparison to the MoS2 flakes (5 × 104 cm−1). The extracted characteristics of the current-limiting part show a difference in the behavior of the extracted current-limiting characteristics between the lateral (linear) and upright mounted (exponential) nanotubes and the MoS2 flakes. In contrast, the WS2 flakes show charge carrier depletion effects.

Real-space light-reflection mapping of atomically thin WSe2 flakes revealing the gradient local strain

The spatially continuous control of the physical properties in semiconductor materials is an important strategy in increasing electron-capturing or light-harvesting efficiencies, which is highly desirable for the application of optoelectronic devices including photodetectors, solar cells and biosensors. Unlike the multi-layer growth of chemical composition modulation, local strain offers a convenient way to continuously tune the physical properties of a single semiconductor layer, and open up new possibility for band engineering within the 2D plane. Here, we demonstrate that the gradient refractive index and bandgap can be generated in atomically thin transition metal dichalcogenide flakes due to the effect of thermal strain difference. A highly resolved confocal scanning optical microscopy is used to perform a real-space light-reflection mapping of suspended atomically thin WSe2 flakes at the low temperature of 4.2 K, in which the parabolic light-reflection profiles have been observed on suspended monolayer and bilayer WSe2 flakes. This finding is corroborated by our theoretical model which includes the effect of strain on both the refractive index and bandgap of nanostructures. The inhomogeneous local strain observed here will allow new device functionalities to be integrated within 2D layered materials, such as in-plane photodetectors and photovoltaic devices.

Fundamental limitation of van der Waals homoepitaxy by stacking fault formation in WSe2

As interest in layered van der Waals (vdW) materials keeps increasing, fundamental knowledge about their synthesis is gaining more value. The defect-free heteroepitaxial integration of vdW materials on large-area substrates is currently thoroughly being researched since it might encompass a successful transition to industrial applications. Transition metal dichalcogenides (TMDs) are considered as promising vdW materials. However, the electrical characterization of heteroepitaxially grown TMDs shows inferior performance as compared to exfoliated TMD flakes. This is mainly attributed to the high defect density resulting from the challenging heteroepitaxy. We have investigated in-depth the vdW homoepitaxy of the WSe2 TMD compound. We demonstrate that also for homoepitaxy, challenges such as the formation 60° twins need to be addressed. The presence of these stacking faults is associated with their very similar binding energy as revealed by density functional theory (DFT) calculations. Stacking faults are therefore identified as the fundamental limitation of lowly-defective multilayer TMD vdW epitaxy. Furthermore, a generalized model is developed that determines the defect density based on the stacking control and the nucleation density. This model therefore assesses and quantifies for the first time the ultimate defect density level that can be achieved with vdW epitaxially grown 2D materials.