Types Of Transition Metal Dichalcogenides Research Articles

Passively harmonic mode-locked erbium-doped fiber lasers based on PbSnS2 saturable absorbers

The two-dimensional (2D) material PbSnS2, a type of transition metal dichalcogenides (TMD), is a highly anisotropic layered compound with potential applications in ultrafast optics. We prepared PbSnS2 nanosheets by liquid phase exfoliation, attached them to microfibers to fabricate saturable absorbers (SAs) by optical deposition method, and successfully applied them to a passive erbium-doped fiber laser (EDFL). In addition, the saturable absorption properties of PbSnS2-based SA were confirmed using a balanced two-detector measurement system. The results demonstrate that the PbSnS2-based SA can realize different stable mode-locked states in the same EDFL cavity, including fundamental frequency conventional soliton and 15th harmonic mode-locked states. Among them, the laser produced fundamental frequency mode-locked state with a signal-to-noise ratio of 59.51 dB (6.58 MHz repetition frequency). The HML pulse with a maximum repetition frequency of 98.71 MHz (corresponding to the 15th harmonic) was obtained. The results demonstrate that PbSnS2 is a candidate material for generating ultrafast pulses and has excellent potential for application in ultrafast lasers.

Doping‐Induced Performance Improvement in ReS2 Field Effect Transistors: Exploring a Heterostructure with In2O3 Quantum Dots

AbstractRhenium disulfide (ReS2) is a type of transition metal dichalcogenides (TMDs) that has potential electronic and photoelectrical applications. However, limited research has been conducted on improving its electrical properties and understanding the effect of doping on ReS2‐based devices. In this study, the enhanced electrical and photoelectrical performance of a 2D/0D heterostructure constructed by decorating the In2O3 quantum dots (QDs) on a multilayer ReS2 field‐effect transistor (FET) is reported. The In2O3 QDs are characterized by using a transmission electron microscope, optical absorption, and photoluminescence spectroscopy. The n‐doping effects with improved mobility are clearly observed, which is attributed to the electron transfer induced by the relatively high conduction band level of In2O3 QDs. Owing to the channel migration of ReS2 and traps at the ReS2/In2O3 QDs interface, additional performance improvements are observed, including reduced contact resistance, improved subthreshold swing, and increased photoresponsivity; however, the photoresponse speed is decreased. In summary, the findings suggest a novel mixed‐dimensional heterostructure for enhancing the performance of ReS2 transistors and provide insights into doping‐induced channel migration for 2D materials.

Simultaneous Electrochemical Exfoliation and Functionalization of 2H-MoS2 for Supercapacitor Electrodes.

MoS2 is a promising semiconducting material that has been widely studied for applications in catalysis and energy storage. The covalent chemical functionalization of MoS2 can be used to tune the optoelectronic and chemical properties of MoS2 for different applications. However, 2H-MoS2 is typically chemically inert and difficult to functionalize directly and thus requires pretreatments such as a phase transition to 1T-MoS2 or argon plasma bombardment to introduce reactive defects. Apart from being inefficient and inconvenient, these methods can cause degradation of the desirable properties and introduce unwanted defects. Here, we demonstrate that 2H-MoS2 can be simultaneously electrochemically exfoliated and chemically functionalized in a facile and scalable procedure to fabricate functionalized thin (∼4 nm) MoS2 layers. The aryl diazonium salts used for functionalization have not only been successfully covalently grafted onto the 2H-MoS2, as verified by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy, but also aid the exfoliation process by increasing the interlayer spacing and preventing restacking. Electrochemical energy storage is one application area to which this material is particularly suited, and characterization of supercapacitor electrodes using this exfoliated and functionalized material revealed that the specific capacitance was increased by ∼25% when functionalized. The methodology demonstrated for the simultaneous production and functionalization of two-dimensional (2D) materials is significant, as it allows for control over the flake morphology with increased repeatability. This electrochemical functionalization technique could also be extended to other types of transition-metal dichalcogenides (TMDs), which are also typically chemically inert with different functional species to adjust to specific applications.

Highly Nonlinear Memory Selectors with Ultrathin MoS2/WSe2/MoS2 Heterojunction

AbstractResistive random access memory (RRAM) crossbar arrays require the highly nonlinear selector with high current density to address a specific memory cell and suppress leakage current through the unselected cell. 3D monolithic integration of RRAM array requires selector devices with a small footprint and low‐temperature processing for ultrahigh‐density data storage. Here, an ultrathin two‐terminal n‐p‐n selector with 2D transition metal dichalcogenides (TMDs) is designed by a low‐temperature transfer method. The van der Waals contact between transferred Au electrodes and TMDs reduces the Fermi level pinning and retains the intrinsic transport behavior of TMDs. The selector with a single type of TMD exhibits a trade‐off between current density and nonlinearity depending on the barrier height. By tuning the Schottky barrier height and controlling the thickness of p‐type WSe2 in MoS2/WSe2/MoS2 n‐p‐n selector for a punch‐through transport, the selector shows high nonlinearity (≈ 230) and high current density (2 × 103 A cm−2) simultaneously. The n‐p‐n selectors are further integrated with a bipolar hexagonal boron nitride memory and calculate the maximum crossbar size of the 2D material‐based one‐selector one‐resistor according to a 10% read margin, which offers the possible realization of future 3D monolithic integration.

Gum Arabic-mediated liquid exfoliation of transition metal dichalcogenides as photothermic anti-breast cancer candidates

Transition metal dichalcogenides (TMDs) have gained considerable attention for a broad range of applications, including cancer therapy. Production of TMD nanosheets using liquid exfoliation provides an inexpensive and facile route to achieve high yields. In this study, we developed TMD nanosheets using gum arabic as an exfoliating and stabilizing agent. Different types of TMDs, including MoS2, WS2, MoSe2, and WSe2 nanosheets, were produced using gum arabic and were characterized physicochemically. The developed gum arabic TMD nanosheets exhibited a remarkable photothermal absorption capacity in the near-infrared (NIR) region (808 nm and 1 W⋅cm−2). The drug doxorubicin was loaded on the gum arabic–MoSe2 nanosheets (Dox–G–MoSe2), and the anticancer activity was evaluated using MDA-MB-231 cells and a water-soluble tetrazolium salt (WST-1) assay, live and dead cell assays, and flow cytometry. Dox–G–MoSe2 significantly inhibited MDA-MB-231 cancer cell proliferation under the illumination of an NIR laser at 808 nm. These results indicate that Dox-G-MoSe2 is a potentially valuable biomaterial for breast cancer therapy.

Effect of Solution pH on the Synthesis of Two-Dimensional Molybdenum–Tungsten Sulfide Nanostructures

Compared with binary transition-metal dichalcogenides (TMDCs), ternary alloys or heterojunctions have more abundant properties. The spin-coating method has been widely used in the synthesis of TMDCs. However, there is still a lack of research on the effect of acidity and alkalinity of precursor solutions on the epitaxial growth of TMDCs. It is found that the MoxW1–xS2 ternary alloy is formed when an acidic solution of (NH4)2MoO4 and (NH4)2WO4 is used for spin-coating, while the MoS2/WS2 lateral heterojunction with a sharp boundary is formed when an alkaline solution of Na2MoO4, Na2WO4, and NaOH is used. According to the calculation, under alkaline conditions, sulfur atoms preferentially bind to MoO42– due to lower energy and finally form a lateral heterojunction. However, under acidic and neutral conditions, MoO42– and WO42– in the precursor solution will undergo a complex reaction, respectively. Because there is no significant difference in the binding energy of the reaction between the sulfur atom and two complexes, a ternary alloy will be formed. The controllable synthesis of different types of TMDCs can be achieved by regulating acidity and alkalinity.

N- and p-type doping of transition-metal dichalcogenides by Ar plasma treatment and its application in CMOS

Doping of two-dimensional (2D) semiconductors is necessary to achieve high performance and low power consumption in optoelectronic and logic devices. Herein, we report controllable p- and n-type doping of the transition-metal dichalcogenides (TMDs), tungsten diselenide (WSe2), and molybdenum ditelluride (MoTe2) via argon (Ar) plasma treatment. The doping of TMDs was tuned by controlling Ar plasma treatment conditions. The desired n-type doping in WSe2 and MoTe2 was obtained by applying a short treatment time, resulting in increased electron current and an upshift in binding energy. Owing to prolonged plasma treatment, abnormal p-type doping was achieved in WSe2 and MoTe2. Increased hole current, downshift in binding energy, appearance of oxygen bonds (O–W, Mo, Se, and Te), and redshift in Raman peaks revealed that the abnormal p-type doping behavior for WSe2 and MoTe2 was owing to considerable vacancies and edge defects induced in the top layer of TMDs by Ar plasma treatment. These were immediately occupied by oxygen atoms or oxidized to introduce oxygen doping when TMDs were exposed to air. The formation of a homogeneous oxide film on the top layer of TMDs was further demonstrated by the smooth surface and higher thickness of TMDs with heavy p-type doping compared to those of the pristine sample. A complementary metal-oxide-semiconductor (CMOS) inverter based on p- and n-WSe2 was demonstrated herein. Our study proposes a controllable way to modulate the doping type of TMDs, which has potential applications in the performance modulation of devices, design of novel device structures, and realization of 2D material-based logic circuits.

Sensitivity Enhancement of Hybrid Two-Dimensional Nanomaterials-Based Surface Plasmon Resonance Biosensor.

In this work, we designed structures based on copper nanosubstrate with graphene and two-dimensional transition metal dichalcogenides (TMDC) in order to achieve an ultrasensitive surface plasmon resonance biosensor. This system contains seven components: SF11 triangular prism, BK-7 glass, Chromium (Cr) adhesion layer, thin copper film, layers of one of the types of transition metal dichalcogenides: MoS2, MoSe2, WS2 or WSe2 (defined as MX2), graphene, sensing layer with biomolecular analyte. Copper was chosen as a plasmonic material because it has a higher conductivity than gold which is commonly used in plasmonic sensors. Moreover, copper is a cheap and widespread material that is easy to produce on a large scale. We have carried out both theoretical and numerical sensitivity calculations of these kinds of structures using the Goos–Hänchen (GH) shift method. GH shift is lateral position displacement of the p-polarized reflected beam from a boundary of two media having different indices of refraction under total internal reflection condition and its value can be retrieved from the phase change of the beam. The SPR signal based on the GH shift is much more sensitive compared to other methods, including angular and wavelength scanning, due to much more abrupt phase change of the SPR reflected light than its intensity ones. By optimizing the parameters of the SPR sensing substrate, such as thickness of copper, number of layers of 2D materials and excitation wavelength, we theoretically showed an enhanced sensitivity with a detection limit 10−9 refractive index unit (RIU).

Giant Effects of Interlayer Interaction on Valence-Band Splitting in Transition Metal Dichalcogenides

Understanding the origin of valence band maxima (VBM) splitting in transition metal dichalcogenides (TMDs) is important because it governs the unique spin and valley physics in monolayer and multilayer TMDs. In this work, we present our systematic study of VBM splitting ($\Delta$) in atomically thin MoS$_2$ and WS$_2$ by employing photocurrent spectroscopy as we change the temperature and the layer numbers. We found that VBM splitting in monolayer MoS$_2$ and WS$_2$ depends strongly on temperature, which contradicts the theory that spin-orbit coupling solely determines the VBM splitting in monolayer TMDs. We also found that the rate of change of VBM splitting with respect to temperature ($m=\frac{\partial\Delta}{\partial T}$) is the highest for monolayer (-0.14 meV/K for MoS$_2$) and the rate decreases as the layer number increases ($m ~ 0$ meV/K for 5 layers MoS$_2$). We performed density functional theory (DFT) and the GW with Bethe-Salpeter Equation (GW-BSE) calculations to determine the electronic band structure and optical absorption for a bilayer MoS$_2$ with different interlayer separations. Our simulations agree with the experimental observations and demonstrate that the temperature dependence of VBM splitting in atomically thin monolayer and multilayer TMDs originates from the changes in the interlayer coupling strength between the neighboring layers. By studying two different types of TMDs and many different layer thicknesses, we also demonstrate that VBM splitting also depends on the layer numbers and type of transition metals. Our study will help understand the role spin-orbit coupling and interlayer interaction play in determining the VBM splitting in quantum materials and develop next-generation devices based on spin-orbit interactions.

Molecular Dopant-Dependent Charge Transport in Surface-Charge-Transfer-Doped Tungsten Diselenide Field Effect Transistors.

The controllability of carrier density and major carrier type of transition metal dichalcogenides(TMDCs) is critical for electronic and optoelectronic device applications. To utilize doping in TMDC devices, it is important to understand the role of dopants in charge transport properties of TMDCs. Here, the effects of molecular doping on the charge transport properties of tungsten diselenide (WSe2 ) are investigated using three p-type molecular dopants, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 -TCNQ), tris(4-bromophenyl)ammoniumyl hexachloroantimonate (magic blue), and molybdenum tris(1,2-bis(trifluoromethyl)ethane-1,2-dithiolene) (Mo(tfd-COCF3 )3 ). The temperature-dependent transport measurements show that the dopant counterions on WSe2 surface can induce Coulomb scattering in WSe2 channel and the degree of scattering is significantly dependent on the dopant. Furthermore, the quantitative analysis revealed that the amount of charge transfer between WSe2 and dopants is related to not only doping density, but also the contribution of each dopant ion toward Coulomb scattering. The first-principles density functional theory calculations show that the amount of charge transfer is mainly determined by intrinsic properties of the dopant molecules such as relative frontier orbital positions and their spin configurations. The authors' systematic investigation of the charge transport of doped TMDCs will be directly relevant for pursuing molecular routes for efficient and controllable doping in TMDC nanoelectronic devices.

Vertically Aligned MoS2 with In-Plane Selectively Cleaved Mo-S Bond for Hydrogen Production.

Perturbing the periodic electronic structure of the MoS2 basal plane via vacancy engineering offers an opportunity to explore its intrinsic activity. A significant challenge is the design of vacancy states, which include its type, distribution, and accessibility. Here, well-dispersed and vertically aligned MoS2 nanosheets with an in-plane selectively cleaved Mo-S bond on a carbon matrix (c-MoS2-C) have been prepared by a self-engaged strategy, which synergistically realizes uniform vacancy manufacturing and three-dimensional (3D) self-assembly of the defective MoS2 nanosheets. X-ray adsorption spectroscopy investigation confirms that the cleaved MoS2 basal plane generates newly active edge sites, where the Mo centers feature unsaturated coordination geometry. Theoretical calculations reveal that the exposed interior edge Mo sites represent new active centers for hydrogen adsorption/desorption. As expected, the synthesized c-MoS2-C exhibits markedly enhanced hydrogen evolution activity and superior stability. This in-plane activation strategy could be extended to other types of transition-metal dichalcogenides and catalytic reaction systems.

Probing the structure and composition of van der Waals heterostructures using the nonlocality of Dirac plasmons in the terahertz regime

Dirac plasmons in graphene are very sensitive to the dielectric properties of the environment. We show that this can be used to probe the structure and composition of van der Waals heterostructures (vdWh) put underneath a single graphene layer. In order to do so, we assess vdWh composed of hexagonal boron nitride and different types of transition metal dichalcogenides (TMDs). By performing realistic simulations that account for the contribution of each layer of the vdWh separately and including the importance of the substrate phonons, we show that one can achieve single-layer resolution by investigating the nonlocal nature of the Dirac plasmon-polaritons. The composition of the vdWh stack can be inferred from the plasmon-phonon coupling once it is composed by more than two TMD layers. Furthermore, we show that the bulk character of TMD stacks for plasmonic screening properties in the terahertz regime is reached only beyond 100 layers.

Diode-Pumped Solid-State Q-Switched Laser with Rhenium Diselenide as Saturable Absorber

We report a solid-state passively Q-switched Nd:YVO4 laser adopting rhenium diselenide (ReSe2) as saturable absorber (SA) materials. ReSe2 belongs to a type of transition metal dichalcogenides (TMDs) materials and it has the weak-layered dependent feature beneficial for the preparation of few-layer materials. The few-layer ReSe2 was prepared by ultrasonic exfoliation method. Using a power-dependent transmission experiment, its modulation depth and saturation intensity were measured to be 1.89% and 6.37 MW/cm2. Pumped by diode laser and based on few-layer ReSe2 SA, the Q-switched Nd:YVO4 laser obtained the shortest Q-switched pulse width of 682 ns with the highest repetition rate of 84.16 kHz. The maximum average output power was 125 mW with the slope efficiency of 17.27%. Our experiment, to the best of our knowledge, is the first demonstration that used ReSe2 as SA materials in an all-solid-state laser. The results show that the few-layer ReSe2 owns the nonlinear saturable absorption properties and it has the capacity to act as SA in an all-solid-state laser.

Adjustable Intermolecular Interactions Allowing 2D Transition Metal Dichalcogenides with Prolonged Scavenging Activity for Reactive Oxygen Species.

There is an increasing demand for control over the dimensions and functions of transition metal dichalcogenides (TMDs) in aqueous solution toward biological and medical applications. Herein, an approach for the exfoliation and functionalization of TMDs in water via modulation of the hydrophobic interaction between poly(ε-caprolactone)-b-poly(ethylene glycol) (PCL-b-PEG) and the basal planes of TMDs is reported. Decreasing the hydrophobic PCL length of PCL-b-PEG from 5000 g mol-1 (PCL5000 ) to 460 g mol-1 (PCL460 ) significantly increases the exfoliation efficiency of TMD nanosheets because the polymer-TMD hydrophobic interaction becomes dominant over the polymer-polymer interaction. The TMD nanosheets exfoliated by PCL460 -b-PEG5000 (460-WS2 , 460-WSe2 , 460-MoS2 , and 460-MoSe2 ) show excellent and prolonged scavenging activity for reactive oxygen species (ROS), but each type of TMD displays a different scavenging tendency against hydroxyl, superoxide, and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radicals. A mechanistic study based on electron paramagnetic resonance spectroscopy and density functional theory simulations suggests that radical-mediated oxidation of TMDs and hydrogen transfer from the oxidized TMDs to radicals are crucial steps for ROS scavenging by TMD nanosheets. As-prepared 460-TMDs are able to effectively scavenge ROS in HaCaT human keratinocytes, and also exhibit excellent biocompatibility.

Exploration of channel width scaling and edge states in transition metal dichalcogenides

We explore the impact of edge states in three types of transition metal dichalcogenides (TMDs), namely metallic Td-phase WTe2 and semiconducting 2H-phase MoTe2 and MoS2, by patterning thin flakes into ribbons with varying channel widths. No obvious charge depletion at the edges is observed for any of these three materials, in contrast to observations made for graphene nanoribbon devices. The semiconducting ribbons are characterized in a three-terminal field-effect transistor (FET) geometry. In addition, two ribbon array designs have been carefully investigated and found to exhibit current levels higher than those observed for conventional one-channel devices. Our results suggest that device structures incorporating a high number of edges can improve the performance of TMD FETs. This improvement is attributed to a higher local electric field, resulting from the edges, increasing the effective number of charge carriers, and the absence of any detrimental edge-related scattering.

Concurrent Synthesis of High‐Performance Monolayer Transition Metal Disulfides

To date, the chemical vapor deposition (CVD) approach has been widely used for the growth of transition metal dichalcogenides (TMDs). However, the reported CVD methods to synthesize TMDs cannot be used to grow more than one type of TMDs. This work reports a promising CVD technique to concurrently synthesize multiple monolayer transition metal disulfides once. The optoelectrical characterization and high‐resolution transmission electron microscopy show the high quality of monolayer crystals, and, more importantly, there is no mixing between different precursors during the growth process, which has been investigated by considering the gas flow dynamics and concentration distribution of precursors in our setup. This strategy indicates the promising future for the batch production of 2D materials and the concurrent synthesis techniques in standard state‐of‐the‐art complementary metal‐oxide‐semiconductor (CMOS) fabrication technology.

In Vivo Long-Term Biodistribution, Excretion, and Toxicology of PEGylated Transition-Metal Dichalcogenides MS2 (M = Mo, W, Ti) Nanosheets.

With unique 2D structures and intriguing physicochemical properties, various types of transition metal dichalcogenides (TMDCs) have attracted much attention in many fields including nanomedicine. Hence, it is of great importance to carefully study the in vivo biodistribution, excretion, and toxicology profiles of different TMDCs, and hopefully to identify the most promising type of TMDCs with low toxicity and fast excretion for further biomedical applications. Herein, the in vivo behaviors of three representative TMDCs including molybdenum dichalcogenides (MoS2), tungsten dichalcogenides (WS2), and titanium dichalcogenides (TiS2) nanosheets are systematically investigated. Without showing significant in vitro cytotoxicity, all the three types of polyethylene glycol (PEG) functionalized TMDCs show dominate accumulation in reticuloendothelial systems (RES) such as liver and spleen after intravenous injection. In marked contrast to WS2‐PEG and TiS2‐PEG, which show high levels in the organs for months, MoS2‐PEG can be degraded and then excreted almost completely within one month. Further degradation experiments indicate that the distinctive in vivo excretion behaviors of TDMCs can be attributed to their different chemical properties. This work suggests that MoS2, among various TMDCs, may be particularly interesting for further biomedical applications owning to its low toxicity, capability of biodegradation, and rapid excretion.