Transition Metal Dichalcogenides Devices Research Articles

Locally Phase-Engineered MoTe2 for Near-Infrared Photodetectors.

Transition-metal dichalcogenides (TMDs) are ideal systems for two-dimensional (2D) optoelectronic applications owing to their strong light-matter interaction and various band gap energies. New techniques to modify the crystallographic phase of TMDs have recently been discovered, allowing the creation of lateral heterostructures and the design of all-2D circuitry. Thus, far, the potential benefits of phase-engineered TMD devices for optoelectronic applications are still largely unexplored. The dominant mechanisms involved in photocurrent generation in these systems remain unclear, hindering further development of new all-2D optoelectronic devices. Here, we fabricate locally phase-engineered MoTe2 optoelectronic devices, creating a metal (1T') semiconductor (2H) lateral junction and unveil the main mechanisms at play for photocurrent generation. We find that the photocurrent originates from the 1T'-2H junction, with a maximum at the 2H MoTe2 side of the junction. This observation, together with the nonlinear IV-curve, indicates that the photovoltaic effect plays a major role in the photon-to-charge current conversion in these systems. Additionally, the 1T'-2H MoTe2 heterojunction device exhibits a fast optoelectronic response over a wavelength range of 700-1100 nm, with a rise and fall times of 113 and 110 μs, respectively, 2 orders of magnitude faster when compared to a directly contacted 2H MoTe2 device. These results show the potential of local phase-engineering for all-2D optoelectronic circuitry.

Characteristics of secondary ions and their impact on single-event upset in TMD devices under proton irradiation

Transition metal dichalcogenide (TMD) materials are emerging candidates for next-generation electronics due to their unique properties, such as high carrier mobility and on/off ratios. However, their introduction may significantly alter single-event effects (SEEs) in devices compared to traditional silicon devices. This work investigates the SEE sensitivity of TMD devices under proton irradiation using the Geant4 simulation toolkit. Secondary ions generated by proton irradiation of TMD devices with different proton energies were simulated and analyzed. The energy deposition in the device's sensitive volume array was also examined. The results show that TMD devices are more susceptible to SEEs than silicon devices, and that their SEE sensitivity depends on the TMD material, proton energy, and critical charge. These findings provide valuable insights into the aerospace application of TMD material devices and the design of radiation-hardened TMD-based electronics.

(Invited) Exciton Transport in Strained 2D Semiconductors

Being atomically thin, flexible, and exhibiting considerable light emission and ultrafast non-equilibrium dynamics, semiconducting transition metal dichalcogenides (TMDs) have been considered as promising candidates for next-generation optoelectronic devices. The optical and electronic properties of TMDs are governed by a rich landscape of tightly bound excitons, including regular bright excitons, as well as optically inaccessible dark exciton states. Recently, strain engineering of monolayer TMDs has been introduced to tune their optical properties, such as the exciton transition energy, exciton-phonon coupling, or the Stokes shift [1-3].Transport of charge carriers is crucial for nanoelectronics. In conventional materials, electronic transport can be conveniently controlled by external electric fields. However, the tightly bound excitons, being neutral particles, are only weakly affected by electrical fields. We demonstrate that mechanical strain can also be used to manipulate the transport of excitons in TMDs. To this end, we apply homogeneous tensile strain to a WS2 monolayer by bending the substrate [1], which causes a redshift of the X0 exciton photoluminescence. By measuring the spatiotemporal photoluminescence after near-resonant excitation with femtosecond laser pulses, we map the spread of excitons and extract the strain-dependent diffusion coefficient [4].Furthermore, we demonstrate the propagation of excitons in an inhomogeneous strain landscape. We create inhomogeneous tensile strain in TMD monolayers by transferring them onto patterned substrates with nanopillars or by a nanoimprint technique [5]. Due to the redshift of the exciton resonances with applied strain, excitons are expected to move towards high-strain regions in an inhomogeneous strain field - the so-called "funneling" effect. We verify this behavior for the "bright" TMD material monolayer MoSe2. In the case of the "dark" monolayer WS2, we observe exactly the opposite effect. Here, the excitons are expelled from the high-strain regions ("anti-funneling") [6]. By comparing our experimental results with a microscopic theory, we explain this observation by the drift of momentum-dark KΛ excitons, which, in contrast to bright excitons, shift to higher energies with strain.Our joint experiment-theory study highlights the dominant role of momentum-dark excitons for the dynamics in monolayer TMDs and provides crucial design guidelines for TMD devices based on exciton transport.

The Role of Vacancy Dynamics in Two‐Dimensional Memristive Devices

AbstractTwo‐dimensional layered transition metal dichalcogenides (TMDCs) are promising memristive materials for neuromorphic computing systems. Despite extensive experimental work, the underlying switching mechanisms are still not understood, impeding progress in material and device functionality. This study reveals the dominant role of defect dynamics in the switching process of 2D TMDC materials. The switching process is governed by the formation and annihilation dynamics of a local vacancy depletion zone. It explains the distinct features of the device characteristics observed experimentally, including fundamentally different device behavior previously thought to originate from multiple mechanisms. Key influence factors are identified and discussed with a fully coupled and dynamic charge transport model for electrons, holes, and ionic point defects, including image‐charge‐induced Schottky barrier lowering (SBL). Thermal effects and local Joule heating are considered by coupling the transient heat transfer equation to the electronic properties. The model is validated with hysteresis and pulse measurements for various lateral 2D MoS2‐based devices, strongly corroborating the relevance of vacancy dynamics in TMDC devices and offering a new perspective on the switching mechanisms. The insights gained from this study can be used to extend the functional behavior of 2D TMDC memristive devices in future neuromorphic computing applications.

Atmospheric Degradation and Performance Recovery of Two‐Dimensional MoS2 Field Effect Transistor†

Comprehensive SummaryTwo‐dimensional (2D) transition metal dichalcogenides (TMDCs) showed great potentials in 2D nanoelectronic devices due to their abundant and unique properties. The performance stability of the 2D TMDCs devices turns into one of the keys for their practical applications but has been rarely explored. Here, we investigated stability of MoS2 devices in ambient condition and contributed the device performance degradation to the surface oxidation of the contact metals with low work function, which increased the contact barrier and hindered the electron injection. We developed a new approach to recover the performance of the aged devices through the selective doping of contacts with organolithium, which prolonged the lifetime of MoS2 devices. Our work not only provides important insights into the stability of 2D TMDCs devices, but also opens up a new avenue for optimizing the performance of 2D MoS2 devices.

Atomic-Scale Mechanisms of MoS2 Oxidation for Kinetic Control of MoS2/MoO3 Interfaces.

Oxidation of transition metal dichalcogenides (TMDs) occurs readily under a variety of conditions. Therefore, understanding the oxidation processes is necessary for successful TMD handling and device fabrication. Here, we investigate atomic-scale oxidation mechanisms of the most widely studied TMD, MoS2. We find that thermal oxidation results in α-phase crystalline MoO3 with sharp interfaces, voids, and crystallographic alignment with the underlying MoS2. Experiments with remote substrates prove that thermal oxidation proceeds via vapor-phase mass transport and redeposition, a challenge to forming thin, conformal films. Oxygen plasma accelerates the kinetics of oxidation relative to the kinetics of mass transport, forming smooth and conformal oxides. The resulting amorphous MoO3 can be grown with subnanometer to several-nanometer thickness, and we calibrate the oxidation rate for different instruments and process parameters. Our results provide quantitative guidance for managing both the atomic scale structure and thin-film morphology of oxides in the design and processing of TMD devices.

Concentration Phase Separation of Substitution-Doped Atoms in TMDCs Monolayer.

The density and spatial distribution of substituted dopants affect the transition metal dichalcogenides (TMDCs) materials properties. Previous studies have demonstrated that the density of dopants in TMDCs increases with the amount of doping, and the phenomenon of doping concentration difference between the nucleation center and the edge is observed, but the spatial distribution law of doping atoms has not been carefully studied. Here, it is demonstrated that the spatial distribution of dopants changes at high doping concentrations. The spontaneous formation of an interface with a steep doping concentration change is named concentration phase separation (CPS). The difference in the spatial distribution of dopants on both sides of the interface can be identified by an optical microscope. This is consistent with the results of spectral analysis and microstructure characterization of scanning transmission electron microscope. According to the calculation results of density functional theory, the chemical potential has two relatively stable energies as the doping concentration increases, which leads to the spontaneous formation of CPS. Understanding the abnormal phenomena is important for the design of TMDCs devices. This work has great significance in the establishment and improvement of the doping theory and the design of the doping process for 2D materials.

Atomically-thin single-photon sources for quantum communication

To date, quantum communication widely relies on attenuated lasers for secret key generation. In future quantum networks, fundamental limitations resulting from their probabilistic photon distribution must be overcome by using deterministic quantum light sources. Confined excitons in monolayers of transition metal dichalcogenides (TMDCs) constitute an emerging type of emitter for quantum light generation. These atomically thin solid-state sources show appealing prospects for large-scale and low-cost device integration, meeting the demands of quantum information technologies. Here, we pioneer the practical suitability of TMDC devices in quantum communication. We employ a WSe2 monolayer single-photon source to emulate the BB84 protocol in a quantum key distribution (QKD) setup and achieve click rates of up to 66.95 kHz and antibunching values down to 0.034—a performance competitive with QKD experiments using semiconductor quantum dots or color centers in diamond. Our work opens the route towards wider applications of quantum information technologies using TMDC single-photon sources.

Epitaxial van der Waals contacts of 2D TaSe2-WSe2 metal-semiconductor heterostructures.

The electronic contact between two-dimensional (2D) transition metal dichalcogenide (TMD) semiconductors and metal electrodes is a formidable challenge due to the undesired Schottky barrier, which severely limits the electrical performance of TMD devices and impedes the exploration of their unconventional physical properties and potential electronic applications. In this study, we report a two-step chemical vapor deposition (CVD) growth of 2D TaSe2-WSe2 metal-semiconductor heterostructures. Raman mapping confirms the precise spatial modulation of the as-grown 2D TaSe2-WSe2 heterostructures. Transmission electron microscopy (TEM) characterization reveals that this two-step method provides a high-quality and clean interface of the 2D TaSe2-WSe2 heterostructures. Meanwhile, the upper 1T-TaSe2 is formed heteroepitaxially on/around the pre-synthesized 2H-WSe2 monolayers, exhibiting an epitaxial relationship of (20-20)TaSe2//(20-20)WSe2 and [0001]TaSe2//[0001]WSe2. Furthermore, characterization studies using a Kelvin probe force microscope (KPFM) and electrical transport measurements present compelling evidence that the 2D metal-semiconductor heterostructures under investigation can improve the performance of electrical devices. These results bear substantial significance in augmenting the properties of field-effect transistors (FETs), leading to notable improvements in FET mobility and on/off ratio. Our study not only broadens the horizons of direct growth of high-quality 2D metal-semiconductor heterostructures but also sheds light on potential applications in future high-performance integrated circuits.

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.

One-dimensional bandgap modulation at continuous few-layer MoS2 steps

In pursuit of novel two-dimensional devices, lateral heterostructures based on transition metal dichalcogenides (TMDCs) have been intensively proposed and demonstrated. For instance, heterojunctions composed of TMDCs with different thicknesses function attractively in electronics and optoelectronics. Using scanning tunneling microscopy and spectroscopy, we resolved electronic structures of three types of few-layer MoS2 steps: flake edges, continuous bilayer–monolayer steps, and monolayers sitting on highly oriented pyrolytic graphite steps. Each type possesses unique bandgap features, including in-gap states and npn-like band alignment, which suggests modifiable 1D bandgaps via choices of edge conditions for the development of lateral TMDC devices.

Statistical Assessment of High-Performance Scaled Double-Gate Transistors from Monolayer WS2.

Scaling of monolayer transition metal dichalcogenide (TMD) field-effect transistors (FETs) is an important step toward evaluating the application space of TMD materials. Although some work on ultrashort channel monolayer (ML) TMD FETs has been published, there exist no comprehensive studies that assess their performance in a statistically relevant manner, providing critical insights into the impact of the device geometry. Part of the reason for the absence of such a study is the substantial variability of TMD devices when processes are not carefully controlled. In this work, we show a statistical study of ultrashort channel double-gated ML WS2 FETs exhibiting excellent device performance and limited device-to-device variations. From a detailed analysis of cross-sectional scanning transmission electron microscopy (STEM) images and careful technology computer aided design (TCAD) simulations, we evaluated, in particular, an unexpected deterioration of the subthreshold characteristics for our shortest devices. Two potential candidates for the observed behavior were identified, i.e., buckling of the TMD on the substrate and loss of gate control due to the source geometry and the high-k dielectric between the metal gate and the metal source electrode.

Research progress on improving the performance of MoS2 photodetector

Two-dimensional layered materials have attracted increasing attention due to their unique structures and outstanding mechanical and physical properties. Transition metal dichalcogenides (TMDs) possess unique physical properties and optical properties that meet the basic requirements of photodetectors. As representative TMDs, MoS2 has excellent mechanical properties due to its strong covalent bonds and great elasticity. The monolayer MoS2 has a direct bandgap of around 1.8 eV. In addition, MoS2-based optoelectronic devices have high switching ratio and carrier mobility. However, due to the characteristic of atomic-scale thickness, the light-harvesting ability of layered TMDs is very weak, which largely limits the responsivity and detection rate of photodetectors, thus inhibiting the practical application of such devices. The slow photo response rate is also a problem that often occurs in TMDs devices. Researchers have reported several strategies to improve the performance of TMDs-based photodetectors. At present, there are two main optimization schemes, namely surface modification, and heterostructure construction. The utilization of metal plasmon effect and the construction of heterojunctions are both effective means to improve the performance of MoS2 photodetectors. These schemes can improve the light absorption capability of MoS2 and broaden the range of light detection. However, there are also disadvantages of the complex processes and limited enhancement effects in large-area fabrication. Therefore, it is of vital significance to further explore the response range and performance of MoS2 photodetectors.

Epitaxy of NiTe2 on WS2 for the p-Type Schottky Contact and Increased Photoresponse.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have great potential applications in the electronic and optoelectronic devices. Nevertheless, due to the difficulty in the efficient doping of atomic-thickness TMDCs or Fermi level pinning (FLP) effects at the metal/semiconductor interface, most TMDC devices exhibit the n-type conduction polarity, which significantly limits their functional applications based on the p-n junction. Here, 2D semi-metal NiTe2 nanosheets were epitaxially grown on the WS2 monolayer by a two-step chemical vapor deposition route. The microstructure and optical characterizations confirm that the vertically stacked NiTe2/WS2 heterostructures are formed by van der Waals epitaxy. Interestingly, p-type WS2 field-effect transistors can be obtained with the hole mobility of ∼4.22 cm2/V·s, when the epitaxial NiTe2 sheets act as the source/drain electrodes. This is attributed to the decreased FLP effect and hence the low potential barrier for holes at the van der Waals contacts. Furthermore, the photodetectors based on the heterostructures show a 2 orders of magnitude increase in the switch ratio, responsivity, and detectivity and a 1 order of magnitude increase in the rise and decay speeds relative to those based on pristine WS2. This work paves the way to realize the p-type contact for monolayer WS2 with significantly enhanced optoelectronic performance.

Directly Visualizing Photoinduced Renormalized Momentum-Forbidden Electronic Quantum States in an Atomically Thin Semiconductor.

Resolving the momentum degree of freedom of photoexcited charge carriers and exploring the excited-state physics in the hexagonal Brillouin zone of atomically thin semiconductors have recently attracted great interest for optoelectronic technologies. We demonstrate a combination of light-modulated scanning tunneling microscopy and the quasiparticle interference (QPI) technique to offer a directly accessible approach to reveal and quantify the unexplored momentum-forbidden electronic quantum states in transition metal dichalcogenide (TMD) monolayers. Our QPI results affirm the large spin-splitting energy at the spin-valley-coupled Q valleys in the conduction band (CB) of a tungsten disulfide monolayer. Furthermore, we also quantify the photoexcited carrier density-dependent band renormalization at the Q valleys. Our findings directly highlight the importance of the excited-state distribution at the Q valley in the band renormalization in TMDs and support the critical role of the CB Q valley in engineering the quantum electronic valley degree of freedom in TMD devices.

Performance enhancement of WS2 transistors via double annealing

Herein, we report the double annealing strategy to improve the device performance of WS2 transistors fabricated using multilayer WS2 flakes on SiO2/p++-Si substrates. In the double annealing approach, the annealing is performed twice, both before and after electrode formation. The statistical analysis of 50 WS2 transistors indicated that, compared to the conventional single annealing, the double annealing increased the average field-effect mobility and reduced the average contact resistance. The enhanced device performance could be attributed to the improved interface quality between WS2 and the electrodes, owing to the removal of organic residues and desorption of surface adsorbents during the first annealing before the electrode formation. These results demonstrate the effectiveness of double annealing in enhancing the device performance of WS2 transistors, suggesting the important role of process optimization in fabricating WS2 transistors and other transition metal dichalcogenide devices.

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.

Illuminating the Electronic Properties of WS2 Polytypism with Electron Microscopy

AbstractTailoring the specific stacking sequence (polytypes) of layered materials represents a powerful strategy to identify and design novel physical properties. While nanostructures built upon transition‐metal dichalcogenides (TMDs) with either the 2H or 3R crystalline phases have been routinely studied, knowledge of TMD nanomaterials based on mixed 2H/3R polytypes is far more limited. In this work, mixed 2H/3R free‐standing WS2 nanostructures displaying a flower‐like configuration are fingerprinted by means of state‐of‐the‐art transmission electron microscopy. Their rich variety of shape‐morphology configurations is correlated with relevant local electronic properties such as edge, surface, and bulk plasmons. Machine learning is deployed to establish that the 2H/3R polytype displays an indirect band gap of . Further, high resolution electron energy‐loss spectroscopy reveals energy‐gain peaks exhibiting a gain‐to‐loss ratio greater than unity, a property that can be exploited for cooling strategies of atomically‐thin TMD nanostructures and devices built upon them. The findings of this work represent a stepping stone towards an improved understanding of TMD nanomaterials based on mixed crystalline phases.

Thickness Trends of Electron and Hole Conduction and Contact Carrier Injection in Surface Charge Transfer Doped 2D Field Effect Transistors.

One of the main limiting factors in the performance of devices based on two-dimensional (2D) materials is Fermi level pinning at the contacts, which creates Schottky barriers (SBs) that increase contact resistance and, for most transition metal dichalcogenides (TMDs), limit hole conduction. A promising method to mitigate these problems is surface charge transfer doping (SCTD), which places fixed charge at the surface of the material and thins the SBs by locally shifting the energy bands. We use a mild O2 plasma to convert the top few layers of a given TMD into a substoichiometric oxide that serves as a p-type SCTD layer. A comprehensive experimental study, backed by TCAD simulations, involving MoS2, MoSe2, MoTe2, WS2, and WSe2 flakes of various thicknesses exposed to different plasma times is used to investigate the underlying mechanisms responsible for SCTD. The surface charge at the top of the channel and the gate-modulated surface potential at the bottom are found to have competing effects on the channel potential, which results in a decrease in the doping-induced threshold shift and an increase in minimum OFF state current with increasing thickness. Additionally, an undoped channel region is shown to mitigate carrier injection issues in sufficiently thin flakes. Notably, the band movements underlying the SCTD effects are independent of the particular semiconductor material, SCTD strategy, and doping polarity. Consequently, our findings provide critical insights for the design of high-performance transistors for a wide range of materials and SCTD mechanisms including TMD devices with strong hole conduction.

Intrinsic and Extrinsic Defect-Related Excitons in TMDCs.

We investigate the excitonic peak associated with defects and disorder in low-temperature photoluminescence of monolayer transition metal dichalcogenides (TMDCs). To uncover the intrinsic origin of defect-related (D) excitons, we study their dependence on gate voltage, excitation power, and temperature in a prototypical TMDC monolayer MoS2. Our results suggest that D excitons are neutral excitons bound to ionized donor levels, likely related to sulfur vacancies, with a density of 7 × 1011 cm-2. To study the extrinsic contribution to D excitons, we controllably deposit oxygen molecules in situ onto the surface of MoS2 kept at cryogenic temperature. We find that, in addition to trivial p-doping of 3 × 1012 cm-2, oxygen affects the D excitons, likely by functionalizing the defect sites. Combined, our results uncover the origin of D excitons, suggest an approach to track the functionalization of TMDCs, to benchmark device quality, and pave the way toward exciton engineering in hybrid organic-inorganic TMDC devices.