Multilayer Transition Metal Dichalcogenides Research Articles

Indirect-To-Direct Bandgap Crossover and Room-Temperature Valley Polarization of Multilayer MoS2 Achieved by Electrochemical Intercalation.

Monolayer (1L) group VI transition metal dichalcogenides (TMDs) exhibit broken inversion symmetry and strong spin-orbit coupling, offering promising applications in optoelectronics and valleytronics. Despite their direct bandgap, high absorption coefficient, and spin-valley locking in K or K' valleys, the ultra-short valley lifetime limits their room-temperature applications. In contrast, multilayer TMDs, with more absorptive layers, sacrifice the direct bandgap and valley polarization upon gaining inversion symmetry from the bilayer structure. It is demonstrated that multilayer molybdenum disulfide (MoS2) can maintain 1) a structure with broken inversion symmetry and strong spin-orbit coupling, 2) a direct bandgap with high photoluminescence (PL) intensity, and 3) stable valley polarization up to room temperature. Through the intercalation of organic 1-ethyl-3-methylimidazolium (EMIM+) ions, multilayer MoS2 not only exhibits layer decoupling but also benefits from an electron doping effect. This results in a hundredfold increase in PL intensity and stable valley polarization, achieving 55% and 16% degrees of valley polarization at 3 K and room temperature, respectively. The persistent valley polarization at room temperature, due to interlayer decoupling and trion dominance facilitated by a gate-free method, opens up potential applications in valley-selective optoelectronics and valley transistors.

Toward Mass Production of Transition Metal Dichalcogenide Solar Cells: Scalable Growth of Photovoltaic-Grade Multilayer WSe2 by Tungsten Selenization.

Semiconducting transition metal dichalcogenides (TMDs) are promising for high-specific-power photovoltaics due to their desirable band gaps, high absorption coefficients, and ideally dangling-bond-free surfaces. Despite their potential, the majority of TMD solar cells to date are fabricated in a nonscalable fashion, with exfoliated materials, due to the lack of high-quality, large-area, multilayer TMDs. Here, we present the scalable, thickness-tunable synthesis of multilayer WSe2 films by selenizing prepatterned tungsten with either solid-source selenium at 900 °C or H2Se precursors at 650 °C. Both methods yield photovoltaic-grade, wafer-scale WSe2 films with a layered van der Waals structure and superior characteristics, including charge carrier lifetimes up to 144 ns, over 14× higher than those of any other large-area TMD films previously demonstrated. Simulations show that such carrier lifetimes correspond to ∼22% power conversion efficiency and ∼64 W g-1 specific power in a packaged solar cell, or ∼3 W g-1 in a fully packaged solar module. The results of this study could facilitate the mass production of high-efficiency multilayer WSe2 solar cells at low cost.

Analysis of the heterojunction band offset of h-BN/TMDCs

In order to analyze the effect of the chalcogen on the band alignment of the Transition metal dichalcogenides (TMDCs) and hexagonal Boron Nitride (h-BN) heterojunction, we fabricated the h-BN/TMDCs heterojunction by vertically stacking mono-layer h-BN and multi-layer TMDCs by the wet transfer method. The four heterojunctions are h-BN/WS2, h-BN/WSe2, h-BN/MoS2 and h-BN/MoSe2. X-ray photoelectron spectroscopy (XPS) has been employed to ascertain the Valence Band Offset (VBO) at the junctions created among these heterojunctions. All heterojunction band alignment styles are type-I. When the chalcogen changes from S to Se, the heterojunction VBO values increase. Specifically, in case of h-BN/WS2 and h-BN/WSe2 the VBO is 2.42 eV and 2.81 eV, respectively, and the magnitude of the difference is 0.39 eV. In the same case for h-BN/MoS2 and h-BN/MoSe2 the VBO is 2.52 eV and 2.55 eV, respectively, and the magnitude of the difference is 0.03 eV. The aforementioned research has obtained the band alignment for four heterojunctions, which provides a valuable reference for the design and analysis of the correlation devices in the future.

Optical Enhancement of Indirect Bandgap 2D Transition Metal Dichalcogenides for Multi-Functional Optoelectronic Sensors.

The unique electrical and optical properties of transition metal dichalcogenides (TMDs) make them attractive nanomaterials for optoelectronic applications, especially optical sensors. However, the optical characteristics of these materials are dependent on the number of layers. Monolayer TMDs have a direct bandgap that provides higher photoresponsivity compared to multilayer TMDs with an indirect bandgap. Nevertheless, multilayer TMDs are more appropriate for various photodetection applications due to their high carrier density, broad spectral response from UV to near-infrared, and ease of large-scale synthesis. Therefore, this review focuses on the modification of the optical properties of devices based on indirect bandgap TMDs and their emerging applications. Several successful developments in optical devices are examined, including band structure engineering, device structure optimization, and heterostructures. Furthermore, it introduces cutting-edge techniques and future directions for optoelectronic devices based on multilayer TMDs.

Pressure Dependence of Intra- and Interlayer Excitons in 2H-MoS2 Bilayers.

The optical and electronic properties of multilayer transition metal dichalcogenides differ significantly from their monolayer counterparts due to interlayer interactions. The separation of individual layers can be tuned in a controlled way by applying pressure. Here, we use a diamond anvil cell to compress bilayers of 2H-MoS2 in the gigapascal range. By measuring optical transmission spectra, we find that increasing pressure leads to a decrease in the energy splitting between the A and the interlayer exciton. Comparing our experimental findings with ab initio calculations, we conclude that the observed changes are not due to the commonly assumed hydrostatic compression. This effect is attributed to the MoS2 bilayer adhering to the diamond, which reduces the in-plane compression. Moreover, we demonstrate that the distinct real-space distributions and resulting contributions from the valence band account for the different pressure dependencies of the inter- and intralayer excitons in compressed MoS2 bilayers.

Ultrafast Hidden Spin Polarization Dynamics of Bright and Dark Excitons in 2H-WSe_{2}.

We performed spin-, time- and angle-resolved extreme ultraviolet photoemission spectroscopy of excitons prepared by photoexcitation of inversion-symmetric 2H-WSe_{2} with circularly polarized light. The very short probing depth of XUV photoemission permits selective measurement of photoelectrons originating from the top-most WSe_{2} layer, allowing for direct measurement of hidden spin polarization of bright and momentum-forbidden dark excitons. Our results reveal efficient chiroptical control of bright excitons' hidden spin polarization. Following optical photoexcitation, intervalley scattering between nonequivalent K-K^{'} valleys leads to a decay of bright excitons' hidden spin polarization. Conversely, the ultrafast formation of momentum-forbidden dark excitons acts as a local spin polarization reservoir, which could be used for spin injection in van der Waals heterostructures involving multilayer transition metal dichalcogenides.

Modelling the structural disorder in trigonal-prismatic coordinated transition metal dichalcogenides.

Trigonal-prismatic coordinated transition metal dichalcogenides (TMDCs) are formed from stacked (chalcogen)-(transition metal)-(chalcogen) triple layers, where the chemical bond is covalent within the triple layers and van der Waals (vdW) forces are effective between the layers. Bonding is at the origin of the great interest in these compounds, which are used as 2D materials in applications such as catalysis, electronics, photoelectronics, sensors, batteries and thermoelectricity. This paper addresses the issue of modelling the structural disorder in multilayer TMDCs. The structural model takes into account stacking faults, correlated displacement of atoms and average crystallite size/shape, and is assessed by simulation of the X-ray diffraction pattern and fitting to the experimental data relative to a powdered sample of MoS2 exfoliated and restacked via lithiation. From fitting, an average crystallite size of about 50 Å, nearly spherical crystallites and a definite probability of deviation from the fully eclipsed atomic arrangement present in the ordered structure are determined. The increased interlayer distance and correlated intralayer and interlayer atomic displacement are attributed to the presence of lithium intercalated in the vdW gap between triple layers (Li/Mo molar ratio of about 0.06). The model holds for the whole class of trigonal-prismatic coordinated TMDCs, and is suitably flexible to take into account different preparation routes.

Multilayer In-Plane Heterostructures Based on Transition Metal Dichalcogenides for Advanced Electronics.

In-plane heterostructures of transition metal dichalcogenides (TMDCs) have attracted much attention for high-performance electronic and optoelectronic devices. To date, mainly monolayer-based in-plane heterostructures have been prepared by chemical vapor deposition (CVD), and their optical and electrical properties have been investigated. However, the low dielectric properties of monolayers prevent the generation of high concentrations of thermally excited carriers from doped impurities. To solve this issue, multilayer TMDCs are a promising component for various electronic devices due to the availability of degenerate semiconductors. Here, we report the fabrication and transport properties of multilayer TMDC-based in-plane heterostructures. The multilayer in-plane heterostructures are formed through CVD growth of multilayer MoS2 from the edges of mechanically exfoliated multilayer flakes of WSe2 or NbxMo1-xS2. In addition to the in-plane heterostructures, we also confirmed the vertical growth of MoS2 on the exfoliated flakes. For the WSe2/MoS2 sample, an abrupt composition change is confirmed by cross-sectional high-angle annular dark-field scanning transmission electron microscopy. Electrical transport measurements reveal that a tunneling current flows at the NbxMo1-xS2/MoS2 in-plane heterointerface, and the band alignment is changed from a staggered gap to a broken gap by electrostatic electron doping of MoS2. The formation of a staggered gap band alignment of NbxMo1-xS2/MoS2 is also supported by first-principles calculations.

Surface excitons in multilayer transition metal dichalcogenides in the ground state

We have performed theoretical study on the properties of excitons in multilayer transition metal dichalcogenides (TMDs) in the ground state by using the methods of linear combination operator and unitary transformation. It was found that the LO phonon frequency and exciton self-trapping energy (Etr) are significantly affected by the number of layers (N) when N≤10, when N>10, however, the effect is not obvious. On the other hand, the effect of N on exciton effective potential (Veff) is not obvious.

Bound states in the continuum in all-van der Waals photonic crystals: a route enabling electromagnetically induced transparency.

Recent studies have demonstrated that multilayer transition metal dichalcogenides can serve as promising building blocks for creating new kinds of resonant optical nanostructures due to their very high refractive indices. However, most of such studies have focused on excitonic regimes of light-material interaction, while there are few on the low-loss region below the bandgap. Here, we conceptually propose all-van der Waals photonic crystals made of electronically bulk MoS2 and h-BN, designed to operate in the telecom wavelengths. And we demonstrate that, due to extremely low absorption loss and destructive interaction between symmetry-protected and resonance-trapped bound states in the continuum, high-quality factor transmission peaks associated with electromagnetically induced transparency (EIT) are observed, thus rendering our proposed structures highly useful for applications like slow light and optical sensing. Furthermore, EIT-like effects are demonstrated in well-engineered MoS2 nanostructures with broken symmetry. We argue that this work is not only of significance for light harvesting in nanostructured van der Waals materials, but provides also a simple path of constructing classical analogues of EIT using dielectric photonic crystals.

Disorder-induced two-dimensional metal-insulator transition in moiré transition metal dichalcogenide multilayers

We develop a minimal theory for the recently observed metal-insulator transition (MIT) in two-dimensional (2D) moir\'e multilayer transition metal dichalcogenides (mTMD) using Coulomb disorder in the environment as the underlying mechanism. In particular, carrier scattering by random charged impurities leads to an effective 2D MIT approximately controlled by the Ioffe-Regel criterion, which is qualitatively consistent with the experiments. We find the necessary disorder to be around $5$-$10\times10^{10}$cm$^{-2}$ random charged impurities in order to quantitatively explain much, but not all, of the observed MIT phenomenology as reported by two different experimental groups. Our estimate is consistent with the known disorder content in TMDs.

Simulations of ultrathin monolayer/multilayer molybdenum disulfide heterojunction solar cell

Ultrathin solar cell has good potential in photovoltaics, monolayer and multilayer transition metal dichalcogenide materials could be used to make ultrathin solar cell because of their high absorption coefficients. The photovoltaic characteristics of monolayer MoS2/multilayer MoS2 vertical heterojunction ultrathin solar cell was calculated in this work based on SCAPS simulation software, monolayer MoS2 was used to make window layers and transparent conducting layers at the same time, multilayer MoS2 was used to make absorber layer. The highest efficiency of the cell with the thickness of 200 nm could reach 16.8% when the lifetime of multilayer MoS2 was larger than 250 ns, the electron and hole mobility of multilayer MoS2 was larger than 14 cm2/V, the recombination velocity of monolayer/multilayer MoS2 interface was smaller than 1 × 106 cm/s. The transmittance of the cell with the thickness of 200 nm approached 1 when wavelength was larger than 740 nm. Thus, monolayer/multilayer MoS2 vertical heterojunction solar cell has good potential in semitransparent solar cell, and the cell could be used as the top cell of silicon based tandem cell.

Thermal properties of single-layer MoS2-WS2 alloys enabled by machine-learned interatomic potentials.

Two-dimensional (2D) quantum materials are poised to transform conventional electronics for a wide spectrum of applications that will encompass chemical sciences. For the study of thermal transport in single-layer (1L) or multi-layer transition metal dichalcogenides (TMDs), this work explores the combination of density functional theory (DFT) and algorithmic training for the generation of a moment tensor potential (MTP) that models 1L-MoS2, 1L-WS2 and their alloys, and demonstrates a synergy of theoretical techniques that is anticipated to play an important role in the field. From a high-performance computing perspective, these yield very convenient inter-atomic (or inter-molecular in other contexts) potentials that are useful to predict the response of quantum materials to thermal perturbations, or other driving forces. We show that our trained MTP functions successfully describe vibrational properties of the systems, and their thermal conductivities. The trained potential displays consistent agreement with DFT calculations, as well as the Stillinger-Weber (SW) potential. We also find that the thermal conductivity of the 2D alloys is little affected by sulfur vacancies. This is a behavior that may aid the fine-tuning of material's thermal properties for heat management and energy storage and conversion applications.

Mechanical scanning probe lithography of nanophotonic devices based on multilayer TMDCs

In this work, we demonstrate the possibility of using mechanical Scanning probe lithography (m-SPL) for fabricating nanophotonic devices based on multilayered transition metal dichalcogenides (TMDCs). By m-SPM, we created a nanophotonic resonator from a 70-nm thick MoSe2 flake transferred on Si/Au substrate. The optical properties of the created structure were investigated by measuring microphotoluminescence. The resonator exhibits four resonance PL peaks shifted in the long-wavelength area from the flake PL peak. Thus, here we demonstrate that m-SPL is a high-precision lithography method suitable for creating nanophotonic devices based on multilayered TMDCs.

The role of device asymmetries and Schottky barriers on the helicity-dependent photoresponse of 2D phototransistors

Circular photocurrents (CPC), namely circular photogalvanic (CPGE) and photon drag effects, have recently been reported both in monolayer and multilayer transition metal dichalcogenide (TMD) phototransistors. However, the underlying physics for the emergence of these effects are not yet fully understood. In particular, the emergence of CPGE is not compatible with the D3h crystal symmetry of two-dimensional TMDs, and should only be possible if the symmetry of the electronic states is reduced by influences such as an external electric field or mechanical strain. Schottky contacts, nearly ubiquitous in TMD-based transistors, can provide the high electric fields causing a symmetry breaking in the devices. Here, we investigate the effect of these Schottky contacts on the CPC by characterizing the helicity-dependent photoresponse of monolayer MoSe2 devices both with direct metal-MoSe2 Schottky contacts and with h-BN tunnel barriers at the contacts. We find that, when Schottky barriers are present in the device, additional contributions to CPC become allowed, resulting in emergence of CPC for illumination at normal incidence.

Hybrid exciton-plasmon-polaritons in van der Waals semiconductor gratings

Van der Waals materials and heterostructures that manifest strongly bound exciton states at room temperature also exhibit emergent physical phenomena and are of great promise for optoelectronic applications. Here, we demonstrate that nanostructured, multilayer transition metal dichalcogenides (TMDCs) by themselves provide an ideal platform for excitation and control of excitonic modes, paving the way to exciton-photonics. Hence, we show that by patterning the TMDCs into nanoresonators, strong dispersion and avoided crossing of exciton, cavity photons and plasmon polaritons with effective separation energy exceeding 410 meV can be controlled with great precision. We further observe that inherently strong TMDC exciton absorption resonances may be completely suppressed due to excitation of hybrid light-matter states and their interference. Our work paves the way to the next generation of integrated exciton optoelectronic nano-devices and applications in light generation, computing, and sensing.

Substitutional Fluorine Doping of Large-Area Molybdenum Disulfide Monolayer Films for Flexible Inverter Device Arrays.

Reliable and controllable doping of transition metal dichalcogenides (TMDCs) is a mandatory requirement for practical large-scale electronic applications. However, most of the literature on the doping methodologies of TMDCs has focused on n-type doping and multilayer TMDC rather than a monolayer one enabling large-scale growth. Herein, we report substitutional fluorine doping of a chemical vapor deposition (CVD)-grown molybdenum disulfide (MoS2) monolayer film using a delicate SF6 plasma treatment. Our SF6-treated MoS2 monolayer shows a p-type doping effect with fluorine substitution. The doping concentration is controlled by the plasma treatment time (2-4.9 atom %) while maintaining the structural integrity of the MoS2 monolayer. Such reliable and tunable substitutional doping is attributed to preventing direct ion bombardment to the MoS2 monolayer by our gentle plasma treatment system. Finally, we fabricated MoS2 homojunction flexible inverter device arrays based on the pristine and SF6-treated MoS2 monolayer. A clear switching behavior is observed, and the voltage gain is approximately 8 at an applied VDD of 2 V, which is comparable to that of CVD-grown MoS2-based inverter devices reported previously. Obtained voltage gain is also stable even after 500 bending cycles at an applied strain of 0.5%.

Optical material anisotropy in high-index transition metal dichalcogenide Mie nanoresonators

Resonant optical antennas provide unprecedented opportunities to control light on length scales far below the diffraction limit. Recent studies have demonstrated that nanostructures made of multilayer transition metal dichalcogenides (TMDCs) can exhibit well-defined and intense Mie resonances in the visible to the near-infrared spectral range. These resonances are realizable because the TMDC materials exhibit very high in-plane refractive indices, in fact higher than what is found in typical high-index dielectric materials like Si or GaAs. However, their out-of-plane refractive indices are comparatively low. Here we experimentally and theoretically investigate how this unusually large material anisotropy influences the optical response of individual TMDC nanoresonators made of MoS 2 . We find that anisotropy strongly affects the far-field optical response of the resonators, as well as complex interference effects, such as anapole and resonant Kerker conditions. Moreover, we show that it is possible to utilize the material anisotropy to probe the vectorial nature of the nanoresonator internal near fields. Specifically, we show that Raman spectra originating from individual MoS 2 nanoresonators exhibit mode-specific anisotropic enhancement factors that vary with the nanoresonator size and correlate with specific modes supported at resonance. Our study indicates that exploring material anisotropy in novel high-index dielectrics may lead to new nanophotonic effects and applications.

Density functionals combined with van der Waals corrections for graphene adsorbed on layered materials

Standard density functionals like Perdew-Burke-Ernzerhof (PBE) or Strongly Constrained and Appropriately Normed (SCAN) need a correction to account for long-range van der Waals (vdW) interaction. The damped Zaremba-Kohn model (dZK) [J. Tao, H. Tang, A. Patra, P. Bhattarai, and J. P. Perdew, Phys. Rev. B 97, 165403 (2018)] starts from a formula for the vdW interaction of a distant atom with a solid surface, both with known dielectric properties, damps this formula at short range, and then treats an adsorbed molecule or atomic layer as a collection of renormalized atoms. We extend this model to graphene adsorbed on semiconducting layered materials [bulk graphite and hBN, and multilayer transition metal dichalcogenides (TMD)] by including the ${C}_{4}$ asymptotic term and multiple electrostatic image effects due to the two surfaces of the substrate slabs in the vdW calculations. The resulting SCAN-vdW-dZK and PBE-vdW-dZK give approximately the same results for the systems considered here, in agreement with available reference values. The predicted binding energies are roughly 25% lower than those from SCAN+rVV10 (revised Vydrov and Van Voorhis 2010), and $\ensuremath{\sim}15%$ lower than those from PBE+rVV10. Since SCAN+rVV10 usually overbinds, the predicted binding energies by SCAN-vdW-dZK and PBE-vdW-dZK are expected to be closer to the true values. The predicted equilibrium binding distances from SCAN-vdW-dZK and PBE-vdW-dZK are slightly larger ($\ensuremath{\sim}0.1\phantom{\rule{0.16em}{0ex}}\AA{}$) than those from SCAN+rVV10, and close to those from SCAN. The binding energy depends upon the number of substrate layers more strongly in vdW-dZK than in rVV10. The ${C}_{4}$-term contributions can be 40% of the total vdW interactions, and the ${C}_{5}$ term contributes about 10%. The effects of images and the back surfaces of slabs can contribute about 4--10%. The vdW interaction energy power laws from the vdW-dZK model for graphene adsorbed on multilayer $\mathrm{Mo}{\mathrm{S}}_{2}$ show slowly varying decay to the pairwise exponent \ensuremath{-}4 with increasing separation $D$, very similar to those obtained from the random-phase approximation and renormalization group approaches by Ambrosetti et al. Both the PBE-vdW-dZK and SCAN-vdW-dZK give a greater increase in interlayer binding energy when the TMD substrate changes from monolayer to four-layer for the graphene/TMD adsorption systems. This is consistent with the relevant electron-energy-loss spectroscopy experimental results showing increased dielectric response from the substrate with increasing substrate layer number.

Unveiling Bandgap Evolution and Carrier Redistribution in Multilayer WSe2: Enhanced Photon Emission via Heat Engineering

AbstractManipulating the bandgap structure and carrier distribution of multilayer transition metal dichalcogenides (TMDs) is crucial for improving their fluorescence efficiency and extending their optoelectronic applications. Herein, the evolution of the conduction band minimum of multilayer WSe2 as a function of the temperature and thickness is experimentally demonstrated and an ≈70‐fold fluorescence enhancement of the K–K direct emission is observed at 560 K in multilayer WSe2 flakes (≈170 nm) by heat engineering. This abnormal enhancement is attributed to thermally driven carrier redistribution achieved via intervalley transfer, which is confirmed by the theoretical calculations and temperature‐dependent time‐resolved photoluminescence. In addition, a threshold temperature of the intervalley transfer is proposed to describe the on‐state of the carrier redistribution model. The corresponding threshold temperature is determined to be ≈580 K, which is consistent with the temperature at which the maximum photoluminescence enhancement is observed. The study provides a useful strategy to optimize the optical and electric performances of multilayer WSe2 and other TMDs materials.