Bilayer Transition Metal Dichalcogenides Research Articles

Theory of phonon sidebands in the absorption spectra of moiré exciton–polaritons

Excitons in twisted bilayers of transition metal dichalcogenides have strongly modified dispersion relations due to the formation of periodic moiré potentials. The strong coupling to a light field in an optical cavity leads to the appearance of moiré polaritons. In this paper, we derive a theoretical model for the linear absorption spectrum of the coupled moiré polariton–phonon system based on the time-convolutionless (TCL) approach. Results obtained by numerically solving the TCL equation are compared to those obtained in the Markovian limit and from a perturbative treatment of non-Markovian corrections. A key quantity for the interpretation of the findings is the generalized phonon spectral density. We discuss the phonon impact on the spectrum for realistic moiré exciton dispersions by varying twist angle and temperature. Key features introduced by the coupling to phonons are broadenings and energy shifts of the upper and lower polariton peak and the appearance of phonon sidebands between them. We analyze these features with respect to the role of Markovian and non-Markovian effects and find that they strongly depend on the twist angle. We can distinguish between the regimes of large, small, and intermediate twist angles. In the latter phonon effects are particularly pronounced due to dominating phonon transitions into regions which are characterized by van Hove singularities in the density of states.

Tunnel junctions based on interfacial two dimensional ferroelectrics

Van der Waals heterostructures have opened new opportunities to develop atomically thin (opto)electronic devices with a wide range of functionalities. The recent focus on manipulating the interlayer twist angle has led to the observation of out-of-plane room temperature ferroelectricity in twisted rhombohedral bilayers of transition metal dichalcogenides. Here we explore the switching behaviour of sliding ferroelectricity using scanning probe microscopy domain mapping and tunnelling transport measurements. We observe well-pronounced ambipolar switching behaviour in ferroelectric tunnelling junctions with composite ferroelectric/non-polar insulator barriers and support our experimental results with complementary theoretical modelling. Furthermore, we show that the switching behaviour is strongly influenced by the underlying domain structure, allowing the fabrication of diverse ferroelectric tunnelling junction devices with various functionalities. We show that to observe the polarisation reversal, at least one partial dislocation must be present in the device area. This behaviour is drastically different from that of conventional ferroelectric materials, and its understanding is an important milestone for the future development of optoelectronic devices based on sliding ferroelectricity.

Programmable Retention Characteristics in MoS2-Based Atomristors for Neuromorphic and Reservoir Computing Systems.

In this study, we investigate the coexistence of short- and long-term memory effects owing to the programmable retention characteristics of a two-dimensional Au/MoS2/Au atomristor device and determine the impact of these effects on synaptic properties. This device is constructed using bilayer MoS2 in a crossbar structure. The presence of both short- and long-term memory characteristics is proposed by using a filament model within the bilayer transition-metal dichalcogenide. Short- and long-term properties are validated based on programmable multilevel retention tests. Moreover, we confirm various synaptic characteristics of the device, demonstrating its potential use as a synaptic device in a neuromorphic system. Excitatory postsynaptic current, paired-pulse facilitation, spike-rate-dependent plasticity, and spike-number-dependent plasticity synaptic applications are implemented by operating the device at a low-conductance level. Furthermore, long-term potentiation and depression exhibit symmetrical properties at high-conductance levels. Synaptic learning and forgetting characteristics are emulated using programmable retention properties and composite synaptic plasticity. The learning process of artificial neural networks is used to achieve high pattern recognition accuracy, thereby demonstrating the suitability of the use of the device in a neuromorphic system. Finally, the device is used as a physical reservoir with time-dependent inputs to realize reservoir computing by using short-term memory properties. Our study reveals that the proposed device can be applied in artificial intelligence-based computing applications by utilizing its programmable retention properties.

Strong-Coupling Phases of Trions and Excitons in Electron-Hole Bilayers at Commensurate Densities.

We introduce density imbalanced electron-hole bilayers at a commensurate 2:1 density ratio as a platform for realizing novel phases of electrons, excitons, and trions. Through the independently tunable carrier densities and interlayer spacing, competition between kinetic energy, intralayer repulsion, and interlayer attraction yields a rich phase diagram. By a combination of theoretical analysis and numerical calculation, we find a variety of strong-coupling phases in different parameter regions, including quantum crystals of electrons, excitons, and trions. We also propose an "electron-exciton supersolid" phase that features electron crystallization and exciton superfluidity simultaneously. The material realization and experimental signature of these phases are discussed in the context of semiconductor transition metal dichalcogenide bilayers.

Nonbosonic Moiré Excitons.

Optical excitations in moiré transition metal dichalcogenide bilayers lead to the creation of excitons, as electron-hole bound states, that are generically considered within a Bose-Hubbard framework. Here, we demonstrate that these composite particles obey an angular momentum commutation relation that is generally nonbosonic. This emergent spin description of excitons indicates a limitation to their occupancy on each site, which is substantial in the weak electron-hole binding regime. The effective exciton theory is accordingly a spin Hamiltonian, which further becomes a Hubbard model of emergent bosons subject to an occupancy constraint after a Holstein-Primakoff transformation. We apply our theory to three commonly studied bilayers (MoSe_{2}/WSe_{2}, WSe_{2}/WS_{2}, and WSe_{2}/MoS_{2}) and show that in the relevant parameter regimes their allowed occupancies never exceed three excitons. Our systematic theory provides guidelines for future research on the many-body physics of moiré excitons.

The Rotating Excitons in 2D Materials: Valley Zeeman Effect and Chirality

The rotational dynamics of the intralayer and interlayer excitons with their inherent momenta of inertia in the monolayer and bilayer transition metal dichalcogenides, respectively, where the new chirality of exciton is endowed by the rotational angular momentum, namely, the formations of left‐ and right‐handed excitons at the +K and −K valleys, respectively, is proposed. It is found that angular momenta exchange between excitons and its surrounding phononic bath result in the large fluctuation of the effective g‐factor and the asymmetry of valley Zeeman splitting observed in most recently experiments, both of which sensitively depend on the magnetic moments provided by the phononic environment. This rotating exciton model not only proposes a new controllable knob in valleytronics, but opens the door to explore the angular momentum exchange of the chiral quasiparticles with the many‐body environment.

Growth of tungsten disulfide bilayers featuring Moiré superlattices: A surface energy perspective

The bilayer (BL) transition metal dichalcogenides (TMDs), with their elevated carrier mobility and narrowed bandgap, are advantageous for future electronic applications in comparison with their monolayer (ML) counterparts. Here, we introduce a facile and efficient approach for the chemical vapor deposition synthesis of BL WS2. The method involves an acetic acid sonication treatment to modify the substrate surface morphology and the surface energy, which regulates the nucleation processes and shapes the growth mode of WS2 crystals. Further modifications to the growth conditions yield high-quality ML and BL WS2 films. A comparative study confirms the superior valley polarization and higher carrier mobility of BL WS2 compared with its ML counterpart. Additionally, a minor twist angle existed between the upper and lower layers, featuring a Moiré superlattice. This work reveals the role of surface morphology and surface energy in the growth of TMDs. Simultaneously, it offers insights into the controlled preparation of vertically stacked homo- and heterojunctions.

Atom-by-atom imaging of moiré transformations in 2D transition metal dichalcogenides.

Understanding the atomic-scale mechanisms that govern the structure of interfaces is critical across materials systems but particularly so for two-dimensional (2D) moiré materials. Here, we image, atom-by-atom, the thermally induced structural evolution of twisted bilayer transition metal dichalcogenides using in situ transmission electron microscopy. We observe low-temperature, local conversion of moiré superlattice into nanoscale aligned domains. Unexpectedly, this process occurs by nucleating a new grain within one monolayer, whose crystal orientation is templated by the other. The aligned domains grow through collective rotation of moiré supercells and hopping of 5|7 defect pairs at moiré boundaries. This provides mechanistic insight into the atomic-scale interactions controlling moiré structures and illustrates the potential to pattern interfacial structure and properties of 2D materials at the nanoscale.

Chemically Tailored Semiconductor Moiré Superlattices of Janus Heterobilayers

Janus monolayers of transition metal dichalcogenides (TMDCs) are promising building blocks for moiré superlattices because of their built‐in electric field and clean fabrication process. In particular, Janus TMDC monolayers can be chemically converted from conventional TMDC monolayers by atomic substitution, enabling the direct formation of lattice‐mismatched heterobilayers from TMDC bilayers. However, the moiré superlattices of Janus heterobilayers have not been studied experimentally. Herein, this work reports the fabrication and characterization of semiconductor moiré superlattices in chemically tailored Janus heterobilayers. The MoSSe/MoSe2 (or WSSe/WSe2) Janus heterobilayers are prepared by replacing the top layer Se atoms with S atoms in MoSe2 (or WSe2) bilayer using H2 plasma treatment. Scanning transmission electron microscopy reveals that an average moiré period of about 14 nm formed due to lattice mismatch resulting from the chalcogen substitutions. The cryogenic photoluminescence spectra show sharp, near‐infrared emissions, which are attributed to excitons trapped by moiré potentials based on comparison with theoretical calculations. The Janus‐based heterostructures provide a long‐period moiré system with built‐in potential even for nontwisted heterobilayers, allowing the functionalization of confined and correlated electron systems.

Identification and Structural Characterization of Twisted Atomically Thin Bilayer Materials by Deep Learning.

Two-dimensional materials are expected to play an important role in next-generation electronics and optoelectronic devices. Recently, twisted bilayer graphene and transition metal dichalcogenides have attracted significant attention due to their unique physical properties and potential applications. In this study, we describe the use of optical microscopy to collect the color space of chemical vapor deposition (CVD) of molybdenum disulfide (MoS2) and the application of a semantic segmentation convolutional neural network (CNN) to accurately and rapidly identify thicknesses of MoS2 flakes. A second CNN model is trained to provide precise predictions on the twist angle of CVD-grown bilayer flakes. This model harnessed a data set comprising over 10,000 synthetic images, encompassing geometries spanning from hexagonal to triangular shapes. Subsequent validation of the deep learning predictions on twist angles was executed through the second harmonic generation and Raman spectroscopy. Our results introduce a scalable methodology for automated inspection of twisted atomically thin CVD-grown bilayers.

CVD Synthesis of Twisted Bilayer WS2 with Tunable Second Harmonic Generation.

The introduction of rotational freedom by twist angles in twisted bilayer (TB) transition metal dichalcogenides (TMDCs) can tailor the inherent properties of the TMDCs, which provides a promising platform to investigate the exotic physical properties. However, direct synthesis of high-quality TB-TMDCs with full twist angles is significantly challenging due to the substantial energy barriers during crystal growth. Here, a modified chemical vapor deposition strategy is proposed to synthesize TB-WS2 with a wide twist angle range from 0° to 120°. Utilizing a tilted SiO2/Si substrate, a gas flow disturbance is generated in the furnace tube to create a heterogeneous concentration gradient of the metal precursor, which provides an extra driving force for the growth of TB-WS2. The Raman and photoluminescence results confirm a weak interlayer coupling of the TB-WS2. High-quality periodic Moiré patterns are observed in the scanning transmission electron microscopy images. Moreover, owing to the strong correlation between the nonlinear optical response and the twisted crystal structure, tunable second harmonic generation behaviors are realized in the TB-WS2. This approach opens up a new avenue for the direct growth of high-crystalline-quality and pristine TB-TMDCs and their potential applications in nonlinear optical devices.

Synthesis of NbSe2/Bilayer Nb‐Doped WSe2 Heterostructure from Exfoliated WSe2 Flakes

Forming heterostructures of 2D metals and semiconductors using chemical vapor deposition (CVD) has significant potential to effectively reduce contact resistance in electronic devices. However, semiconducting transition metal dichalcogenide (TMD) layers in metal–semiconductor heterostructures are currently restricted to monolayers despite the superior mobility and density of states in bilayer TMDs. Herein, NbSe2/bilayer Nb‐doped WSe2 metal/semiconductor heterostructure from exfoliated WSe2 flakes are synthesized first. The exfoliated WSe2 bulk crystals on an Nb‐coated substrate are heated to 950 °C under a flow of selenium vapor, and then the NbSe2/bilayer Nb‐doped WSe2 heterostructures are formed. Statistics on the number of Nb‐doped WSe2 layers grown on a 1 cm × 1 cm CVD substrate shows that 65% of the Nb‐doped WSe2 layers are grown as bilayers. X‐ray photoelectron spectroscopy, optical microscopy, and transmission electron microscopy clearly clarify the number of Nb‐doped WSe2 layers and heterostructure of NbSe2/bilayer Nb‐doped WSe2. Electrical measurements using Cr contacts show that bilayer Nb‐doped WSe2 displays 7‐ and 10‐times higher mobility and on/off ratio than monolayer Nb‐doped WSe2. The mobility and on/off ratio are further doubled in NbSe2/bilayer Nb‐doped WSe2 contact compared to Cr/bilayer Nb‐doped WSe2 contact, attributed to a clean interface in vertical stack heterostructure, enhancing electrical performance.

Doping Ability Modulated by Interlayer Coupling in AA' and AB Stacked Bilayer V-WS2 Grown with Chemical Vapor Deposition.

Doping in transition metal dichalcogenide (TMD) has received extensive attention for its prospect in the application of photoelectric devices. Currently researchers focus on the doping ability and doping distribution in monolayer TMD and have obtained a series of achievements. Bilayer TMD has more excellent properties compared with monolayer TMD. Moreover, bilayer TMD with different stacking structures presents varying performance due to the difference in interlayer coupling. Herein, this work focuses on doping ability of dopants in different bilayer stacking structures that has not been studied yet. Results of this work show that the doping ability of V atoms in bilayer AA' and AB stacked WS2 is different, and the doping concentration of V atoms in AB stacked WS2 is higher than in AA' stacked WS2 . Moreover, dopants from top and bottom layer can be distinguished by scanning transmission electron microscopy (STEM)image. Density functional theory (DFT) calculation further confirms the doping rule. This study reveals the mechanism of the different doping ability caused by stacking structures in bilayer TMD and lays a foundation for further preparation of controllable-doping bilayer TMD materials.

Reconfiguring nucleation for CVD growth of twisted bilayer MoS2 with a wide range of twist angles

Twisted bilayer (TB) transition metal dichalcogenides (TMDCs) beyond TB-graphene are considered an ideal platform for investigating condensed matter physics, due to the moiré superlattices-related peculiar band structures and distinct electronic properties. The growth of large-area and high-quality TB-TMDCs with wide twist angles would be significant for exploring twist angle-dependent physics and applications, but remains challenging to implement. Here, we propose a reconfiguring nucleation chemical vapor deposition (CVD) strategy for directly synthesizing TB-MoS2 with twist angles from 0° to 120°. The twist angles-dependent Moiré periodicity can be clearly observed, and the interlayer coupling shows a strong relationship to the twist angles. Moreover, the yield of TB-MoS2 in bilayer MoS2 and density of TB-MoS2 are significantly improved to 17.2% and 28.9 pieces/mm2 by tailoring gas flow rate and molar ratio of NaCl to MoO3. The proposed reconfiguring nucleation approach opens an avenue for the precise growth of TB-TMDCs for both fundamental research and practical applications.

Magnetism and metallicity in moiré transition metal dichalcogenides.

The ability to control the properties of twisted bilayer transition metal dichalcogenides in situ makes them an ideal platform for investigating the interplay of strong correlations and geometric frustration. Of particular interest are the low energy scales, which make it possible to experimentally access both temperature and magnetic fields that are of the order of the bandwidth or the correlation scale. In this manuscript, we analyze the moiré Hubbard model, believed to describe the low energy physics of an important subclass of the twisted bilayer compounds. We establish its magnetic and the metal-insulator phase diagram for the full range of magnetic fields up to the fully spin-polarized state. We find a rich phase diagram including fully and partially polarized insulating and metallic phases of which we determine the interplay of magnetic order, Zeeman-field, and metallicity, and make connection to recent experiments.

Second-harmonic generation in 2D moiré superlattices composed of bilayer transition metal dichalcogenides.

Moiré superlattices (MSLs) in twisted two-dimensional van der Waals materials feature twist-angle-dependent crystal symmetry and strong optical nonlinearities. By adjusting the twist angle in bilayer van der Waals materials, the second-harmonic generation (SHG) can be controlled. Here, we focus on exploring the electronic and SHG properties of MSLs in 2D bilayer transition metal dichalcogenides (TMDs) with different twist angles through first-principles calculations. We constructed MSL structures of five TMD materials, including three single-phase materials (MoS2, WS2, and MoSe2) and two heterojunctions (MoS2/MoSe2 and MoS2/WS2) with twist angles of 9.4°, 13.2°, 21.8°, 32.2°, and 42.1° without lattice mismatch. Our findings demonstrate a consistent variation in the SHG susceptibility among different TMD MSLs as a response to twist-angle changes. The underlying reason for the twist-angle dependence of SHG is that the twist angle regulates the interlayer coupling strength, affecting the optical band gap of MSLs and subsequently tuning the SHG susceptibility. Through a comparison of the static SHG susceptibility values, we identified the twist angle of 9.4° as the configuration that yields the highest SHG susceptibility (e.g. 358.5 pm V-1 for the 9.4° MoSe2 MSL). This value is even twice that of the monolayer (173.3 pm V-1 for monolayer MoSe2) and AA'-stacked bilayer structures (139.8 pm V-1 for AA' MoSe2). This high SHG susceptibility is attributed to the strong interlayer coupling in the 9.4° MSL, which enhances the valence band energy (contributed by the antibonding orbitals of chalcogen-pz and transition metal-dz2) and consequently leads to a small optical band gap, thus improving the optical transitions. The findings of this study provide a straightforward way to improve the SHG performance of bilayer TMDs and also throw light on the sensitive relationship between the twist angle, band structure and SHG properties of TMD MSLs.

Influence of Atomic Relaxations on the Moiré Flat Band Wave Functions in Antiparallel Twisted Bilayer WS2.

Twisting bilayers of transition metal dichalcogenides gives rise to a moiré potential resulting in flat bands with localized wave functions and enhanced correlation effects. In this work, scanning tunneling microscopy is used to image a WS2 bilayer twisted approximately 3° off the antiparallel alignment. Scanning tunneling spectroscopy reveals localized states in the vicinity of the valence band onset, which is observed to occur first in regions with S-on-S Bernal stacking. In contrast, density functional theory calculations on twisted bilayers that have been relaxed in vacuum predict the highest-lying flat valence band to be localized in regions of AA' stacking. However, agreement with experiment is recovered when the calculations are performed on bilayers in which the atomic displacements from the unrelaxed positions have been reduced, reflecting the influence of the substrate and finite temperature. This demonstrates the delicate interplay of atomic relaxations and the electronic structure of twisted bilayer materials.

Half-metallic magnetism in 2D MX2 (M = V, Cr, Mn, and Fe; X = S, Se, and Te) intercalated with 1D MX chains

Intercalation has attracted considerable attention due to its extensive ability to modify the electronic, optical, and magnetic properties of two-dimensional (2D) layered nanomaterials. Typically, dispersed atoms or molecules are inserted into the van der Waals gap of the 2D materials. Recently, Guo et al. experimentally reported the novel VS2–VS superlattice, where the intercalation takes the form of atomic chain arrays. In this study, we employed the first-principles calculations based on density functional theory to investigate a series of analogous 2D MX2–MX–MX2 nanomaterials, which, consisting of 2D transition metal dichalcogenide bilayers, intercalated with a one-dimensional transition metal chalcogenide MX chain array, forming a hotdog-like structure. Some of the 2D MX2–MX–MX2 are thermally and dynamically stable, suggesting their potential for experimental fabrication similar to VS2–VS–VS2. MnS2–MnS–MnS2 and MnSe2–MnSe–MnSe2 have been found to exhibit ferromagnetic half-metallic properties. In addition, VSe2–VSe–VSe2, CrS2–CrS–CrS2, and CrSe2–CrSe–CrSe2 have been found to be thermally and dynamically stable. Under appropriate external stress, doping, or bias, they could become ferromagnetic half-metals, revealing their potential for spintronic applications.

Fabrications of twisted moiré photonic crystal and random moiré photonic crystal and their potential applications in light extraction

Twisted moiré photonic crystal is an optical analog of twisted graphene or twisted transition metal dichalcogenide bilayers. In this paper, we report the fabrication of twisted moiré photonic crystals and randomized moiré photonic crystals and their use in enhanced extraction of light in light-emitting diodes (LEDs). Fractional diffraction orders from randomized moiré photonic crystals are more uniform than those from moiré photonic crystals. Extraction efficiencies of 76.5%, 77.8% and 79.5% into glass substrate are predicted in simulations of LED patterned with twisted moiré photonic crystals, defect-containing photonic crystals and random moiré photonic crystals, respectively, at 584 nm. Extraction efficiencies of optically pumped LEDs with 2D perovskite (BA)2(MA) n−1PbnI3n+1 of n = 3 and (5-(2′-pyridyl)-tetrazolato)(3-CF3−5-(2′-pyridyl)pyrazolato) platinum(II) (PtD) have been measured.

Probing the Twist-Controlled Interlayer Coupling in Artificially Stacked Transition Metal Dichalcogenide Bilayers by Second-Harmonic Generation.

Interlayer coupling plays a critical role in the electronic band structures and optoelectronic properties of van der Waals (vdW) materials and heterostructures. Here, we utilize optical second-harmonic generation (SHG) measurements to probe the twist-controlled interlayer coupling in artificially stacked WSe2/WSe2 homobilayers and WSe2/WS2 and WSe2/MoS2 heterobilayers with a postannealing procedure. In the large angle twisted WSe2/WSe2 and WSe2/WS2, the angular dependence of the SHG intensity follows the interference relations up to angles above 10°. For lower angles, the SHG is significantly suppressed. Furthermore, for the twisted WSe2/MoS2 the SHG intensity largely deviates from the coherent superposition model and shows consistent quenching for all the stacking angles. The suppressed SHG in twisted transition metal dichalcogenide (TMDC) bilayers is predominantly attributed to the interlayer coupling between the two adjacent monolayers. The evolution of the interlayer Raman mode in WSe2 demonstrates that the interlayer coupling in the twisted WSe2/WSe2 and WSe2/WS2 is highly angle-dependent. Alternatively, the interlayer coupling generally exists in the twisted WSe2/MoS2, regardless of the different angles. The interlayer coupling is further confirmed by the quenching and red-shift of the photoluminescence of WSe2 in the twisted TMDC bilayers. Combined with density functional theory calculations, we reveal that the stacking-angle-modulated interlayer coupling originates from the variation of the interlayer spacing and the binding energy in the twisted TMDC bilayers.