Diffusion-Controlled Epitaxy of Large Area Coalesced WSe2 Monolayers on Sapphire.

A multistep diffusion-mediated process was developed to control the nucleation density, size, and lateral growth rate of WSe2 domains on c-plane sapphire for the epitaxial growth of large area monolayer films by gas source chemical vapor deposition (CVD). The process consists of an initial nucleation step followed by an annealing period in H2Se to promote surface diffusion of tungsten-containing species to form oriented WSe2 islands with uniform size and controlled density. The growth conditions were then adjusted to suppress further nucleation and laterally grow the WSe2 islands to form a fully coalesced monolayer film in less than 1 h. Postgrowth structural characterization demonstrates that the WSe2 monolayers are single crystal and epitaxially oriented with respect to the sapphire and contain antiphase grain boundaries due to coalescence of 0° and 60° oriented WSe2 domains. The process also provides fundamental insights into the two-dimensional (2D) growth mechanism. For example, the evolution of domain size and cluster density with annealing time follows a 2D ripening process, enabling an estimate of the tungsten-species surface diffusivity. The lateral growth rate of domains was found to be relatively independent of substrate temperature over the range of 700-900 °C suggesting a mass transport limited process, however, the domain shape (triangular versus truncated triangular) varied with temperature over this same range due to local variations in the Se/W adatom ratio. The results provide an important step toward atomic level control of the epitaxial growth of WSe2 monolayers in a scalable process that is suitable for large area device fabrication.

Quantum-Confined Electronic States Arising from the Moiré Pattern of MoS2-WSe2 Heterobilayers.

A two-dimensional (2D) heterobilayer system consisting of MoS2 on WSe2, deposited on epitaxial graphene, is studied by scanning tunneling microscopy and spectroscopy at temperatures of 5 and 80 K. A moiré pattern is observed, arising from lattice mismatch of 3.7% between the MoS2 and WSe2. Significant energy shifts are observed in tunneling spectra observed at the maxima of the moiré corrugation, as compared with spectra obtained at corrugation minima, consistent with prior work. Furthermore, at the minima of the moiré corrugation, sharp peaks in the spectra at energies near the band edges are observed for spectra acquired at 5 K. The peaks correspond to discrete states that are confined within the moiré unit cells. Conductance mapping is employed to reveal the detailed structure of the wave functions of the states. For measurements at 80 K, the sharp peaks in the spectra are absent, and conductance maps of the band edges reveal little structure.

Probing in-plane anisotropy in few-layer ReS2 using low frequency noise measurement.

ReS2, a layered two-dimensional material popular for its in-plane anisotropic properties, is emerging as one of the potential candidates for flexible electronics and ultrafast optical applications. It is an n-type semiconducting material having a layer independent bandgap of 1.55 eV. In this paper we have characterized the intrinsic electronic noise level of few-layer ReS2 for the first time. Few-layer ReS2 field effect transistor devices show a 1/f nature of noise for frequency ranging over three orders of magnitude. We have also observed that not only the electrical response of the material is anisotropic; the noise level is also dependent on direction. In fact the noise is found to be more sensitive towards the anisotropy. This fact has been explained by evoking the theory where the Hooge parameter is not a constant quantity, but has a distinct power law dependence on mobility along the two-axes direction. The anisotropy in 1/f noise measurement will pave the way to quantify the anisotropic nature of two-dimensional (2D) materials, which will be helpful for the design of low-noise transistors in future.

Highly Anisotropic in-Plane Excitons in Atomically Thin and Bulklike 1T'-ReSe2.

Atomically thin materials such as graphene or MoS2 are of high in-plane symmetry. Crystals with reduced symmetry hold the promise for novel optoelectronic devices based on their anisotropy in current flow or light polarization. Here, we present polarization-resolved optical transmission and photoluminescence spectroscopy of excitons in 1T'-ReSe2. On reducing the crystal thickness from bulk to a monolayer, we observe a strong blue shift of the optical band gap from 1.37 to 1.50 eV. The excitons are strongly polarized with dipole vectors along different crystal directions, which persist from bulk down to monolayer thickness. The experimental results are well reproduced by ab initio calculations based on the GW-BSE approach within LDA+GdW approximation. The excitons have high binding energies of 860 meV for the monolayer and 120 meV for bulk. They are strongly confined within a single layer even for the bulk crystal. In addition, we find in our calculations a direct band gap in 1T'-ReSe2 regardless of crystal thickness, indicating weak interlayer coupling effects on the band gap characteristics. Our results pave the way for polarization-sensitive applications, such as optical logic circuits operating in the infrared spectral region.

Interface Transparency and Rashba Spin Torque Enhancement in WSe2 Heterostructures.

Rashba spin current generation emerges in heterostructures of ferromagnets and transition metal dichalcogenides (TMDs) due to an interface polarization and associated inversion symmetry breaking. Recent work exploring the synthesis and transfer of epitaxial films on the top of low layer count 2D materials reveals that atomic potentials from the underlying substrate interface are not completely screened. The extension of this transparency effect to other interfacial phenomena, such as the Rashba effect and associated spin torques, has not yet been demonstrated. Here, we report enhanced spin transfer torques from the Rashba spin current in heterostructures of permalloy (Py) and WSe2. We show that insertion of up to two monolayers of WSe2 enhances the spin transfer torques in a Rashba system by up to 3×, without changing the fieldlike Rashba spin-orbit torque (SOT), a measure of interface polarization. Our results indicate that low layer count TMD films can be used as an interfacial "scattering promoter" in heterostructure interfaces without quenching the original polarization.

Doping controlled Fano resonance in bilayer 1T'-ReS2: Raman experiments and first-principles theoretical analysis.

In the bilayer ReS2 channel of a field-effect transistor (FET), we demonstrate using Raman spectroscopy that electron doping (n) results in softening of frequency and broadening of linewidth for the in-plane vibrational modes, leaving the out-of-plane vibrational modes unaffected. The largest change is observed for the in-plane Raman mode at ∼151 cm-1, which also shows doping induced Fano resonance with the Fano parameter 1/q = -0.17 at a doping concentration of ∼3.7 × 1013 cm-2. A quantitative understanding of our results is provided by first-principles density functional theory (DFT), showing that the electron-phonon coupling (EPC) of in-plane modes is stronger than that of out-of-plane modes, and its variation with doping is independent of the layer stacking. The origin of large EPC is traced to 1T to 1T' structural phase transition of ReS2 involving in-plane displacement of atoms whose instability is driven by the nested Fermi surface of the 1T structure. Results are compared with those of the isostructural trilayer ReSe2.

Flat Bands and Mechanical Deformation Effects in the Moiré Superlattice of MoS2-WSe2 Heterobilayers.

It has recently been shown that quantum-confined states can appear in epitaxially grown van der Waals material heterobilayers without a rotational misalignment (θ = 0°), associated with flat bands in the Brillouin zone of the moiré pattern formed due to the lattice mismatch of the two layers. Peaks in the local density of states and confinement in a MoS2/WSe2 system was qualitatively described only considering local stacking arrangements, which cause band edge energies to vary spatially. In this work, we report the presence of large in-plane strain variation across the moiré unit cell of a θ = 0° MoS2/WSe2 heterobilayer and show that inclusion of strain variation and out-of-plane displacement in density functional theory calculations greatly improves their agreement with the experimental data. We further explore the role of a twist angle by showing experimental data for a twisted MoS2/WSe2 heterobilayer structure with a twist angle of θ = 15°, which exhibits a moiré pattern but no confinement.

Realizing Large-Scale, Electronic-Grade Two-Dimensional Semiconductors.

Atomically thin transition metal dichalcogenides (TMDs) are of interest for next-generation electronics and optoelectronics. Here, we demonstrate device-ready synthetic tungsten diselenide (WSe2) via metal-organic chemical vapor deposition and provide key insights into the phenomena that control the properties of large-area, epitaxial TMDs. When epitaxy is achieved, the sapphire surface reconstructs, leading to strong 2D/3D (i.e., TMD/substrate) interactions that impact carrier transport. Furthermore, we demonstrate that substrate step edges are a major source of carrier doping and scattering. Even with 2D/3D coupling, transistors utilizing transfer-free epitaxial WSe2/sapphire exhibit ambipolar behavior with excellent on/off ratios (∼107), high current density (1-10 µA·µm-1), and good field-effect transistor mobility (∼30 cm2·V-1·s-1) at room temperature. This work establishes that realization of electronic-grade epitaxial TMDs must consider the impact of the TMD precursors, substrate, and the 2D/3D interface as leading factors in electronic performance.

Large scale 2D/3D hybrids based on gallium nitride and transition metal dichalcogenides.

Two and three-dimensional (2D/3D) hybrid materials have the potential to advance communication and sensing technologies by enabling new or improved device functionality. To date, most 2D/3D hybrid devices utilize mechanical exfoliation or post-synthesis transfer, which can be fundamentally different from directly synthesized layers that are compatible with large scale industrial needs. Therefore, understanding the process/property relationship of synthetic heterostructures is priority for industrially relevant material architectures. Here we demonstrate the scalable synthesis of molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) via metal organic chemical vapor deposition (MOCVD) on gallium nitride (GaN), and elucidate the structure, chemistry, and vertical transport properties of the 2D/3D hybrid. We find that the 2D layer thickness and transition metal dichalcogenide (TMD) choice plays an important role in the transport properties of the hybrid structure, where monolayer TMDs exhibit direct tunneling through the layer, while transport in few layer TMDs on GaN is dominated by p-n diode behavior and varies with the 2D/3D hybrid structure. Kelvin probe force microscopy (KPFM), low energy electron microscopy (LEEM) and X-ray photoelectron spectroscopy (XPS) reveal a strong intrinsic dipole and charge transfer between n-MoS2 and p-GaN, leading to a degraded interface and high p-type leakage current. Finally, we demonstrate integration of heterogeneous 2D layer stacks of MoS2/WSe2 on GaN with atomically sharp interface. Monolayer MoS2/WSe2/n-GaN stacks lead to near Ohmic transport due to the tunneling and non-degenerated doping, while few layer stacking is Schottky barrier dominated.