Atomically thin transition metal dichalcogenides (TMDs) are of interest for next-generation electronics and optoelectronics. Here, we demonstrate device-ready synthetic tungsten diselenide (WSe) 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 WSe/sapphire exhibit ambipolar behavior with excellent on/off ratios (∼10), high current density (1-10 μA·μm), and good field-effect transistor mobility (∼30 cm·V·s) 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.
A multistep diffusion-mediated process was developed to control the nucleation density, size, and lateral growth rate of WSe 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 HSe to promote surface diffusion of tungsten-containing species to form oriented WSe islands with uniform size and controlled density. The growth conditions were then adjusted to suppress further nucleation and laterally grow the WSe islands to form a fully coalesced monolayer film in less than 1 h. Postgrowth structural characterization demonstrates that the WSe 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 WSe 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 WSe monolayers in a scalable process that is suitable for large area device fabrication.
Atomically thin materials such as graphene or MoS 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'-ReSe. 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'-ReSe 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.
We report the synthesis of high-quality single crystals of ReS2 and ReSe2 transition metal dichalcogenides using a modified Bridgman method that avoids the use of a halogen transport agent. Comprehensive structural characterization using X-ray diffraction and electron microscopy confirm a distorted triclinic 1T′ structure for both crystals and reveal a lack of Bernal stacking in ReS2. Photoluminescence (PL) measurements on ReS2 show a layer-independent bandgap of 1.51 eV, with increased PL intensity from thicker flakes, confirming interlayer coupling to be negligible in this material. For ReSe2, the bandgap is weakly layer-dependent and decreases from 1.31 eV for thin layers to 1.29 eV in thick flakes. Both chalcogenides show feature-rich Raman spectra whose excitation energy dependence was studied. The lower background doping inherent to our crystal growth process results in high field-effect mobility values of 79 and 0.8 cm2/(V s) for ReS2 and ReSe2, respectively, as extracted from FET structures fabricated from exfoliated flakes. Our work shows ReX2 chalcogenides to be promising 2D materials candidates, especially for optoelectronic devices, without the requirement of having monolayer thin flakes to achieve a direct bandgap.
A two-dimensional (2D) heterobilayer system consisting of MoS on WSe, 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 MoS and WSe. 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.
The residue of common photo‐ and electron‐beam resists, such as poly(methyl methacrylate) (PMMA), is often present on the surface of 2D crystals after device fabrication. The residue degrades device properties by decreasing carrier mobility and creating unwanted doping. Here, MoS2 and WSe2 field effect transistors (FETs) with residue are cleaned by contact mode atomic force microscopy (AFM) and the impact of the residue on: 1) the intrinsic electrical properties, and 2) the effectiveness of electric double layer (EDL) gating are measured. After cleaning, AFM measurements confirm that the surface roughness decreases to its intrinsic state (i.e., ≈0.23 nm for exfoliated MoS2 and WSe2) and Raman spectroscopy shows that the characteristic peak intensities (E2g and A1g) increase. PMMA residue causes p‐type doping corresponding to a charge density of ≈7 × 1011 cm−2 on back‐gated MoS2 and WSe2 FETs. For FETs gated with polyethylene oxide (PEO)76:CsClO4, removing the residue increases the charge density by 4.5 × 1012 cm−2, and the maximum drain current by 247% (statistically significant, p < 0.05). Removing the residue likely allows the ions to be positioned closer to the channel surface, which is essential for achieving the best possible electrostatic gate control in ion‐gated devices.
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.
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 (MoS) and tungsten diselenide (WSe) 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-MoS and p-GaN, leading to a degraded interface and high p-type leakage current. Finally, we demonstrate integration of heterogeneous 2D layer stacks of MoS/WSe on GaN with atomically sharp interface. Monolayer MoS/WSe/n-GaN stacks lead to near Ohmic transport due to the tunneling and non-degenerated doping, while few layer stacking is Schottky barrier dominated.
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