Transition Metal Dichalcogenides Single Crystals Research Articles

The growth mechanism of PtS2 single crystal.

PtS2, a member of the group 10 transition metal dichalcogenides (TMDs), has received extensive attention because of its excellent electrical properties and air stability. However, there are few reports on the preparation of single-crystal PtS2 in the literature, and the growth mechanism of single crystal PtS2 is not well elucidated. In this work, we proposed a method of preparation that combines magnetron sputtering and chemical vapor transport to obtain monocrystalline PtS2 on a SiO2/Si substrate. By controlling the growth temperature and time, we have synthesized a single crystalline PtS2 of hexagonal shape and size of 1-2 μm on a silicon substrate. Combining the molecular dynamics simulation, the growth mechanism of single crystal PtS2 was investigated both experimentally and theoretically. The synthesis method has a short production cycle and low cost, which opens the door for the fabrication of other TMDs single crystals.

Controlled Sixfold Symmetric Exfoliation of Oriented MoS2 Monolayers by Coulomb Force

AbstractAtoms, molecules, and nanoparticles can be spatially manipulated by an atomic force microscopy (AFM) tip, through van der Waals (vdW) and/or Coulomb forces. These point‐to‐point manipulations are highly accurate at nanoscale, facilitating the construction and modification of nanostructures. Nevertheless, it is difficult to manipulate 2D layers in vdW crystals by an AFM tip, because the tip‐induced attractive force is usually insufficient to outcompete the interlaminar vdW forces. Herein, manipulation of the surface layers on a MoS2 single crystal by a conductive AFM tip is successfully reported. By applying a bias between the tip and MoS2, the Coulomb attractive force allows the topmost MoS2 layers to be picked up. These exfoliated layers are deformed into micron‐sized bubbles with sixfold symmetry, which are composed of high‐quality monolayers and visually reflecting the hexagonal lattice orientation. The underlying mechanisms of the sixfold symmetric exfoliation and the formation of monolayers are discussed by in situ monitoring of the tunneling volt‐ampere characteristics and simulation of the force distribution. The findings open a new route to obtain high‐quality transition metal dichalcogenide (TMD) monolayers and their derived nanostructures on the surface of TMD single crystals for optoelectronic and photonic device applications.

Large-area single-crystal TMD growth modulated by sapphire substrates.

Transition metal dichalcogenides (TMDs) have recently attracted extensive attention due to their unique physical and chemical properties; however, the preparation of large-area TMD single crystals is still a great challenge. Chemical vapor deposition (CVD) is an effective method to synthesize large-area and high-quality TMD films, in which sapphires as suitable substrates play a crucial role in anchoring the source material, promoting nucleation and modulating epitaxial growth. In this review, we provide an insightful overview of different epitaxial mechanisms and growth behaviors associated with the atomic structure of sapphire surfaces and the growth parameters. First, we summarize three epitaxial growth mechanisms of TMDs on sapphire substrates, namely, van der Waals epitaxy, step-guided epitaxy, and dual-coupling-guided epitaxy. Second, we introduce the effects of polishing, cutting, and annealing processing of the sapphire surface on the TMD growth. Finally, we discuss the influence of other growth parameters, such as temperature, pressure, carrier gas, and substrate position, on the growth kinetics of TMDs. This review might provide deep insights into the controllable growth of large-area single-crystal TMDs on sapphires, which will propel their practical applications in high-performance nanoelectronics and optoelectronics.

Heteroepitaxy in Organic/TMD Hybrids and Challenge to Achieve it for TMD Monolayers: The Case of Pentacene on WS2 and WSe2.

The intriguing photophysical properties of monolayer stacks of different transition-metal dichalcogenides (TMDs), revealing rich exciton physics including interfacial and moiré excitons, have recently prompted an extension of similar investigations to hybrid systems of TMDs and organic films, as the latter combine large photoabsorption cross sections with the ability to tailor energy levels by targeted synthesis. To go beyond single-molecule photoexcitations and exploit the excitonic signatures of organic solids, crystalline molecular films are required. Moreover, a defined registry on the substrate, ideally an epitaxy, is desirable to also achieve an excitonic coupling in momentum space. This poses a certain challenge as excitonic dipole moments of organic films are closely related to the molecular orientation and film structure, which critically depend on the support roughness. Using X-ray diffraction, optical polarization, and atomic force microscopy, we analyzed the structure of pentacene (PEN) multilayer films grown on WSe2(001) and WS2(001) and identified an epitaxial alignment. While (022)-oriented PEN films are formed on both substrates, their azimuthal orientations are quite different, showing an alignment of the molecular L-axis along the and directions. This intrinsic epitaxial PEN growth depends, however, sensitively on the substrates surface quality. While it occurs on exfoliated TMD single crystals and multilayer flakes, it is hardly found on exfoliated monolayers, which often exhibit bubbles and wrinkles. This enhances the surface roughness and results in (001)-oriented PEN films with upright molecular orientation but without any azimuthal alignment. However, monolayer flakes can be smoothed by AFM operated in contact mode or by transferring to ultrasmooth substrates such as hBN, which again yields epitaxial PEN films. As different PEN orientations result in different characteristic film morphologies (elongated mesa islands vs pyramidal dendrites), which can be easily distinguished by AFM or optical microscopy, this provides a simple means to judge the roughness of the used TMD surface.

Stable Sulfuric Vapor Transport and Liquid Sulfur Growth on Transition Metal Dichalcogenides.

Transition metal dichalcogenides (TMDs) are an emergent class of low-dimensional materials with growing applications in the field of nanoelectronics. However, efficient methods for synthesizing large monocrystals of these systems are still lacking. Here, we describe an efficient synthetic route for a large number of TMDs that were obtained in quartz glass ampoules by sulfuric vapor transport and liquid sulfur. Unlike the sublimation technique, the metal enters the gas phase in the form of molecules, hence containing a greater amount of sulfur than the growing crystal. We have investigated the physical properties for a selection of these crystals and compared them to state-of-the-art findings reported in the literature. The acquired electronic properties features demonstrate the overall high quality of single crystals grown in this work as exemplified by CoS2, ReS2, NbS2, and TaS2. This new approach to synthesize high-quality TMD single crystals can alleviate many material quality concerns and is suitable for emerging electronic devices.

Epitaxial Growth of High-Quality Monolayer MoS2 Single Crystals on Low-Symmetry Vicinal Au(101) Facets with Different Miller Indices

Epitaxial growth of wafer-scale monolayer semiconducting transition metal dichalcogenide single crystals is essential for advancing their applications in next-generation transistors and highly integrated circuits. Several efforts have been made for the growth of monolayer MoS2 single crystals on high-symmetry Au(111) and sapphire substrates, while more prototype growth systems still need to be discovered for clarifying the internal mechanisms. Herein, we report the epitaxial growth of unidirectionally aligned monolayer MoS2 domains and single-crystal films on low-symmetry Au(101) vicinal facets via a facile chemical vapor deposition method. On-site scanning tunneling microscopy observations reveal the formation of a specific rectangular Moiré pattern along the [101̅] step edge of Au(101) and along its perpendicular direction. The perfect lattice constant matching of MoS2/Au(101) along the substrate high-symmetry directions (i.e., Au[101̅], Au [010]) as well as the step-edge-guiding effect are proposed to facilitate the robust epitaxy. Multiscale characterizations further confirm the domain-boundary-free feature of the monolayer MoS2 films merged by unidirectionally aligned monolayer domains. This work hereby puts forward a symmetry mismatched epitaxial system for the direct synthesis of monolayer MoS2 single crystals, which should deepen our understanding about the epitaxy of 2D layered materials and propel their applications in various fields.

Epitaxial growth of inch-scale single-crystal transition metal dichalcogenides through the patching of unidirectionally orientated ribbons

Two-dimensional (2D) semiconductors, especially transition metal dichalcogenides (TMDs), have been envisioned as promising candidates in extending Moore’s law. To achieve this, the controllable growth of wafer-scale TMDs single crystals or periodic single-crystal patterns are fundamental issues. Herein, we present a universal route for synthesizing arrays of unidirectionally orientated monolayer TMDs ribbons (e.g., MoS2, WS2, MoSe2, WSe2, MoSxSe2-x), by using the step edges of high-miller-index Au facets as templates. Density functional theory calculations regarding the growth kinetics of specific edges have been performed to reveal the morphological transition from triangular domains to patterned ribbons. More intriguingly, we find that, the uniformly aligned TMDs ribbons can merge into single-crystal films through a one-dimensional edge epitaxial growth mode. This work hereby puts forward an alternative pathway for the direct synthesis of inch-scale uniform monolayer TMDs single-crystals or patterned ribbons, which should promote their applications as channel materials in high-performance electronics or other fields.

Ultrafast growth of large single crystals of monolayer WS2 and WSe2.

Monolayer transition metal dichalcogenides (TMDs) have attracted considerable attention as atomically thin semiconductors for the ultimate transistor scaling. For practical applications in integrated electronics, large monolayer single crystals are essential for ensuring consistent electronic properties and high device yield. The TMDs available today are generally obtained by mechanical exfoliation or chemical vapor deposition (CVD) growth, but are often of mixed layer thickness, limited single crystal domain size or have very slow growth rate. Scalable and rapid growth of large single crystals of monolayer TMDs requires maximization of lateral growth rate while completely suppressing the vertical growth, which represents a fundamental synthetic challenge and has motivated considerable efforts. Herein we report a modified CVD approach with controllable reverse flow for rapid growth of large domain single crystals of monolayer TMDs. With the use of reverse flow to precisely control the chemical vapor supply in the thermal CVD process, we can effectively prevent undesired nucleation before reaching optimum growth temperature and enable rapid nucleation and growth of monolayer TMD single crystals at a high temperature that is difficult to attain with use of a typical thermal CVD process. We show that monolayer single crystals of 450 μm lateral size can be prepared in 10 s, with the highest lateral growth rate up to 45 μm/s. Electronic characterization shows that the resulting monolayer WSe2 material exhibits excellent electronic properties with carrier mobility up to 90 cm2 V−1 s−1, comparable to that of the best exfoliated monolayers. Our study provides a robust pathway for rapid growth of high-quality TMD single crystals.

Seeded growth of high-quality transition metal dichalcogenide single crystals via chemical vapor transport

Seeded chemical vapor transport growth gives high-quality and millimeter-sized transition metal dichalcogenide single crystals in a short period.

An approach to high-throughput growth of submillimeter transition metal dichalcogenide single crystals.

High-throughput growth of large size transition metal dichalcogenide (TMD) single crystals is an important challenge for their applications in the next generation electronic and optoelectronic integration devices. Here we report the high-throughput growth of submillimeter monolayer TMD single crystals by two-stage space confined chemical vapor deposition, where the nucleation density of TMD crystals is significantly decreased for the growth of large size monolayer crystals by the space confinement effect. Moreover, high-throughput growth of submillimeter TMD crystals is also achieved by stacking the substrates along the perpendicular direction to the flow of the reaction gases. The mobilities of the TMD materials produced in this way are up to 1.2, 17.0 and 25.0 cm2 (V s)-1 for monolayer WS2, WSe2 and MoS2 single crystals, respectively. The results demonstrate that two-stage space confined growth is a highly promising method for high-throughput fabrication of high-quality submillimeter monolayer TMD single crystals, which will pave a new pathway to large-scale production of TMD-based electronic and optoelectronic devices.

Low‐Temperature Eutectic Synthesis of PtTe2 with Weak Antilocalization and Controlled Layer Thinning

AbstractMetallic transition metal dichalcogenides (TMDs) have exhibited various exotic physical properties and hold the promise of novel optoelectronic and topological devices applications. However, the synthesis of metallic TMDs is based on gas‐phase methods and requires high‐temperature condition. As an alternative to the gas‐phase synthetic approach, lower temperature eutectic liquid‐phase synthesis presents a very promising approach with the potential for larger‐scale and controllable growth of high‐quality thin metallic TMD single crystals. Here, the first realization of low‐temperature eutectic liquid‐phase synthesis of type‐II Dirac semimetal PtTe2 single crystals with thickness ranging from 2 to 200 nm is presented. The electrical measurement of synthesized PtTe2 reveals a record‐high conductivity of as high as 3.3 × 106 S m−1 at room temperature. Besides, the weak antilocalization behavior is identified experimentally in the type‐II Dirac semimetal PtTe2 for the first time. Furthermore, a simple and general strategy is developed to obtain atomically thin PtTe2 crystal by thinning as‐synthesized bulk samples, which can still retain highly crystalline and exhibits excellent electrical conductivity. The results of controllable and scalable low‐temperature eutectic liquid‐phase synthesis and layer‐by‐layer thinning of high‐quality thin PtTe2 single crystals offer a simple and general approach for obtaining different thickness metallic TMDs with high melting‐point transition metal.

The growth and thermodynamical feasibility of tungsten diselenide single crystals using chemical vapour transport technique

Thermodynamical feasibility study and the growth of layer structured transition metal dichalcogenide single crystals of WSe2, using iodine as transporting agent, has been reported in this paper. The characterization of the grown samples have been done by X-ray analysis.