van der Waals Metallic Transition Metal Dichalcogenides.

Transition metal dichalcogenides are layered materials which are composed of transition metals and chalcogens of the group VIA in a 1:2 ratio. These layered materials have been extensively investigated over synthesis and optical and electrical properties for several decades. It can be insulators, semiconductors, or metals revealing all types of condensed matter properties from a magnetic lattice distorted to superconducting characteristics. Some of these also feature the topological manner. Instead of covering the semiconducting properties of transition metal dichalcogenides, which have been extensively revisited and reviewed elsewhere, here we present the structures of metallic transition metal dichalcogenides and their synthetic approaches for not only high-quality wafer-scale samples using conventional methods (e.g., chemical vapor transport, chemical vapor deposition) but also local small areas by a modification of the materials using Li intercalation, electron beam irradiation, light illumination, pressures, and strains. Some representative band structures of metallic transition metal dichalcogenides and their strong layer-dependence are reviewed and updated, both in theoretical calculations and experiments. In addition, we discuss the physical properties of metallic transition metal dichalcogenides such as periodic lattice distortion, magnetoresistance, superconductivity, topological insulator, and Weyl semimetal. Approaches to overcome current challenges related to these materials are also proposed.

Role of alkali metal promoter in enhancing lateral growth of monolayer transition metal dichalcogenides.

Synthesis of monolayer transition metal dichalcogenides (TMDs) via chemical vapor deposition relies on several factors such as precursor, promoter, substrate, and surface treatment of substrate. Among them, the use of promoter is crucial for obtaining uniform and large-area monolayer TMDs. Although promoters have been speculated to enhance adhesion of precursors to the substrate, their precise role in the growth mechanism has rarely been discussed. Here, we report the role of alkali metal promoter in growing monolayer TMDs. The growth occurred via the formation of sodium metal oxides which prevent the evaporation of metal precursor. Furthermore, the silicon oxide substrate helped to decrease the Gibbs free energy by forming sodium silicon oxide compounds. The resulting sodium metal oxide was anchored within such concavities created by corrosion of silicon oxide. Consequently, the wettability of the precursors to silicon oxide was improved, leading to enhance lateral growth of monolayer TMDs.

Room Temperature Semiconductor-Metal Transition of MoTe2 Thin Films Engineered by Strain.

We demonstrate a room temperature semiconductor-metal transition in thin film MoTe2 engineered by strain. Reduction of the 2H-1T' phase transition temperature of MoTe2 to room temperature was realized by introducing a tensile strain of 0.2%. The observed first-order SM transition improved conductance ∼10 000 times and was made possible by an unusually large temperature-stress coefficient, which results from a large volume change and small latent heat. The demonstrated strain-modulation of the phase transition temperature is expected to be compatible with other TMDs enabling the 2D electronics utilizing polymorphism of TMDs along with the established materials.

Hyperdislocations in van der Waals Layered Materials.

Dislocations are one-dimensional line defects in three-dimensional crystals or periodic structures. It is common that the dislocation networks made of interactive dislocations be generated during plastic deformation. In van der Waals layered materials, the highly anisotropic nature facilitates the formation of such dislocation networks, which is critical for the friction or exfoliation behavior for these materials. By transmission electron microscopy analysis, we found the topological defects in such dislocation networks can be perfectly rationalized in the framework of traditional dislocation theory, which we applied the name "hyperdislocations". Due to the strong pinning effect of hyperdislocations, the state of exfoliation can be easily triggered by 1° twisting between two layers, which also explains the origin of disregistry and frictionlessness for all of the superlubricants that are widely used for friction reduction and wear protection.

Synthesis of Large-Scale Monolayer 1T'-MoTe2 and Its Stabilization via Scalable hBN Encapsulation.

Out of the different structural phases of molybdenum ditelluride (MoTe2), the distorted octahedral 1T' possesses great interest for fundamental physics and is a promising candidate for the implementation of innovative devices such as topological transistors. Indeed, 1T'-MoTe2 is a semimetal with superconductivity, which has been predicted to be a Weyl semimetal and a quantum spin Hall insulator in bulk and monolayer form, respectively. Large instability of monolayer 1T'-MoTe2 in environmental conditions, however, has made its investigation extremely challenging so far. In this work, we demonstrate homogeneous growth of large single-crystal (up to 500 µm) monolayer 1T'-MoTe2 via chemical vapor deposition (CVD) and its stabilization in air with a scalable encapsulation approach. The encapsulant is obtained by electrochemically delaminating CVD hexagonal boron nitride (hBN) from copper foil, and it is applied on the freshly grown 1T'-MoTe2 via a top-down dry lamination step. The structural and electrical properties of encapsulated 1T'-MoTe2 have been monitored over several months to assess the degree of degradation of the material. We find that when encapsulated with hBN, the lifetime of monolayer 1T'-MoTe2 successfully increases from a few minutes to more than a month. Furthermore, the encapsulated monolayer can be subjected to transfer, device processing, and heating and cooling cycles without degradation of its properties. The potential of this scalable heterostack is confirmed by the observation of signatures of low-temperature phase transition in monolayer 1T'-MoTe2 by both Raman spectroscopy and electrical measurements. The growth and encapsulation methods reported in this work can be employed for further fundamental studies of this enticing material as well as facilitate the technological development of monolayer 1T'-MoTe2.

Lifshitz Transition and Non-Fermi Liquid Behavior in Highly Doped Semimetals.

The classical Fermi liquid theory and Drude model have provided fundamental ways to understand the resistivity of most metals. The violation of the classical theory, known as non-Fermi liquid (NFL) transport, appears in certain metals, including topological semimetals, but quantitative understanding of the NFL behavior has not yet been established. In particular, the determination of the non-quadratic temperature exponent in the resistivity, a sign of NFL behavior, remains a puzzling issue. Here, a physical model to quantitatively explain the Lifshitz transition and NFL behavior in highly doped (a carrier density of ≈1022 cm-3 ) monoclinic Nb2 Se3 is reported. Hall and magnetoresistance measurements, the two-band Drude model, and first-principles calculations demonstrate an apparent chemical potential shift by temperature in monoclinic Nb2 Se3 , which induces a Lifshitz transition and NFL behavior in the material. Accordingly, the non-quadratic temperature exponent in the resistivity can be quantitatively determined by the chemical potential shift under the framework of Fermi liquid theory. This model provides a new experimental insight for nontrivial transport with NFL behavior or sign inversion of Seebeck coefficients in emerging materials.

Low-voltage 2D materials-based printed field-effect transistors for integrated digital and analog electronics on paper.

Paper is the ideal substrate for the development of flexible and environmentally sustainable ubiquitous electronic systems, which, combined with two-dimensional materials, could be exploited in many Internet-of-Things applications, ranging from wearable electronics to smart packaging. Here we report high-performance MoS2 field-effect transistors on paper fabricated with a "channel array" approach, combining the advantages of two large-area techniques: chemical vapor deposition and inkjet-printing. The first allows the pre-deposition of a pattern of MoS2; the second, the printing of dielectric layers, contacts, and connections to complete transistors and circuits fabrication. Average ION/IOFF of 8 × 103 (up to 5 × 104) and mobility of 5.5 cm2 V-1 s-1 (up to 26 cm2 V-1 s-1) are obtained. Fully functional integrated circuits of digital and analog building blocks, such as logic gates and current mirrors, are demonstrated, highlighting the potential of this approach for ubiquitous electronics on paper.

Intragranular Dispersion of Carbon Nanotubes Comprehensively Improves Aluminum Alloys.

The room-temperature tensile strength, toughness, and high-temperature creep strength of 2000, 6000, and 7000 series aluminum alloys can be improved significantly by dispersing up to 1 wt% carbon nanotubes (CNTs) into the alloys without sacrificing tensile ductility, electrical conductivity, or thermal conductivity. CNTs act like forest dislocations, except mobile dislocations cannot annihilate with them. Dislocations cannot climb over 1D CNTs unlike 0D dispersoids/precipitates. Also, unlike 2D grain boundaries, even if some debonding happens along 1D CNT/alloy interface, it will be less damaging because fracture intrinsically favors 2D percolating flaws. Good intragranular dispersion of these 1D strengtheners is critical for comprehensive enhancement of composite properties, which entails change of wetting properties and encapsulation of CNTs inside Al grains via surface diffusion-driven cold welding. In situ transmission electron microscopy demonstrates liquid-like envelopment of CNTs into Al nanoparticles by cold welding.

Heterogeneous Defect Domains in Single-Crystalline Hexagonal WS2.

Single-crystalline monolayer hexagonal WS2 is segmented into alternating triangular domains: sulfur-vacancy (SV)-rich and tungsten-vacancy (WV)-rich domains. The WV-rich domain with deep-trap states reveals an electron-dedoping effect, and the electron mobility and photoluminescence are lower than those of the SV-rich domain with shallow-donor states by one order of magnitude. The vacancy-induced strain and doping effects are investigated via Raman and scanning photoelectron microscopy.

A Van Der Waals Homojunction: Ideal p-n Diode Behavior in MoSe2.

A MoSe2 p-n diode with a van der Waals homojunction is demonstrated by stacking undoped (n-type) and Nb-doped (p-type) semiconducting MoSe2 synthesized by chemical vapor transport for Nb substitutional doping. The p-n diode reveals an ideality factor of ≈1.0 and a high external quantum efficiency (≈52%), which increases in response to light intensity due to the negligible recombination rate at the clean homojunction interface.

DEVICE TECHNOLOGY. Phase patterning for ohmic homojunction contact in MoTe2.

Artificial van der Waals heterostructures with two-dimensional (2D) atomic crystals are promising as an active channel or as a buffer contact layer for next-generation devices. However, genuine 2D heterostructure devices remain limited because of impurity-involved transfer process and metastable and inhomogeneous heterostructure formation. We used laser-induced phase patterning, a polymorph engineering, to fabricate an ohmic heterophase homojunction between semiconducting hexagonal (2H) and metallic monoclinic (1T') molybdenum ditelluride (MoTe2) that is stable up to 300°C and increases the carrier mobility of the MoTe2 transistor by a factor of about 50, while retaining a high on/off current ratio of 10(6). In situ scanning transmission electron microscopy results combined with theoretical calculations reveal that the Te vacancy triggers the local phase transition in MoTe2, achieving a true 2D device with an ohmic contact.