Thermally induced atomic reconstruction into fully commensurate structures of transition metal dichalcogenide layers.

Twist angle between two-dimensional layers is a critical parameter that determines their interfacial properties, such as moiré excitons and interfacial ferro-electricity. To achieve better control over these properties for fundamental studies and various applications, considerable efforts have been made to manipulate twist angle. However, due to mechanical limitations and the inevitable formation of incommensurate regions, there remains a challenge in attaining perfect alignment of crystalline orientation. Here we report a thermally induced atomic reconstruction of randomly stacked transition metal dichalcogenide multilayers into fully commensurate heterostructures with zero twist angle by encapsulation annealing, regardless of twist angles of as-stacked samples and lattice mismatches. We also demonstrate the selective formation of R- and H-type fully commensurate phases with a seamless lateral junction using chemical vapour-deposited transition metal dichalcogenides. The resulting fully commensurate phases exhibit strong photoluminescence enhancement of the interlayer excitons, even at room temperature, due to their commensurate structure with aligned momentum coordinates. Our work not only demonstrates a way to fabricate zero-twisted, two-dimensional bilayers with R- and H-type configurations, but also provides a platform for studying their unexplored properties.

In Situ Imaging of an Anisotropic Layer-by-Layer Phase Transition in Few-Layer MoTe2.

Understanding the phase transition mechanisms in two-dimensional (2D) materials is a key to precisely tailor their properties at the nanoscale. Molybdenum ditelluride (MoTe2) exhibits multiple phases at room temperature, making it a promising candidate for phase-change applications. Here, we fabricate lateral 2H-Td interfaces with laser irradiation and probe their phase transitions from micro- to atomic scales with in situ heating in the transmission electron microscope (TEM). By encapsulating the MoTe2 with graphene protection layers, we create an in situ reaction cell compatible with atomic resolution imaging. We find that the Td-to-2H phase transition initiates at phase boundaries at low temperatures (200-225 °C) and propagates anisotropically along the b-axis in a layer-by-layer fashion. We also demonstrate a fully reversible 2H-Td-2H phase transition cycle, which generates a coherent 2H lattice containing inversion domain boundaries. Our results provide insights on fabricating 2D heterophase devices with atomically sharp and coherent interfaces.

Laser-Induced Phase Transition and Patterning of hBN-Encapsulated MoTe2.

Transition metal dichalcogenides exhibit phase transitions through atomic migration when triggered by various stimuli, such as strain, doping, and annealing. However, since atomically thin 2D materials are easily damaged and evaporated from these strategies, studies on the crystal structure and composition of transformed 2D phases are limited. Here, the phase and composition change behavior of laser-irradiated molybdenum ditelluride (MoTe2 ) in various stacked geometry are investigated, and the stable laser-induced phase patterning in hexagonal boron nitride (hBN)-encapsulated MoTe2 is demonstrated. When air-exposed or single-side passivated 2H-MoTe2 are irradiated by a laser, MoTe2 is transformed into Te or Mo3 Te4 due to the highly accumulated heat and atomic evaporation. Conversely, hBN-encapsulated 2H-MoTe2 transformed into a 1T' phase without evaporation or structural degradation, enabling stable phase transitions in desired regions. The laser-induced phase transition shows layer number dependence; thinner MoTe2 has a higher phase transition temperature. From the stable phase patterning method, the low contact resistivity of 1.13 kΩ µm in 2H-MoTe2 field-effect transistors with 1T' contacts from the seamless heterophase junction geometry is achieved. This study paves an effective way to fabricate monolithic 2D electronic devices with laterally stitched phases and provides insights into phase and compositional changes in 2D materials.

Improved Crystallinity of Graphene Grown on Cu/Ni (111) through Sequential Mobile Hot-Wire Heat Treatment.

Over the past few years, many efforts have been devoted to growing single-crystal graphene due to its great potential in future applications. However, a number of issues remain for single-crystal graphene growth, such as control of nanoscale defects and the substrate-dependent nonuniformity of graphene quality. In this work, we demonstrate a possible route toward single-crystal graphene by combining aligned nucleation of graphene nanograins on Cu/Ni (111) and sequential heat treatment over pregrown graphene grains. By use of a mobile hot-wire CVD system, prealigned grains were stitched into one continuous film with up to ∼97% single-crystal domains, compared to graphene grown on polycrystalline Cu, which was predominantly high-angle tilt boundary (HATB) domains. The single-crystal-like graphene showed remarkably high thermal conductivity and carrier mobility of ∼1349 W/mK at 350 K and ∼33 600 (38 400) cm2 V-1 s-1 for electrons (holes), respectively, which indicates that the crystallinity is high due to suppression of HATB domains.

Tailoring Single- and Double-Sided Fluorination of Bilayer Graphene via Substrate Interactions.

While many technologies rely on multilayer heterostructures, most of the studies on chemical functionalization have been limited to monolayer graphene. In order to use functionalization in multilayer systems, we must first understand the interlayer interactions between functionalized and nonfunctionalized (intact) layers and how to selectively functionalize one layer at a time. Here, we demonstrate a method to fabricate single- or double-sided fluorinated bilayer graphene (FBG) by tailoring substrate interactions. Both the top and bottom surfaces of bilayer graphene on the rough silicon dioxide (SiO2) are fluorinated; meanwhile, only the top surface of graphene on hexagonal boron nitride (hBN) is fluorinated. The functionalization type affects electronic properties; double-sided FBG on SiO2 is insulating, whereas single-sided FBG on hBN maintains conducting, showing that the intact bottom layer becomes electrically decoupled from the fluorinated top insulating layer. Our results define a straightforward method to selectively functionalize the top and bottom surfaces of bilayer graphene.

Van der Waals Epitaxially Grown Molecular Crystal Dielectric Sb2O3 for 2D Electronics.

Two-dimensional (2D) semiconducting materials have attracted significant interest as promising candidates for channel materials owing to their high mobility and gate tunability at atomic-layer thickness. However, the development of 2D electronics is impeded due to the difficulty in formation of high-quality dielectrics with a clean and nondestructive interface. Here, we report the direct van der Waals epitaxial growth of a molecular crystal dielectric, Sb2O3, on 2D materials by physical vapor deposition. The grown Sb2O3 nanosheets showed epitaxial relations of 0 and 180° with the 2D template, maintaining high crystallinity and an ultrasharp vdW interface with the 2D materials. As a result, the Sb2O3 nanosheets exhibited a high breakdown field of 18.6 MV/cm for 2L Sb2O3 with a thickness of 1.3 nm and a very low leakage current of 2.47 × 10-7 A/cm2 for 3L Sb2O3 with a thickness of 1.96 nm. We also observed two types of grain boundaries (GBs) with misorientation angles of 0 and 60°. The 0°-GB with a well-stitched boundary showed higher electrical and thermal stabilities than those of the 60°-GB with a disordered boundary. Our work demonstrates a method to epitaxially grow molecular crystal dielectrics on 2D materials without causing any damage, a requirement for high-performance 2D electronics.

The future of two-dimensional semiconductors beyond Moore's law.

The primary challenge facing silicon-based electronics, crucial for modern technological progress, is difficulty in dimensional scaling. This stems from a severe deterioration of transistor performance due to carrier scattering when silicon thickness is reduced below a few nanometres. Atomically thin two-dimensional (2D) semiconductors still maintain their electrical characteristics even at sub-nanometre scales and offer the potential for monolithic three-dimensional (3D) integration. Here we explore a strategic shift aimed at addressing the scaling bottleneck of silicon by adopting 2D semiconductors as new channel materials. Examining both academic and industrial viewpoints, we delve into the latest trends in channel materials, the integration of metal contacts and gate dielectrics, and offer insights into the emerging landscape of industrializing 2D semiconductor-based transistors for monolithic 3D integration.

Optical grade transformation of monolayer transition metal dichalcogenides via encapsulation annealing.

Monolayer transition metal dichalcogenides (TMDs) have emerged as highly promising candidates for optoelectronic applications due to their direct band gap and strong light-matter interactions. However, exfoliated TMDs have demonstrated optical characteristics that fall short of expectations, primarily because of significant defects and associated doping in the synthesized TMD crystals. Here, we report the improvement of optical properties in monolayer TMDs of MoS2, MoSe2, WS2, and WSe2, by hBN-encapsulation annealing. Monolayer WSe2 showed 2000% enhanced photoluminescence quantum yield (PLQY) and 1000% increased lifetime after encapsulation annealing at 1000 °C, which are attributed to dominant radiative recombination of excitons through dedoping of monolayer TMDs. Furthermore, after encapsulation annealing, the transport characteristics of monolayer WS2 changed from n-type to ambipolar, along with an enhanced hole transport, which also support dedoping of annealed TMDs. This work provides an innovative approach to elevate the optical grade of monolayer TMDs, enabling the fabrication of high-performance optoelectronic devices.

Quasi-van der Waals Epitaxial Recrystallization of a Gold Thin Film into Crystallographically Aligned Single Crystals.

Heterointerfaces between two-dimensional (2D) materials and bulk metals determine the electrical and optical properties of their heterostructures. Although deposition of various metals on 2D materials has been studied, there is still a lack of studies on the interaction at the van der Waals (vdW) heterointerface between 2D materials and metals. Here, we report quasi-van der Waals (qvdW) epitaxial recrystallization of a gold thin film into crystallographically aligned single crystals by encapsulation annealing of a gold thin film with hexagonal boron nitride (hBN). When a polycrystalline gold thin film passivated with hBN was annealed, it was recrystallized into single gold crystals with a planar shape and crystallographic alignment with hBN due to a strong interaction between the gold film and hBN at the heterointerface. This reflects that a weak vdW force at the heterointerface is sufficiently strong to induce epitaxial recrystallization. Using this method, we fabricated a gold nanocrystal array with the same crystalline orientation and smooth top surface. Our work demonstrates a new method for epitaxial recrystallization of bulk crystals and provides a deep understanding of the interaction at the vdW heterointerface of 2D materials and metals.

Nucleation and Growth of Monolayer MoS2 at Multisteps of MoO2 Crystals by Sulfurization.

Two-dimensional (2D) materials and their heterostructures are promising for next-generation optoelectronics, spintronics, valleytronics, and electronics. Despite recent progress in various growth studies of 2D materials, mechanical exfoliation of flakes is still the most common method to obtain high-quality 2D materials because precisely controlling material growth and synthesizing a single domain during the growth process of 2D materials, for the desired shape and quality, is challenging. Here, we report the nucleation and growth behaviors of monolayer MoS2 by sulfurizing a faceted monoclinic MoO2 crystal. The MoS2 layers nucleated at the thickness steps of the MoO2 crystal and grew epitaxially with crystalline correlation to the MoO2 surface. The epitaxially grown MoS2 layer expands outwardly on the SiO2 substrate, resulting in a monolayer single-crystal film, despite multiple nucleations of MoS2 layers on the MoO2 surface owing to several thickness steps. Although the photoluminescence of MoS2 is quenched owing to efficient charge transfer between MoS2 and metallic MoO2, the MoS2 stretched out to the SiO2 substrate shows a high carrier mobility of (15 cm2 V-1 s-1), indicating that a high-quality monolayer MoS2 film can be grown using the MoO2 crystal as a seed and precursor. Our work shows a method to grow high-quality MoS2 using a faceted MoO2 crystal and provides a deeper understanding of the nucleation and growth of 2D materials on a step-like surface.

Multioperation-Mode Light-Emitting Field-Effect Transistors Based on van der Waals Heterostructure.

2D semiconductors have shown great potential for application to electrically tunable optoelectronics. Despite the strong excitonic photoluminescence (PL) of monolayer transition metal dichalcogenides (TMDs), their efficient electroluminescence (EL) has not been achieved due to the low efficiency of charge injection and electron-hole recombination. Here, multioperation-mode light-emitting field-effect transistors (LEFETs) consisting of a monolayer WSe2 channel and graphene contacts coupled with two top gates for selective and balanced injection of charge carriers are demonstrated. Visibly observable EL is achieved with the high external quantum efficiency of ≈6% at room temperature due to efficient recombination of injected electrons and holes in a confined 2D channel. Further, electrical tunability of both the channel and contacts enables multioperation modes, such as antiambipolar, depletion,and unipolar regions, which can be utilized for polarity-tunable field-effect transistors and photodetectors. The work exhibits great potential for use in 2D semiconductor LEFETs for novel optoelectronics capable of high efficiency, multifunctions, and heterointegration.

Tailoring Surface Properties via Functionalized Hydrofluorinated Graphene Compounds.

A new compound material of 2D hydrofluorinated graphene (HFG) is demonstrated whose relative hydrogen/fluorine concentrations can be tailored between the extremes of either hydrogenated graphene (HG) and fluorinated graphene (FG). The material is fabricated through subsequent exposures to indirect hydrogen plasma and xenon difluoride (XeF2 ). Controlling the relative concentration in the HFG compound enables tailoring of material properties between the extremes offered by the constituent materials and in-plane patterning produces micrometer-scale regions with different surface properties. The utility of the technique to tailor the surface wettability, surface friction, and electrical conductivity is demonstrated. HFG compounds display wettability between the extremes of pure FG with contact angle of 95° ± 5° and pure HG with contact angle of 42° ± 2°. Similarly, the HFG surface friction may be tailored between the two extremes. Finally, the HFG electrical conductivity tunes through five orders of magnitude when transitioning from FG to HG. When combined with simulation, the electrical measurements reveal the mechanism producing the compound to be a dynamic process of adatom desorption and replacement. This study opens a new class of 2D compound materials and innovative chemical patterning with applications for atomically thin 2D circuits consisting of chemically/electrically modulated regions.

Atomically precise graphene etch stops for three dimensional integrated systems from two dimensional material heterostructures.

Atomically precise fabrication methods are critical for the development of next-generation technologies. For example, in nanoelectronics based on van der Waals heterostructures, where two-dimensional materials are stacked to form devices with nanometer thicknesses, a major challenge is patterning with atomic precision and individually addressing each molecular layer. Here we demonstrate an atomically thin graphene etch stop for patterning van der Waals heterostructures through the selective etch of two-dimensional materials with xenon difluoride gas. Graphene etch stops enable one-step patterning of sophisticated devices from heterostructures by accessing buried layers and forming one-dimensional contacts. Graphene transistors with fluorinated graphene contacts show a room temperature mobility of 40,000 cm2 V-1 s-1 at carrier density of 4 × 1012 cm-2 and contact resistivity of 80 Ω·µm. We demonstrate the versatility of graphene etch stops with three-dimensionally integrated nanoelectronics with multiple active layers and nanoelectromechanical devices with performance comparable to the state-of-the-art.

Author Correction: Atomically precise graphene etch stops for three dimensional integrated systems from two dimensional material heterostructures.

The original version of this Article contained an error in the second sentence of the second paragraph of the 'Electrical properties of fluorinated graphene contacts' section of the Results, which incorrectly read 'The mobility was calculated by the Drude model, µ = ne/σ where µ, n, e, and σ are the carrier mobility, carrier density, electron charge, and sheet conductivity, respectively'. The correct version states 'µ = σ/ne ' in place of 'µ = ne/σ '. This has been corrected in both the PDF and HTML versions of the Article.