Vapor-Phase Indium Intercalation in van der Waals Nanofibers of Atomically Thin W6Te6 Wires.

One-dimensional (1D) conducting materials are of great interest as potential building blocks for integrated nanocircuits. Ternary 1D transition-metal chalcogenides, consisting of M6X6 wires with intercalated A atoms (M = Mo or W; X = S, Se, or Te; A = alkali or rare metals, etc.), have attracted much attention due to their 1D metallic behavior, superconductivity, and mechanical flexibility. However, the conventional solid-state reaction usually produces micrometer-scale bulk crystals, limiting their potential use as nanoscale conductors. Here we demonstrate a versatile method to fabricate indium (In)-intercalated W6Te6 (In-W6Te6) bundles with a nanoscale thickness. We first prepared micrometer-long, crystalline bundles of van der Waals W6Te6 wires using chemical vapor deposition and intercalated In into the crystal via a vapor-phase reaction. Atomic-resolution electron microscopy revealed that In atoms were surrounded by three adjacent W6Te6 wires. First-principles calculations suggested that their wire-by-wire stacking can transform through postgrowth intercalation. Individual In-W6Te6 bundles exhibited metallic behavior, as theoretically predicted. We further identified the vibrational modes by combining polarized Raman spectroscopy and nonresonant Raman calculations.

Continuous Color-Tunable Light-Emitting Devices Based on Compositionally Graded Monolayer Transition Metal Dichalcogenide Alloys.

The diverse series of transition metal dichalcogenide (TMDC) materials has been employed in various optoelectronic applications, such as photodetectors, light-emitting diodes, and lasers. Typically, the detection or emission range of optoelectronic devices is unique to the bandgap of the active material. Therefore, to improve the capability of these devices, extensive efforts have been devoted to tune the bandgap, such as gating, strain, and dielectric engineering. However, the controllability of these methods is severely limited (typically ≈0.1 eV). In contrast, alloying TMDCs is an effective approach that yields a composition-dependent bandgap and enables light emissions over a wide range. In this study, a color-tunable light-emitting device using compositionally graded TMDC alloys is fabricated. The monolayer WS2 /WSe2 alloy grown by chemical vapor deposition shows a spatial gradient in the light-emission energy, which varies from 2.1 to 1.7 eV. This alloy is incorporated in an electrolyte-based light-emitting device structure that can tune the recombination zone laterally. Thus, a continuous and reversible color-tunable light-emitting device is successfully fabricated by controlling the light-emitting positions. The results provide a new approach for exploring monolayer semiconductor-based broadband optical applications.

Large-Scale 1T'-Phase Tungsten Disulfide Atomic Layers Grown by Gas-Source Chemical Vapor Deposition.

The control of crystal polymorphism and exploration of metastable, two-dimensional, 1T'-phase, transition-metal dichalcogenides (TMDs) have received considerable research attention. 1T'-phase TMDs are expected to offer various opportunities for the study of basic condensed matter physics and for its use in important applications, such as devices with topological states for quantum computing, low-resistance contact for semiconducting TMDs, energy storage devices, and as hydrogen evolution catalysts. However, due to the high energy difference and phase change barrier between 1T' and the more stable 2H-phase, there are few methods that can be used to obtain monolayer 1T'-phase TMDs. Here, we report on the chemical vapor deposition (CVD) growth of 1T'-phase WS2 atomic layers from gaseous precursors, i.e., H2S and WF6, with alkali metal assistance. The gaseous nature of the precursors, reducing properties of H2S, and presence of Na+, which acts as a countercation, provided an optimal environment for the growth of 1T'-phase WS2, resulting in the formation of high-quality submillimeter-sized crystals. The crystal structure was characterized by atomic-resolution scanning transmission electron microscopy, and the zigzag chain structure of W atoms, which is characteristic of the 1T' structure, was clearly observed. Furthermore, the grown 1T'-phase WS2 showed superconductivity with the transition temperature in the 2.8-3.4 K range and large upper critical field anisotropy. Thus, alkali metal assisted gas-source CVD growth is useful for realizing large-scale, high-quality, phase-engineered TMD atomic layers via a bottom-up synthesis.

Room-Temperature Chiral Light-Emitting Diode Based on Strained Monolayer Semiconductors.

Room-temperature chiral light sources whose optical helicity can be electrically switched are one of the most important devices for future optical quantum information processing. The emerging valley degree of freedom in monolayer semiconductors allows generation of chiral luminescence via valley polarization. However, relevant valley-polarized light-emitting diodes (LEDs) have only been achieved at low temperatures (typically below 80 K). Here, a room-temperature chiral LED with strained transition metal dichalcogenide monolayers is realized. Spatially resolved polarization spectroscopy reveals that strain effects are crucial to yielding robust valley-polarized electroluminescence. The broken threefold rotational symmetry of strained monolayers induce inequivalent valley drifts at the K/K' valleys, resulting in different amounts of spin recombination driven by electric fields. Based on this scenario, ideally strained conditions are designed for LEDs on flexible substrates, in which the helicity of room-temperature valley-polarized electroluminescence is electrically tuned. The results provide a new pathway for practical chiral light sources based on monolayer semiconductors.

Spatial Control of Dynamic p-i-n Junctions in Transition Metal Dichalcogenide Light-Emitting Devices.

Emerging transition metal dichalcogenides (TMDCs) offer an attractive platform for investigating functional light-emitting devices, such as flexible devices, quantum and chiral devices, high-performance optical modulators, and ultralow threshold lasers. In these devices, the key operation is to control the light-emitting position, that is, the spatial position of the recombination zone to generate electroluminescence, which permits precise light guides/passes/confinement to ensure favorable device performance. Although various structures of TMDC light-emitting devices have been demonstrated, including the transistor configuration and heterostructured diodes, it is still difficult to tune the light-emitting position precisely owing to the structural device complexity. In this study, we fabricated two-terminal light-emitting devices with chemically synthesized WSe2, MoSe2, and WS2 monolayers, and performed direct observations of their electroluminescence, from which we discovered a divergence in their light-emitting positions. Subsequently, we propose a method to associate spatial electroluminescence imaging with transport properties among different samples; consequently, a common rule for determining the locations of recombination zones is revealed. Owing to dynamic carrier accumulations and p-i-n junction formations, the light-emitting positions in electrolyte-based devices can be tuned continuously. The proposed method will expand the device applicability for designing functional optoelectronic applications based on TMDCs.

Air-stable and efficient electron doping of monolayer MoS2 by salt-crown ether treatment.

To maximize the potential of transition-metal dichalcogenides (TMDCs) in device applications, the development of a sophisticated technique for stable and highly efficient carrier doping is critical. Here, we report the efficient n-type doping of monolayer MoS2 using KOH/benzo-18-crown-6, resulting in a doped TMDC that is air-stable. MoS2 field-effect transistors show an increase in on-current of three orders of magnitude and degenerate the n-type behaviour with high air-stability for ∼1 month as the dopant concentration increases. Transport measurements indicate a high electron density of 3.4 × 1013 cm-2 and metallic-type temperature dependence for highly doped MoS2. First-principles calculations support electron doping via surface charge transfer from the K/benzo-18-crown-6 complex to monolayer MoS2. Patterned doping is demonstrated to improve the contact resistance in MoS2-based devices.

Wafer-Scale Growth of One-Dimensional Transition-Metal Telluride Nanowires.

The development of bulk synthetic processes to prepare functional nanomaterials is crucial to achieve progress in fundamental and applied science. Transition-metal chalcogenide (TMC) nanowires, which are one-dimensional (1D) structures having three-atom diameters and van der Waals surfaces, have been reported to possess a 1D metallic nature with great potential in electronics and energy devices. However, their mass production remains challenging. Here, a wafer-scale synthesis of highly crystalline transition-metal telluride nanowires is demonstrated by chemical vapor deposition. The present technique enables formation of either aligned, atomically thin two-dimensional (2D) sheets or random networks of three-dimensional (3D) bundles, both composed of individual nanowires. These nanowires exhibit an anisotropic 1D optical response and superior conducting properties. The findings not only shed light on the controlled and large-scale synthesis of conductive thin films but also provide a platform for the study on physics and device applications of nanowire-based 2D and 3D crystals.

CVD growth of large-area InS atomic layers and device applications.

Group-III monochalcogenides of two-dimensional (2D) layered materials have attracted widespread attention among scientists due to their unique electronic performance and interesting chemical and physical properties. Indium sulfide (InS) is attracting increasing interest from scientists because it has two distinct crystal structures. However, studies on the synthesis of highly crystalline, large-area, and atomically thin-film InS have not been reported thus far. Here, the chemical vapor deposition (CVD) synthesis method of atomic InS crystals has been reported in this paper. The direct chemical vapour phase reaction of metal oxides with chalcogen precursors produces a large-sized hexagonal crystal structure and atomic-thickness InS flakes or films. The InS atomic films are merged with a plurality of triangular InS crystals that are uniform and entire and have surface areas of 1 cm2 and controllable thicknesses in bilayers or trilayers. The properties of the as-grown highly crystalline samples were characterized by spectroscopic and microscopic measurements. The ion-gel gated InS field-effect transistors (FETs) reveal n-type transport behavior, and have an on-off current ratio of >103 and a room-temperature electron mobility of ∼2 cm2 V-1 s-1. Moreover, our CVD InS can be transferred from mica to any substrates, so various 2D materials can be reassembled into vertically stacked heterostructures, thus facilitating the development of heterojunctions and exploration of the properties and applications of their interactions.

Thermoelectric properties of a semicrystalline polymer doped beyond the insulator-to-metal transition by electrolyte gating.

Conducting polymer thin films containing inherent structural disorder exhibit complicated electronic, transport, and thermoelectric properties. The unconventional power-law relation between the Seebeck coefficient (S) and the electrical conductivity (σ) is one of the typical consequences of this disorder, where no maximum of the thermoelectric power factor (P = S 2σ) has been observed upon doping, unlike conventional systems. Here, it is demonstrated that a thiophene-based semicrystalline polymer exhibits a clear maximum of P through wide-range carrier doping by the electrolyte gating technique. The maximum value appears around the macroscopic insulator-to-metal transition upon doping, which is firmly confirmed by the temperature dependence of σ and magnetoresistance measurements. The effect of disorder on charge transport is suppressed in the metallic state, resulting in the conventional S-σ relation described by the Mott equation. The present results provide a physical background for controlling the performance of conducting polymers toward the application to thermoelectric devices.

Exciton Polarization and Renormalization Effect for Optical Modulation in Monolayer Semiconductors.

The ideal quantum confinement structure of monolayer semiconductors offers prominent optical modulation capabilities that are mediated by enhanced many-body interactions. Herein, we establish an electrolyte-gating method for tuning the luminescence properties that are in transition metal dichalcogenide (TMDC) monolayers. We fabricate electric double-layer capacitors on TMDC/graphite heterostructures to investigate electric-field- and carrier-density-dependent photoluminescence. The exciton peak energy initially shows a slight quadratic red shift of ∼1 meV without carrier accumulations, which is caused by the quantum-confined Stark effect. In contrast, the exciton resonance exhibits a larger red shift up to 10 meV with the accumulated carrier density above 1013 cm-2. These results indicate that the optical transitions can be largely modulated by the carrier density control in S- and Se-based TMDCs, as triggered by the doping-induced band gap renormalization effect. To further inspire this modulation capability, we also apply our method to electrolyte-based TMDC light-emitting devices. Biasing solely in electrolyte-induced p-i-n junctions yields pronounced red shifts up to 40 meV for exciton and trion electroluminescence. Consequently, our approach reveals that the doping effects in the high-carrier-density regimes are potentially significant for efficient optical modulation in monolayer semiconductors.

Two-dimensional ground-state mapping of a Mott-Hubbard system in a flexible field-effect device.

A Mott insulator sometimes induces unconventional superconductivity in its neighbors when doped and/or pressurized. Because the phase diagram should be strongly related to the microscopic mechanism of the superconductivity, it is important to obtain the global phase diagram surrounding the Mott insulating state. However, the parameter available for controlling the ground state of most Mott insulating materials is one-dimensional owing to technical limitations. Here, we present a two-dimensional ground-state mapping for a Mott insulator using an organic field-effect device by simultaneously tuning the bandwidth and bandfilling. The observed phase diagram showed many unexpected features such as an abrupt first-order superconducting transition under electron doping, a recurrent insulating phase in the heavily electron-doped region, and a nearly constant superconducting transition temperature in a wide parameter range. These results are expected to contribute toward elucidating one of the standard solutions for the Mott-Hubbard model.

Metal-Guided Selective Growth of 2D Materials: Demonstration of a Bottom-Up CMOS Inverter.

2D transition metal dichalcogenide (TMD) layered materials are promising for future electronic and optoelectronic applications. The realization of large-area electronics and circuits strongly relies on wafer-scale, selective growth of quality 2D TMDs. Here, a scalable method, namely, metal-guided selective growth (MGSG), is reported. The success of control over the transition-metal-precursor vapor pressure, the first concurrent growth of two dissimilar monolayer TMDs, is demonstrated in conjunction with lateral or vertical TMD heterojunctions at precisely desired locations over the entire wafer in a single chemical vapor deposition (VCD) process. Owing to the location selectivity, MGSG allows the growth of p- and n-type TMDs with spatial homogeneity and uniform electrical performance for circuit applications. As a demonstration, the first bottom-up complementary metal-oxide-semiconductor inverter based on p-type WSe2 and n-type MoSe2 is achieved, which exhibits a high and reproducible voltage gain of 23 with little dependence on position.

Synthesis of Large-Area InSe Monolayers by Chemical Vapor Deposition.

Recently, 2D materials of indium selenide (InSe) layers have attracted much attention from the scientific community due to their high mobility transport and fascinating physical properties. To date, reports on the synthesis of high-quality and scalable InSe atomic films are limited. Here, a synthesis of InSe atomic layers by vapor phase selenization of In2 O3 in a chemical vapor deposition (CVD) system, resulting in large-area monolayer flakes or thin films, is reported. The atomic films are continuous and uniform over a large area of 1 × 1 cm2 , comprising of primarily InSe monolayers. Spectroscopic and microscopic measurements reveal the highly crystalline nature of the synthesized InSe monolayers. The ion-gel-gated field-effect transistors based on CVD InSe monolayers exhibit n-type channel behaviors, where the field effect electron mobility values can be up to ≈30 cm2 V-1 s-1 along with an on/off current ratio, of >104 at room temperature. In addition, the graphene can serve as a protection layer to prevent the oxidation between InSe and the ambient environment. Meanwhile, the synthesized InSe films can be transferred to arbitrary substrates, enabling the possibility of reassembly of various 2D materials into vertically stacked heterostructures, prompting research efforts to probe its characteristics and applications.

Monolayer Transition Metal Dichalcogenides as Light Sources.

Reducing the dimensions of materials is one of the key approaches to discovering novel optical phenomena. The recent emergence of 2D transition metal dichalcogenides (TMDCs) has provided a promising platform for exploring new optoelectronic device applications, with their tunable electronic properties, structural controllability, and unique spin valley-coupled systems. This progress report provides an overview of recent advances in TMDC-based light-emitting devices discussed from several aspects in terms of device concepts, material designs, device fabrication, and their diverse functionalities. First, the advantages of TMDCs used in light-emitting devices and their possible functionalities are presented. Second, conventional approaches for fabricating TMDC light-emitting devices are emphasized, followed by introducing a newly established, versatile method for generating light emission in TMDCs. Third, current growing technologies for heterostructure fabrication, in which distinct TMDCs are vertically stacked or laterally stitched, are explained as a possible means for designing high-performance light-emitting devices. Finally, utilizing the topological features of TMDCs, the challenges for controlling circularly polarized light emission and its device applications are discussed from both theoretical and experimental points of view.

A Versatile and Simple Approach to Generate Light Emission in Semiconductors Mediated by Electric Double Layers.

The light-emitting device is the primary device for current light sources. In principle, conventional light-emitting devices need heterostructures and/or intentional carrier doping to form a p-n junction. This junction formation is, however, very difficult to achieve for most emerging semiconductors, and the fabrication of light-emitting devices is invariably a significant challenge. This study proposes a versatile and simple approach to realize light-emitting devices. This proposed device requires only a semiconducting film with two electrodes that are covered with an electrolyte. This unique structure achieves light emission at a voltage slightly larger than the bandgap energy of materials. This study applies this concept to emerging direct bandgap semiconductors, such as transition metal dichalcogenide monolayers and zinc oxide single crystals. These devices generate obvious light emission and provide sufficient evidence of the formation of a dynamic p-i-n junction or tunneling junction, presenting a versatile technique to develop optoelectronic devices.

High Current Injection into Dynamic p-n Homojunction in Polymer Light-Emitting Electrochemical Cells.

Ions and electrons in blends of polymer-electrolyte can work in ensemble to operate light-emitting electrochemical cells (LECs), in which the unique features of in situ formed p-n homojunctions offer efficient charge injection and transport. However, electrochemical features give rise to significant stability and speed issues due to limited electrochemical stability and low ion mobility, resulting in low brightness and a slow response of LECs. Here, these issues are overcome by the separate control of ionic and electronic charges, using a simple driving pulse superimposed on a small base voltage; ions with slow response are rearranged by a constant base voltage, while a high-voltage pulse, superimposed upon the base, injects electrons/holes which have fast response, with minimal effect on the ions. This scheme successfully injects an extremely high current density of > 2 kA cm-2 with a balanced electron/hole ratio, at a high-speed response time of ≈ 50 ns; both properties demonstrate advantages of LECs in making polymers brighter. An in situ electron spin resonance measurement on the LECs further revealed that this impressive performance is due to the highly doped polymers, whose spin density reached 7 × 1019 spins cm-3 , and an ordered polymer structure in the active layer blend.

Direct observation of electrically induced Pauli paramagnetism in single-layer graphene using ESR spectroscopy.

Graphene has been actively investigated as an electronic material owing to many excellent physical properties, such as high charge mobility and quantum Hall effect, due to the characteristics of a linear band structure and an ideal two-dimensional electron system. However, the correlations between the transport characteristics and the spin states of charge carriers or atomic vacancies in graphene have not yet been fully elucidated. Here, we show the spin states of single-layer graphene to clarify the correlations using electron spin resonance (ESR) spectroscopy as a function of accumulated charge density using transistor structures. Two different electrically induced ESR signals were observed. One is originated from a Fermi-degenerate two-dimensional electron system, demonstrating the first observation of electrically induced Pauli paramagnetism from a microscopic viewpoint, showing a clear contrast to no ESR observation of Pauli paramagnetism in carbon nanotubes (CNTs) due to a one-dimensional electron system. The other is originated from the electrically induced ambipolar spin vanishments due to atomic vacancies in graphene, showing a universal phenomenon for carbon materials including CNTs. The degenerate electron system with the ambipolar spin vanishments would contribute to high charge mobility due to the decrease in spin scatterings in graphene.

Electron-hole doping asymmetry of Fermi surface reconstructed in a simple Mott insulator.

It is widely recognized that the effect of doping into a Mott insulator is complicated and unpredictable, as can be seen by examining the Hall coefficient in high Tc cuprates. The doping effect, including the electron-hole doping asymmetry, may be more straightforward in doped organic Mott insulators owing to their simple electronic structures. Here we investigate the doping asymmetry of an organic Mott insulator by carrying out electric-double-layer transistor measurements and using cluster perturbation theory. The calculations predict that strongly anisotropic suppression of the spectral weight results in the Fermi arc state under hole doping, while a relatively uniform spectral weight results in the emergence of a non-interacting-like Fermi surface (FS) in the electron-doped state. In accordance with the calculations, the experimentally observed Hall coefficients and resistivity anisotropy correspond to the pocket formed by the Fermi arcs under hole doping and to the non-interacting FS under electron doping.

Protonation-induced red-coloured circularly polarized luminescence of [5]carbohelicene fused by benzimidazole.

Benzimidazole-fused [5]carbohelicene ([5]HeliBI) was newly synthesized to examine the spectroscopic and chiroptical properties. The reversible protonation and deprotonation processes of [5]HeliBI were successfully investigated using (1)H NMR, absorption and fluorescence spectral measurements. We also confirmed the circularly polarized luminescence of protonated [5]HeliBI (H(+)-[5]HeliBI). This is the first observation of red-coloured CPL of a helicene derivative.