Nanoscrolls of Janus Monolayer Transition Metal Dichalcogenides.

Tubular structures of transition metal dichalcogenides (TMDCs) have attracted attention in recent years due to their emergent physical properties, such as the giant bulk photovoltaic effect and chirality-dependent superconductivity. To understand and control these properties, it is highly desirable to develop a sophisticated method to fabricate TMDC tubular structures with smaller diameters and a more uniform crystalline orientation. For this purpose, the rolling up of TMDC monolayers into nanoscrolls is an attractive approach to fabricating such a tubular structure. However, the symmetric atomic arrangement of a monolayer TMDC generally makes its tubular structure energetically unstable due to considerable lattice strain in curved monolayers. Here, we report the fabrication of narrow nanoscrolls by using Janus TMDC monolayers, which have an out-of-plane asymmetric structure. Janus WSSe and MoSSe monolayers were prepared by the plasma-assisted surface atom substitution of WSe2 and MoSe2 monolayers, respectively, and then were rolled by solution treatment. The multilayer tubular structures of Janus nanoscrolls were revealed by scanning transmission electron microscopy observations. Atomic resolution elemental analysis confirmed that the Janus monolayers were rolled up with the Se-side surface on the outside. We found that the present nanoscrolls have the smallest diameter of about 5 nm, which is almost the same as the value predicted by the DFT calculation. The difference in work functions between the S- and Se-side surfaces was measured by Kelvin probe force microscopy, which is in good agreement with the theoretical prediction. Strong interlayer interactions and anisotropic optical responses of the Janus nanoscrolls were also revealed by Raman and photoluminescence spectroscopy.

Observation of the photovoltaic effect in a van der Waals heterostructure.

van der Waals (vdW) heterostructures, which can be assembled with various two-dimensional materials, provide a versatile platform for exploring emergent phenomena. Here, we report an observation of the photovoltaic effect in a WS2/MoS2 vdW heterostructure. Light excitation of WS2/MoS2 at a wavelength of 633 nm yields a photocurrent without applying bias voltages, and the excitation power dependence of the photocurrent shows characteristic crossover from a linear to square root dependence. Photocurrent mapping has clearly shown that the observed photovoltaic effect arises from the WS2/MoS2 region, not from Schottky junctions at electrode contacts. Kelvin probe microscopy observations show no slope in the electrostatic potential, excluding the possibility that the photocurrent originates from an unintentionally formed built-in potential.

Multilayer In-Plane Heterostructures Based on Transition Metal Dichalcogenides for Advanced Electronics.

In-plane heterostructures of transition metal dichalcogenides (TMDCs) have attracted much attention for high-performance electronic and optoelectronic devices. To date, mainly monolayer-based in-plane heterostructures have been prepared by chemical vapor deposition (CVD), and their optical and electrical properties have been investigated. However, the low dielectric properties of monolayers prevent the generation of high concentrations of thermally excited carriers from doped impurities. To solve this issue, multilayer TMDCs are a promising component for various electronic devices due to the availability of degenerate semiconductors. Here, we report the fabrication and transport properties of multilayer TMDC-based in-plane heterostructures. The multilayer in-plane heterostructures are formed through CVD growth of multilayer MoS2 from the edges of mechanically exfoliated multilayer flakes of WSe2 or NbxMo1-xS2. In addition to the in-plane heterostructures, we also confirmed the vertical growth of MoS2 on the exfoliated flakes. For the WSe2/MoS2 sample, an abrupt composition change is confirmed by cross-sectional high-angle annular dark-field scanning transmission electron microscopy. Electrical transport measurements reveal that a tunneling current flows at the NbxMo1-xS2/MoS2 in-plane heterointerface, and the band alignment is changed from a staggered gap to a broken gap by electrostatic electron doping of MoS2. The formation of a staggered gap band alignment of NbxMo1-xS2/MoS2 is also supported by first-principles calculations.

Experimental verification of SO2 and S desorption contributing to defect formation in MoS2 by thermal desorption spectroscopy.

The defect-free surface of MoS2 is of high importance for applications in electronic devices. Theoretical calculations have predicted that oxidative etching could be responsible for sulfur vacancy formation. No direct experimental evidence, however, points out the role of adsorbed oxygen on sulfur vacancy formation for MoS2, especially on an insulating SiO2/Si substrate. Herein, by applying thermal desorption spectroscopy, we found that sulfur loss can be tightly coupled to adsorbed oxygen, as confirmed by observation of SO2 desorption. With annealing MoS2, even under ultrahigh vacuum, oxygen molecules adsorbed on MoS2 assist the sulfur atom in dissociating from MoS2, and thus, defects are formed as the result of SO2 desorption from 200 °C to 600 °C. At higher temperatures (over 800 °C), on the other hand, direct sulfur desorption becomes dominant. This finding can be well explained by combining the morphology investigation enabled by atomic layer deposition at defective sites and optical transitions observed by photoluminescence measurements. Moreover, a preannealing treatment prior to exfoliation was found to be an effective method to remove the adsorbed oxygen, thus preventing defect formation.

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.

Twist Angle-Dependent Molecular Intercalation and Sheet Resistance in Bilayer Graphene.

Bilayer graphene (BLG) has a two-dimensional (2D) interlayer nanospace that can be used to intercalate molecules and ions, resulting in a significant change of its electronic and magnetic properties. Intercalation of BLG with different materials, such as FeCl3, MoCl5, Li ions, and Ca ions, has been demonstrated. However, little is known about how the twist angle of the BLG host affects intercalation. Here, by using artificially stacked BLG with controlled twist angles, we systematically investigated the twist angle dependence of intercalation of metal chlorides. We discovered that BLG with high twist angles of >15° is more favorable for intercalation than BLG with low twist angles. Density functional theory calculations suggested that the weaker interlayer coupling in high twist angle BLG is the key for effective intercalation. Scanning transmission electron microscope observations revealed that co-intercalation of AlCl3 and CuCl2 molecules into BLG gives various 2D structures in the confined interlayer nanospace. Moreover, before intercalation we observed a significantly lower sheet resistance in BLG with high twist angles (281 ± 98 Ω/□) than that in AB stacked BLG (580 ± 124 Ω/□). Intercalation further decreased the sheet resistance, reaching values as low as 48 Ω/□, which is the lowest value reported so far for BLG. This work provides a twist angle-dependent phenomenon, in which enhanced intercalation and drastic changes of the electrical properties can be realized by controlling the stacking angle of adjacent graphene layers.

Magnon-Coupled Intralayer Moiré Trion in Monolayer Semiconductor-Antiferromagnet Heterostructures.

Moiré fringe patterns created by stacking different 2D layered materials as artificial van der Waals (vdW) heterostructures have become a novel platform to study and engineer optically generated excitonic properties. The moiré patterns contribute to the formation of spatially ordered excitonic states (excitons and trions), which can be used in the quantum simulation of many-body systems and ensembles of coherent quantum light emitters. The intriguing moiré excitonic properties are affected by and controlled via the interaction with magnetic elements. Here, a moiré excitonic system interacting with the magnetic elementary excitation of antiferromagnetic orders in MoSe2 /MnPS3 vdW heterostructures is reported. The low-temperature photoluminescence spectra with additional fine spectral structures on the low-energy side, which are coupled magnon-trion peaks below the Néel temperature of MnPS3 , are carefully investigated. The fine spectral structures with long lifetime and coherence time are assigned to intralayer trion-magnon complexes trapped in the moiré potentials (moiré trion-magnon complexes). These findings highlight the emergence of moiré trion-magnon complexes and provide a new way to explore novel quantum phenomena in moiré excitonic systems with magnetic functionalities.

Versatile Post-Doping toward Two-Dimensional Semiconductors.

We have developed a simple and straightforward way to realize controlled postdoping toward 2D transition metal dichalcogenides (TMDs). The key idea is to use low-kinetic-energy dopant beams and a high-flux chalcogen beam simultaneously, leading to substitutional doping with controlled dopant densities. Atomic-resolution transmission electron microscopy has revealed that dopant atoms injected toward TMDs are incorporated substitutionally into the hexagonal framework of TMDs. The electronic properties of doped TMDs (Nb-doped WSe2) have shown drastic change and p-type action with more than 2 orders of magnitude increase in current. Position-selective doping has also been demonstrated by the postdoping toward TMDs with a patterned mask on the surface. The postdoping method developed in this work can be a versatile tool for 2D-based next-generation electronics in the future.

Photoluminescence from Single-Walled MoS2 Nanotubes Coaxially Grown on Boron Nitride Nanotubes.

Single-walled and multiwalled molybdenum disulfide (MoS2) nanotubes have been coaxially synthesized on small-diameter boron nitride nanotubes (BNNTs) that are obtained from removing single-walled carbon nanotubes (SWCNTs) in heteronanotubes of SWCNTs coated by BNNTs. The photoluminescence (PL) from single-walled MoS2 nanotubes supported by core BNNTs is observed in this work, which evidences the direct bandgap structure of single-walled MoS2 nanotubes with a diameter around 6-7 nm. The observation is consistent with our DFT results that the single-walled MoS2 nanotube changes from an indirect-gap to a direct-gap semiconductor when the diameter of a nanotube is more than around 5.2 nm. On the other hand, when there are SWCNTs inside the heteronanotubes of BNNTs and single-walled MoS2 nanotubes, the PL signal from MoS2 nanotubes is considerably quenched. The charge transfer and energy transfer between SWCNTs and single-walled MoS2 nanotubes were examined through characterizations by PL, X-ray photoelectron spectroscopy, and Raman spectroscopy. Moreover, the PL signal from multiwalled MoS2 nanotubes is significantly quenched. Single-walled and multiwalled MoS2 nanotubes exhibit different Raman features in both resonant and nonresonant Raman spectra.

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.

Microscopic Mechanism of Van der Waals Heteroepitaxy in the Formation of MoS2/hBN Vertical Heterostructures.

Recent studies have revealed that van der Waals (vdW) heteroepitaxial growth of 2D materials on crystalline substrates, such as hexagonal boron nitride (hBN), leads to the formation of self-aligned grains, which results in defect-free stitching between the grains. However, how the weak vdW interaction causes a strong limitation on the crystal orientation of grains is still not understood yet. In this work, we have focused on investigating the microscopic mechanism of the self-alignment of MoS2 grains in vdW epitaxial growth on hBN. Using the density functional theory and the Lennard-Jones potential, we found that the interlayer energy between MoS2 and hBN strongly depends on the size and crystal orientation of MoS2. We also found that, when the size of MoS2 is several tens of nanometers, the rotational energy barrier can exceed ∼1 eV, which should suppress rotation to align the crystal orientation of MoS2 even at the growth temperature.

Retraction: Pentadiamond: A Hard Carbon Allotrope of a Pentagonal Network of sp

Retraction of DOI: 10.1103/PhysRevLett.125.016001.

Restoration and Modification of Magnetosome Biosynthesis by Internal Gene Acquisition in a Magnetotactic Bacterium.

Integration of a large-sized DNA fragment into a chromosome is an important strategy for characterization of cellular functions in microorganisms. Magnetotactic bacteria synthesize intracellular organelles comprising membrane-bound single crystalline magnetite, also referred to as magnetosomes. Magnetosomes have gained interest in both scientific and engineering sectors as they can be utilized as a material for biomedical and nanotechnological applications. Although genetic engineering of magnetosome biosynthesis mechanism has been investigated, the current method requires cumbersome gene preparation processes. Here, the chromosomal integration of a plasmid containing ≈27 magnetosome genes (≈26 kbp region) in a non-magnetic mutant of Magnetospirillum magneticum AMB-1 using a broad-host-range plasmid is shown. The genome sequencing of gene-complemented strains reveals the chromosomal integration of the plasmid with magnetosome genes at a specific site, most likely by catalysis of an endogenous transposase. Magnetosome production is successfully enhanced by integrating a variation of magnetosome gene operons in the chromosome. This chromosomal integration mechanism will allow the design of functional magnetosomes de novo and M. magneticum AMB-1 may be used as a chassis for the designed magnetosome production.

Pentadiamond: A Hard Carbon Allotrope of a Pentagonal Network of sp

A pentagonal covalent network consisting of sp^{2} and sp^{3} C atoms has been investigated based on the density functional theory. Our theoretical investigations clarified that the pentagonal covalent network is a metastable three-dimensional carbon allotrope with the Fm3[over ¯]m space group possessing remarkable mechanical properties: relatively high bulk modulus of 381 GPa together with a negative Poisson's ratio of -0.241. Accordingly, the pentagonal covalent network possesses extremely high Young's and shear moduli of 1691 and 1113 GPa, respectively, surpassing those of the diamond. The electronic structure of the pentagonal network is a semiconductor with an indirect band gap of 2.52 eV between L and X points for valence and conduction band edges, respectively, with the relatively small carrier masses.

One-dimensional van der Waals heterostructures.

We present the experimental synthesis of one-dimensional (1D) van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked. We demonstrate the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on single-walled carbon nanotubes (SWCNTs). For the latter, larger-diameter nanotubes that overcome strain effect were more readily synthesized. We also report a 5-nanometer-diameter heterostructure consisting of an inner SWCNT, a middle three-layer BN nanotube, and an outer MoS2 nanotube. Electron diffraction verifies that all shells in the heterostructures are single crystals. This work suggests that all of the materials in the current 2D library could be rolled into their 1D counterparts and a plethora of function-designable 1D heterostructures could be realized.

Vapor Phase Selective Growth of Two-Dimensional Perovskite/WS2 Heterostructures for Optoelectronic Applications.

Organic-inorganic hybrid perovskites have attracted increased interest owing to their exceptional optoelectronic properties and promising applications. Monolayers of transition metal dichalcogenides (TMDCs), such as tungsten disulfide (WS2), are also intriguing because of their unique optoelectronic properties and their atomically thin and flexible structures. Therefore, the combination of these different types of materials is very attractive in terms of fundamental science of interface interaction, as well as for the realization of ultrathin optoelectronic devices with high performance. Here, we demonstrate the controlled synthesis of two-dimensional (2D) perovskite/WS2 heterostructures by an all vapor-phase growth approach. This involves the chemical vapor deposition (CVD) growth of monolayer WS2, followed by the vapor-phase selective deposition of 2D PbI2 onto the WS2 with the successive conversion of PbI2 to organic-inorganic perovskite (CH3NH3PbI3). Moreover, the selective growth of the perovskite on prepatterned WS2 enables the direct synthesis of patterned heterostructures, avoiding any damage to the perovskite. The photodetectors utilizing the perovskite/WS2 heterostructure show increased responsivities compared with isolated thin perovskite obtained by conventional solution methods. The integration of 2D perovskite with TMDCs opens a new avenue to fabricate advanced devices by combining their unique properties and overcoming current processing difficulties of perovskites.

Chemically Tuned p- and n-Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics.

Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post-silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom-thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p- and n-type semiconductors is essential for various device applications, such as complementary metal-oxide-semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe2 is demonstrated by chemical doping. Two different molecules, 4-nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe2 field-effect transistors (FETs) to p- and n-type, respectively. Moreover, the chemically doped WSe2 show increased effective carrier mobilities of 82 and 25 cm2 V-1 s-1 for holes and electrons, respectively, which are much higher than those of the pristine WSe2 . The doping effects are studied by photoluminescence, Raman, X-ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe2 FETs are integrated into CMOS inverters, exhibiting extremely low power consumption (≈0.17 nW). Furthermore, a p-n junction within single WSe2 grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe2 will contribute to the development of TMDC-based advanced electronics.

Continuous Heteroepitaxy of Two-Dimensional Heterostructures Based on Layered Chalcogenides.

The in-plane connection and layer-by-layer stacking of atomically thin layered materials are expected to allow the fabrication of two-dimensional (2D) heterostructures with exotic physical properties and future engineering applications. However, it is currently necessary to develop a continuous growth process that allows the assembly of a wide variety of atomic layers without interface degradation, contamination, and/or alloying. Herein, we report the continuous heteroepitaxial growth of 2D multiheterostructures and nanoribbons based on layered transition metal dichalcogenide (TMDC) monolayers, employing metal organic liquid precursors with high supply controllability. This versatile process can avoid air exposure during growth process and enables the formation of in-plane heterostructures with ultraclean atomically sharp and zigzag-edge straight junctions without defects or alloy formation around the interface. For the samples grown directly on graphite, we have investigated the local electronic density of states of atomically sharp heterointerface by scanning tunneling microscopy and spectroscopy, together with first-principles calculations. These results demonstrate an approach to realizing diverse nanostructures such as atomic layer-based quantum wires and superlattices and suggest advanced applications in the fields of electronics and optoelectronics.

Catalyst-Selective Growth of Single-Orientation Hexagonal Boron Nitride toward High-Performance Atomically Thin Electric Barriers.

The ability to control the crystal orientation of 2D van der Waals (vdW) layered materials grown on large-scale substrates is crucial for tailoring their electrical properties, as well as for integration of functional 2D devices. In general, multiple orientations, i.e., two or four orientations, appear through the crystal rotational symmetry matching between the material and its substrate. Here, it is reported that hexagonal boron nitride (h-BN), an ideal electric barrier in the family of 2D materials, has a single orientation on inclined Cu (1 0 1) surfaces, where the Cu planes are tilted from the (1 0 1) facet around specific in-plane axes. Density functional theory (DFT) calculation indicates that this is a manifestation of only one favored h-BN orientation with the minimum vdW energy on the inclined Cu (1 0 1) surface. Moreover, thanks to the high interfacial strength with the underlying Cu, the single-orientation h-BN is free of thermal wrinkles, and exhibits a spatially homogeneous morphology and tunnel conductance. The findings point to a feasible approach to direct growth of single-orientation, wrinkle-free h-BN thin film for high-performance 2D electrical devices, and will be of benefit for controllable synthesis of other vdW materials.

A novel graphene barrier against moisture by multiple stacking large-grain graphene.

The moisture barrier properties of stacked graphene layers on Cu surfaces were investigated with the goal of improving the moisture barrier efficiency of single-layer graphene (SLG) for Cu metallization. SLG with large grain size were stacked on Cu surfaces coated with CVD-SLG to cover the grain-boundaries and defective areas of the underneath SLG film, which was confirmed to be oxidized by Raman spectroscopy measurements. To evaluate the humidity resistance of the graphene-coated Cu surfaces, temperature humidity storage (THS) testing was conducted under accelerated oxidation conditions (85 °C and 85% relative humidity) for 100 h. The color changes of the Cu surfaces during THS testing were observed by optical microscopy, while the oxidized Cu into Cu2O and CuO was detected by X-ray photoelectron spectroscopy (XPS). The experimental results were accord with the results of first-principle simulation for the energetic barrier against water diffusion through the stacked graphene layers with different overlap. The results demonstrate the efficiency of SLG stacking approach against moisture for Cu metallization.