Xingxing Zhang

Nature Materials. doi:10.1038/nmat4996

Authors: Masaru Onga, Yijin Zhang, Toshiya Ideue & Yoshihiro Iwasa

The spontaneous Hall effect driven by the quantum Berry phase (which serves as an internal magnetic flux in momentum space) manifests the topological nature of quasiparticles and can be used to control the information flow, such as spin and valley. We report a Hall effect of excitons (fundamental composite particles of electrons and holes that dominate optical responses in semiconductors). By polarization-resolved photoluminescence mapping, we directly observed the Hall effect of excitons in monolayer MoS2 and valley-selective spatial transport of excitons on a micrometre scale. The Hall angle of excitons is found to be much larger than that of single electrons in monolayer MoS2 (ref. ), implying that the quantum transport of the composite particles is significantly affected by their internal structures. The present result not only poses a fundamental problem of the Hall effect in composite particles, but also offers a route to explore exciton-based valleytronics in two-dimensional materials.

A facile and universal approach, namely, polar surface‐confined crystallization, is developed to grow highly aligned organic semiconductor single crystals with unitary crystallographic orientation on polymer dielectrics. Organic field‐effect transistors made from the 2,7‐dioctyl[1]benzothieno[3,2‐b]benzothiophene single crystal arrays on flexible substrates exhibit excellent device performance.

Abstract

Polymer dielectrics with intrinsic mechanical flexibility are considered as a key component for flexible organic field‐effect transistors (OFETs). However, it remains a challenge to fabricate highly aligned organic semiconductor single crystal (OSSC) arrays on the polymer dielectrics. Herein, for the first time, a facile and universal strategy, polar surface‐confined crystallization (PSCC), is proposed to grow highly aligned OSSC arrays on poly(4‐vinylphenol) (PVP) dielectric layer. The surface polarity of PVP is altered periodically with oxygen‐plasma treatment, enabling the preferential nucleation of organic crystals on the strong‐polarity regions. Moreover, a geometrical confinement effect of the patterned regions can also prevent multiple nucleation and misaligned molecular packing, enabling the highly aligned growth of OSSC arrays with uniform morphology and unitary crystallographic orientation. Using 2,7‐dioctyl[1]benzothieno[3,2‐b]benzothiophene (C8‐BTBT) as an example, highly aligned C8‐BTBT single crystal arrays with uniform molecular packing and crystal orientation are successfully fabricated on the PVP layer, which can guarantee their uniform electrical properties. OFETs made from the C8‐BTBT single crystal arrays on flexible substrates exhibit a mobility as high as 2.25 cm² V⁻¹ s⁻¹, which has surpassed the C8‐BTBT polycrystalline film‐based flexible devices. This work paves the way toward the fabrication of highly aligned OSSCs on polymer dielectrics for high‐performance, flexible organic devices.

Nature Communications, Published online: 04 June 2019; doi:10.1038/s41467-019-10483-8

Layered materials governed by van der Waals (vdW) interactions offer opportunities for interlayer tuning of the materials' properties. Here, the authors demonstrate that in-plane tensile strain can effectively tune the vdW interactions of few-layered black phosphorus and weaken its interlayer coupling even though the sample shrinks in the vertical direction.

Nature Communications, Published online: 06 June 2019; doi:10.1038/s41467-019-10477-6

The long lifetime and spin properties of dark excitons in atomically thin transition metal dichalcogenides offer opportunities to explore light-matter interactions beyond electric dipole transitions. Here, the authors demonstrate that the coupling of the dark exciton and an optically silent chiral phonon enables the intrinsic photoluminescence of the dark-exciton replica in monolayer WSe2

Atomic layer deposition enables fabrication of microstructures with extraordinarily low stiffness at nanometer‐scale thickness. Low‐stiffness films of SiO₂ and Pt are employed to miniaturize mechanical metamaterials and mechanisms that can withstand repeated actuation and extreme deformation. Sensitive magnetic actuators are presented as an example application of this fabrication platform.

Abstract

Bending and folding techniques such as origami and kirigami enable the scale‐invariant design of 3D structures, metamaterials, and robots from 2D starting materials. These design principles are especially valuable for small systems because most micro‐ and nanofabrication involves lithographic patterning of planar materials. Ultrathin films of inorganic materials serve as an ideal substrate for the fabrication of flexible microsystems because they possess high intrinsic strength, are not susceptible to plasticity, and are easily integrated into microfabrication processes. Here, atomic layer deposition (ALD) is employed to synthesize films down to 2 nm thickness to create membranes, metamaterials, and machines with micrometer‐scale dimensions. Two materials are studied as model systems: ultrathin SiO₂ and Pt. In this thickness limit, ALD films of these materials behave elastically and can be fabricated with fJ‐scale bending stiffnesses. Further, ALD membranes are utilized to design micrometer‐scale mechanical metamaterials and magnetically actuated 3D devices. These results establish thin ALD films as a scalable basis for micrometer‐scale actuators and robotics.

Using in situ microscopy, thermolysis of an amorphous precursor to form 2D MoS₂ crystals is observed at atomic resolution. Critical steps such as nucleation of nanograins and grain growth through aggregation of nanograins are analyzed using atomic resolution STEM images. The research sheds light on the controlled synthesis of 2D MoS₂ thin films through a thermolysis approach.

Abstract

Understanding and controlling the transformations of transition metal dichalcogenides (TMDs) from amorphous precursors into two‐dimensional (2D) materials is important for guiding synthesis, directing fabrication, and tailoring functional properties. Here, the combined effects of thermal energy and electron beam irradiation are explored on the structural evolution of 2D MoS₂ flakes through the thermal decomposition of a (NH₄)₂MoS₄ precursor inside an ultrahigh vacuum (10⁻⁹ Torr) scanning transmission electron microscope (STEM). The influence of reaction temperature, growth substrate, and the initial precursor morphology on the resulting 2D MoS₂ flake morphology, edge structures, and point defects are explored. Although thermal decomposition occurs extremely fast at elevated temperatures and is difficult to capture using current STEM techniques, electron beam irradiation can induce local transformations at lower temperatures, enabling direct observation and interpretation of critical growth steps including oriented attachment and transition from single‐ to multilayer structures at atomic resolution. An increase in the number of layers of the MoS₂ flakes from island growth is investigated using electron beam irradiation. These findings provide insight into the growth mechanisms and factors that control the synthesis of few‐layer MoS₂ flakes through thermolysis and toward the prospect of atomically precise control and growth of 2D TMDs.

The growth mechanism of vertical heterostructures is understood in terms of nucleation and kinetics, where active clusters with a high diffusion barrier promote the nucleation on top of transition metal dichalcogenide templates to realize vertical heterostructures. Benefiting from the efficient control of the diffusion barrier of the active clusters, high‐quality vertical heterostructures with various configurations and compositions are successfully synthesized.

Abstract

The rational control of the nucleation and growth kinetics to enable the growth of 2D vertical heterostructure remains a great challenge. Here, an in‐depth study is provided toward understanding the growth mechanism of transition metal dichalcogenides (TMDCs) vertical heterostructures in terms of the nucleation and kinetics, where active clusters with a high diffusion barrier will induce the nucleation on top of the TMDC templates to realize vertical heterostructures. Based on this mechanism, in the experiment, through rational control of the metal/chalcogenide ratio in the vapor precursors, effective manipulation of the diffusion barrier of the active clusters and precise control of the heteroepitaxy direction are realized. In this way, a family of vertical TMDCs heterostructures is successfully designed. Optical studies and scanning transmission electron microscopy investigations exhibit that the resulting heterostructures possess atomic sharp interfaces without apparent alloying and defects. This study provides a deep understanding regarding the growth mechanism in terms of the nucleation and kinetics and the robust growth of 2D vertical heterostructures, defining a versatile material platform for fundamental studies and potential device applications.

Perpendicular magnetic anisotropy (PMA) and spin‐orbit torque (SOT) efficiency are greatly enhanced by MoS₂. First‐principles calculation and X‐ray absorption reveal that MoS₂ results in the modification of orbital hybridization at the Pt/Co interface. These findings may pave a new way to engineer the PMA and SOT efficiency by 2D materials.

Abstract

2D transition metal dichalcogenides have attracted much attention in the field of spintronics due to their rich spin‐dependent properties. The promise of highly compact and low‐energy‐consumption spin‐orbit torque (SOT) devices motivates the search for structures and materials that can satisfy the requirements of giant perpendicular magnetic anisotropy (PMA) and large SOT simultaneously in SOT‐based magnetic memory. Here, it is demonstrated that PMA and SOT in a heavy metal/transition metal ferromagnet structure, Pt/[Co/Ni]₂, can be greatly enhanced by introducing a molybdenum disulfide (MoS₂) underlayer. According to first‐principles calculation and X‐ray absorption spectroscopy (XAS), the enhancement of the PMA is ascribed to the modification of the orbital hybridization at the interface of Pt/Co due to MoS₂. The enhancement of SOT by the role played by MoS₂ is explained, which is strongly supported by the identical behavior of SOT and PMA as a function of Pt thickness. This work provides new possibilities to integrate 2D materials into promising spintronics devices.

The distorted octahedral structure of 1T′‐MoS₂ is confirmed, and the in‐plane optical and electrical anisotropies of metastable 1T′‐MoS₂ layers are investigated. Importantly, the dependence of electrocatalytic activity on the anisotropic charge transport in 1T′‐MoS₂ layers is demonstrated.

Abstract

Crystal phases play a key role in determining the physicochemical properties of a material. To date, many phases of transition metal dichalcogenides have been discovered, such as octahedral (1T), distorted octahedral (1T′), and trigonal prismatic (2H) phases. Among these, the 1T′ phase offers unique properties and advantages in various applications. Moreover, the 1T′ phase consists of unique zigzag chains of the transition metals, giving rise to interesting in‐plane anisotropic properties. Herein, the in‐plane optical and electrical anisotropies of metastable 1T′‐MoS₂ layers are investigated by the angle‐resolved Raman spectroscopy and electrical measurements, respectively. The deconvolution of J₁ and J₂ peaks in the angle‐resolved Raman spectra is a key characteristic of high‐quality 1T′‐MoS₂ crystal. Moreover, it is found that its electrocatalytic performance may be affected by the crystal orientation of anisotropic material due to the anisotropic charge transport.

Laminar membranes assembled by 2D materials carry numerous sub‐nanoscale channels for selective water and ion transport, which is highly desired in multiple fields including the environment, resources, and energy. An overview of water‐ and ion‐selective laminar membranes is presented to focus on their material and assembly background, transport mechanisms, and selective performance.

Abstract

Selective water and ion transport are essential in fields related to the environment, resources, energy, and more. Membranes, especially those constituted by 2D materials, are promising to control mass transport within nano‐ and sub‐nanoscales. When stacked together, the ultrathin nanosheets of these materials can build up laminar membranes with an ordered layer‐like structure. Numerous channels are thereby created among layers for fast and selective mass transport, which arouses huge research and application interests. This Review aims to present the latest theoretical and experimental advances of 2D laminar membranes for selective water and ion transport, covering three fundamental aspects. Starting with a concise introduction to the materials and assembly for laminar membranes, it then mainly focuses on systematically discussing the transport‐controlling effects caused by intrinsic membrane structure and extrinsic influences. The relation between these effects and current membrane selective performance as well as future membrane designs is then elucidated. The most urgent challenges and corresponding opportunities that emerge around 2D laminar membranes are highlighted thereafter.

For the first time, continuous and homogeneous wafer‐scale monolayer MoS₂ films are grown by a two‐step process, with controllable excitonic and electronic properties. The excitonic and electronic performance of these films are superior to all previously reported two‐step methods. In fact, they are comparable to monolayer MoS₂ films deposited by chemical vapor deposition.

Abstract

To realize multifunctional devices at the wafer scale, the growth process of monolayer (ML) 2D semiconductors must meet two key requirements: 1) growth of continuous and homogeneous ML film at the wafer scale and 2) controllable tuning of the properties of the ML film. However, there is still no growth method available that fulfills both of these criteria. Here, the first report is presented on the preparation of continuous and uniform ML MoS₂ films through a two‐step process at the wafer scale. Unlike in previous ML MoS₂ film growth processes, the ML MoS₂ film can be uniformly modulated across the wafer in terms of material structure and composition, exciton state, and electronic transport performance. A significant result is that the high‐quality wafer‐scale ML MoS₂ films realize superior electronic performance compared to reported two‐step‐grown films, and it even matches or exceeds reported ML MoS₂ films prepared by other processes. The transistor performance of the optimized ML film achieves a field effect mobility of 10 to 30 cm² V⁻¹ s⁻¹, an on/off current ratio of about 10⁷, and hysteresis as low as 0.4 V.

Using in situ microscopy, thermolysis of an amorphous precursor to form 2D MoS₂ crystals is observed at atomic resolution. Critical steps such as nucleation of nanograins and grain growth through aggregation of nanograins are analyzed using atomic resolution STEM images. The research sheds light on the controlled synthesis of 2D MoS₂ thin films through a thermolysis approach.

Abstract

Understanding and controlling the transformations of transition metal dichalcogenides (TMDs) from amorphous precursors into two‐dimensional (2D) materials is important for guiding synthesis, directing fabrication, and tailoring functional properties. Here, the combined effects of thermal energy and electron beam irradiation are explored on the structural evolution of 2D MoS₂ flakes through the thermal decomposition of a (NH₄)₂MoS₄ precursor inside an ultrahigh vacuum (10⁻⁹ Torr) scanning transmission electron microscope (STEM). The influence of reaction temperature, growth substrate, and the initial precursor morphology on the resulting 2D MoS₂ flake morphology, edge structures, and point defects are explored. Although thermal decomposition occurs extremely fast at elevated temperatures and is difficult to capture using current STEM techniques, electron beam irradiation can induce local transformations at lower temperatures, enabling direct observation and interpretation of critical growth steps including oriented attachment and transition from single‐ to multilayer structures at atomic resolution. An increase in the number of layers of the MoS₂ flakes from island growth is investigated using electron beam irradiation. These findings provide insight into the growth mechanisms and factors that control the synthesis of few‐layer MoS₂ flakes through thermolysis and toward the prospect of atomically precise control and growth of 2D TMDs.

The wide range of techniques that can be used toward the production and deposition of 2D materials' inks into space‐confined patterns or continuous thin films are discussed in this review. The importance of reaching precise control over the material's properties through a detailed understanding of their structure and interconnectivity between deposited sheets is discussed.

Abstract

2D materials (2DMs), which can be produced by exfoliating bulk crystals of layered materials, display unique optical and electrical properties, making them attractive components for a wide range of technological applications. This review describes the most recent developments in the production of high‐quality 2DMs based inks using liquid‐phase exfoliation (LPE), combined with the patterning approaches, highlighting convenient and effective methods for generating materials and films with controlled thicknesses down to the atomic scale. Different processing strategies that can be employed to deposit the produced inks as patterns and functional thin‐films are introduced, by focusing on those that can be easily translated to the industrial scale such as coating, spraying, and various printing technologies. By providing insight into the multiscale analyses of numerous physical and chemical properties of these functional films and patterns, with a specific focus on their extraordinary electronic characteristics, this review offers the readers crucial information for a profound understanding of the fundamental properties of these patterned surfaces as the millstone toward the generation of novel multifunctional devices. Finally, the challenges and opportunities associated to the 2DMs' integration into working opto‐electronic (nano)devices is discussed.

Nature Communications, Published online: 27 May 2019; doi:10.1038/s41467-019-10228-7

The unique valley and spin texture of atomically thin transition metal dichalcogenides (TMDs) allows the observation of the valley Zeeman effect for neutral and charged excitons. Here, the authors unveil the underlying physics of the magneto-optical response and valley Zeeman splitting of trions in tungsten-based TMDs.