Covalently-Bonded Laminar Assembly of Van der Waals Semiconductors with Polymers: Toward High-Performance Flexible Devices.

Van der Waals semiconductors (vdWS) offer superior mechanical and electrical properties and are promising for flexible microelectronics when combined with polymer substrates. However, the self-passivated vdWS surfaces and their weak adhesion to polymers tend to cause interfacial sliding and wrinkling, and thus, are still challenging the reliability of vdWS-based flexible devices. Here, an effective covalent vdWS-polymer lamination method with high stretch tolerance and excellent electronic performance is reported. Using molybdenum disulfide (MoS2 )and polydimethylsiloxane (PDMS) as a case study, gold-chalcogen bonding and mercapto silane bridges are leveraged. The resulting composite structures exhibit more uniform and stronger interfacial adhesion. This enhanced coupling also enables the observation of a theoretically predicted tension-induced band structure transition in MoS2 . Moreover, no obvious degradation in the devices' structural and electrical properties is identified after numerous mechanical cycle tests. This high-quality lamination enhances the reliability of vdWS-based flexible microelectronics, accelerating their practical applications in biomedical research and consumer electronics.

Interfacial States and Fano-Feshbach Resonance in Graphene-Silicon Vertical Junction.

Interfacial quantum states are drawing tremendous attention recently because of their importance in design of low-dimensional quantum heterostructures with desired charge, spin, or topological properties. Although most studies of the interfacial exchange interactions were mainly performed across the interface vertically, the lateral transport nowadays is still a major experimental method to probe these interactions indirectly. In this Letter, we fabricated a graphene and hydrogen passivated silicon interface to study the interfacial exchange processes. For the first time we found and confirmed a novel interfacial quantum state, which is specific to the 2D-3D interface. The vertically propagating electrons from silicon to graphene result in electron oscillation states at the 2D-3D interface. A harmonic oscillator model is used to explain this interfacial state. In addition, the interaction between this interfacial state (discrete energy spectrum) and the lateral band structure of graphene (continuous energy spectrum) results in Fano-Feshbach resonance. Our results show that the conventional description of the interfacial interaction in low-dimensional systems is valid only in considering the lateral band structure and its density-of-states and is incomplete for the ease of vertical transport. Our experimental observation and theoretical explanation provide more insightful understanding of various interfacial effects in low-dimensional materials, such as proximity effect, quantum tunneling, etc. More important, the Fano-Feshbach resonance may be used to realize all solid-state and scalable quantum interferometers.

A Study of Vertical Transport through Graphene toward Control of Quantum Tunneling.

Vertical integration of van der Waals (vdW) materials with atomic precision is an intriguing possibility brought forward by these two-dimensional (2D) materials. Essential to the design and analysis of these structures is a fundamental understanding of the vertical transport of charge carriers into and across vdW materials, yet little has been done in this area. In this report, we explore the important roles of single layer graphene in the vertical tunneling process as a tunneling barrier. Although a semimetal in the lateral lattice plane, graphene together with the vdW gap act as a tunneling barrier that is nearly transparent to the vertically tunneling electrons due to its atomic thickness and the transverse momenta mismatch between the injected electrons and the graphene band structure. This is accentuated using electron tunneling spectroscopy (ETS) showing a lack of features corresponding to the Dirac cone band structure. Meanwhile, the graphene acts as a lateral conductor through which the potential and charge distribution across the tunneling barrier can be tuned. These unique properties make graphene an excellent 2D atomic grid, transparent to charge carriers, and yet can control the carrier flux via the electrical potential. A new model on the quantum capacitance's effect on vertical tunneling is developed to further elucidate the role of graphene in modulating the tunneling process. This work may serve as a general guideline for the design and analysis of vdW vertical tunneling devices and heterostructures, as well as the study of electron/spin injection through and into vdW materials.

Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being particularly more sensitive to strain. This demonstration of strain engineering in van der Waals heterostructures opens a new route toward fabricating flexible electronics.

Two-Step Growth of Two-Dimensional WSe2/MoSe2 Heterostructures.

Two dimensional (2D) materials have attracted great attention due to their unique properties and atomic thickness. Although various 2D materials have been successfully synthesized with different optical and electrical properties, a strategy for fabricating 2D heterostructures must be developed in order to construct more complicated devices for practical applications. Here we demonstrate for the first time a two-step chemical vapor deposition (CVD) method for growing transition-metal dichalcogenide (TMD) heterostructures, where MoSe2 was synthesized first and followed by an epitaxial growth of WSe2 on the edge and on the top surface of MoSe2. Compared to previously reported one-step growth methods, this two-step growth has the capability of spatial and size control of each 2D component, leading to much larger (up to 169 µm) heterostructure size, and cross-contamination can be effectively minimized. Furthermore, this two-step growth produces well-defined 2H and 3R stacking in the WSe2/MoSe2 bilayer regions and much sharper in-plane interfaces than the previously reported MoSe2/WSe2 heterojunctions obtained from one-step growth methods. The resultant heterostructures with WSe2/MoSe2 bilayer and the exposed MoSe2 monolayer display rectification characteristics of a p-n junction, as revealed by optoelectronic tests, and an internal quantum efficiency of 91% when functioning as a photodetector. A photovoltaic effect without any external gates was observed, showing incident photon to converted electron (IPCE) efficiencies of approximately 0.12%, providing application potential in electronics and energy harvesting.

Chemical vapor deposition of thin crystals of layered semiconductor SnS2 for fast photodetection application.

Layered two-dimensional (2D) semiconductors, such as MoS(2) and SnS(2), have been receiving intensive attention due to their technological importance for the next-generation electronic/photonic applications. We report a novel approach to the controlled synthesis of thin crystal arrays of SnS(2) at predefined locations on chip by chemical vapor deposition with seed engineering and have demonstrated their application as fast photodetectors with photocurrent response time ∼ 5 µs. This opens a pathway for the large-scale production of layered 2D semiconductor devices, important for applications in integrated nanoelectronic/photonic systems.

3D Band Diagram and Photoexcitation of 2D-3D Semiconductor Heterojunctions.

The emergence of a rich variety of two-dimensional (2D) layered semiconductor materials has enabled the creation of atomically thin heterojunction devices. Junctions between atomically thin 2D layers and 3D bulk semiconductors can lead to junctions that are fundamentally electronically different from the covalently bonded conventional semiconductor junctions. Here we propose a new 3D band diagram for the heterojunction formed between n-type monolayer MoS2 and p-type Si, in which the conduction and valence band-edges of the MoS2 monolayer are drawn for both stacked and in-plane directions. This new band diagram helps visualize the flow of charge carriers inside the device in a 3D manner. Our detailed wavelength-dependent photocurrent measurements fully support the diagrams and unambiguously show that the band alignment is type I for this 2D-3D heterojunction. Photogenerated electron-hole pairs in the atomically thin monolayer are separated and driven by an external bias and control the "on/off" states of the junction photodetector device. Two photoresponse regimes with fast and slow relaxation are also revealed in time-resolved photocurrent measurements, suggesting the important role played by charge trap states.

Optoelectronic memory using two-dimensional materials.

An atomically thin optoelectronic memory array for image sensing is demonstrated with layered CuIn7Se11 and extended to InSe and MoS2 atomic layers. Photogenerated charge carriers are trapped and subsequently retrieved from the potential well formed by gating a 2D material with Schottky barriers. The atomically thin layered optoelectronic memory can accumulate photon-generated charges during light exposure, and the charges can be read out later for data processing and permanent storage. An array of atomically thin image memory pixels was built to illustrate the potential of fabricating large-scale 2D material-based image sensors for image capture and storage.

An Atomically Layered InSe Avalanche Photodetector.

Atomically thin photodetectors based on 2D materials have attracted great interest due to their potential as highly energy-efficient integrated devices. However, photoinduced carrier generation in these media is relatively poor due to low optical absorption, limiting device performance. Current methods for overcoming this problem, such as reducing contact resistances or back gating, tend to increase dark current and suffer slow response times. Here, we realize the avalanche effect in a 2D material-based photodetector and show that avalanche multiplication can greatly enhance the device response of an ultrathin InSe-based photodetector. This is achieved by exploiting the large Schottky barrier formed between InSe and Al electrodes, enabling the application of a large bias voltage. Plasmonic enhancement of the photosensitivity, achieved by patterning arrays of Al nanodisks onto the InSe layer, further improves device efficiency. With an external quantum efficiency approaching 866%, a dark current in the picoamp range, and a fast response time of 87 µs, this atomic layer device exhibits multiple significant advances in overall performance for this class of devices.

Scalable Transfer of Suspended Two-Dimensional Single Crystals.

Large-scale suspended architectures of various two-dimensional (2D) materials (MoS2, MoSe2, WS2, and graphene) are demonstrated on nanoscale patterned substrates with different physical and chemical surface properties, such as flexible polymer substrates (polydimethylsiloxane), rigid Si substrates, and rigid metal substrates (Au/Ag). This transfer method represents a generic, fast, clean, and scalable technique to suspend 2D atomic layers. The underlying principle behind this approach, which employs a capillary-force-free wet-contact printing method, was studied by characterizing the nanoscale solid-liquid-vapor interface of 2D layers with respect to different substrates. As a proof-of-concept, a photodetector of suspended MoS2 has been demonstrated with significantly improved photosensitivity. This strategy could be extended to several other 2D material systems and open the pathway toward better optoelectronic and nanoelectromechnical systems.

Solid-Vapor Reaction Growth of Transition-Metal Dichalcogenide Monolayers.

Two-dimensional (2D) layered semiconducting transition-metal dichalcogenides (TMDCs) are promising candidates for next-generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2 , showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non-stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub-oxides and stepwise reactions with Se vapor to finally form MoSe2 . The experimental results and proposed model were corroborated by ab initio Car-Parrinello molecular dynamics studies.

Vertical and in-plane heterostructures from WS2/MoS2 monolayers.

Layer-by-layer stacking or lateral interfacing of atomic monolayers has opened up unprecedented opportunities to engineer two-dimensional heteromaterials. Fabrication of such artificial heterostructures with atomically clean and sharp interfaces, however, is challenging. Here, we report a one-step growth strategy for the creation of high-quality vertically stacked as well as in-plane interconnected heterostructures of WS2/MoS2 via control of the growth temperature. Vertically stacked bilayers with WS2 epitaxially grown on top of the MoS2 monolayer are formed with preferred stacking order at high temperature. A strong interlayer excitonic transition is observed due to the type II band alignment and to the clean interface of these bilayers. Vapour growth at low temperature, on the other hand, leads to lateral epitaxy of WS2 on MoS2 edges, creating seamless and atomically sharp in-plane heterostructures that generate strong localized photoluminescence enhancement and intrinsic p-n junctions. The fabrication of heterostructures from monolayers, using simple and scalable growth, paves the way for the creation of unprecedented two-dimensional materials with exciting properties.

Tailoring the physical properties of molybdenum disulfide monolayers by control of interfacial chemistry.

We demonstrate how substrate interfacial chemistry can be utilized to tailor the physical properties of single-crystalline molybdenum disulfide (MoS2) atomic-layers. Semiconducting, two-dimensional MoS2 possesses unique properties that are promising for future optical and electrical applications for which the ability to tune its physical properties is essential. We use self-assembled monolayers with a variety of end termination chemistries to functionalize substrates and systematically study their influence on the physical properties of MoS2. Using electrical transport measurements, temperature-dependent photoluminescence spectroscopy, and empirical and first-principles calculations, we explore the possible mechanisms involved. Our data shows that combined interface-related effects of charge transfer, built-in molecular polarities, varied densities of defects, and remote interfacial phonons strongly modify the electrical and optical properties of MoS2. These findings can be used to effectively enhance or modulate the conductivity, field-effect mobility, and photoluminescence in MoS2 monolayers, illustrating an approach for local and universal property modulations in two-dimensional atomic-layers.

Vapour phase growth and grain boundary structure of molybdenum disulphide atomic layers.

Single-layered molybdenum disulphide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for the next generation of nanoelectronics. Here, we report the controlled vapour phase synthesis of molybdenum disulphide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area, single- and few-layered films. Using high-resolution electron microscopy imaging, the atomic structure and morphology of the grains and their boundaries in the polycrystalline molybdenum disulphide atomic layers are examined, and the primary mechanisms for grain boundary formation are evaluated. Grain boundaries consisting of 5- and 7- member rings are directly observed with atomic resolution, and their energy landscape is investigated via first-principles calculations. The uniformity in thickness, large grain sizes, and excellent electrical performance signify the high quality and scalable synthesis of the molybdenum disulphide atomic layers.

Synthesis and photocurrent of amorphous boron nanowires.

Although theoretically feasible, synthesis of boron nanostructures is challenging due to the highly reactive nature, high melting and boiling points of boron. We have developed a thermal vapor transfer approach to synthesizing amorphous boron nanowire using a solid boron source. The amorphous nature and chemical composition of boron nanowires were characterized by high resolution transmission electron microscopy, selected area electron diffraction, and electron energy loss spectroscopy. Optical properties and photoconduction of boron nanowires have not yet been reported. In our investigation, the amorphous boron nanowire showed much better optical and electrical properties than previously reported photo-response of crystalline boron nanobelts. When excited by a blue LED, the photo/dark current ratio (I/I0) is 1.5 and time constants in the order of tens of seconds. I/I0 is 1.17 using a green light.

Synthesis and photoresponse of large GaSe atomic layers.

We report the direct growth of large, atomically thin GaSe single crystals on insulating substrates by vapor phase mass transport. A correlation is identified between the number of layers and a Raman shift and intensity change. We found obvious contrast of the resistance of the material in the dark and when illuminated with visible light. In the photoconductivity measurement we observed a low dark current. The on-off ratio measured with a 405 nm at 0.5 mW/mm(2) light source is in the order of 10(3); the photoresponsivity is 17 mA/W, and the quantum efficiency is 5.2%, suggesting possibility for photodetector and sensor applications. The photocurrent spectrum of few-layer GaSe shows an intense blue shift of the excitation edge and expanded band gap compared with bulk material.

Direct laser-patterned micro-supercapacitors from paintable MoS2 films.

Micrometer-sized electrochemical capacitors have recently attracted attention due to their possible applications in micro-electronic devices. Here, a new approach to large-scale fabrication of high-capacitance, two-dimensional MoS2 film-based micro-supercapacitors is demonstrated via simple and low-cost spray painting of MoS2 nanosheets on Si/SiO2 chip and subsequent laser patterning. The obtained micro-supercapacitors are well defined by ten interdigitated electrodes (five electrodes per polarity) with 4.5 mm length, 820 µm wide for each electrode, 200 µm spacing between two electrodes and the thickness of electrode is ∼0.45 µm. The optimum MoS2 -based micro-supercapacitor exhibits excellent electrochemical performance for energy storage with aqueous electrolytes, with a high area capacitance of 8 mF cm(-2) (volumetric capacitance of 178 F cm(-3) ) and excellent cyclic performance, superior to reported graphene-based micro-supercapacitors. This strategy could provide a good opportunity to develop various micro-/nanosized energy storage devices to satisfy the requirements of portable, flexible, and transparent micro-electronic devices.

van der Waals Semiconductor Empowered Vertical Color Sensor.

Biomimetic artificial vision is receiving significant attention nowadays, particularly for the development of neuromorphic electronic devices, artificial intelligence, and microrobotics. Nevertheless, color recognition, the most critical vision function, is missed in the current research due to the difficulty of downscaling of the prevailing color sensing devices. Conventional color sensors typically adopt a lateral color sensing channel layout and consume a large amount of physical space, whereas compact designs suffer from an unsatisfactory color detection accuracy. In this work, we report a van der Waals semiconductor-empowered vertical color sensing structure with the emphasis on compact device profile and precise color recognition capability. More attractive, we endow color sensor hardware with the function of chromatic aberration correction, which can simplify the design of an optical lens system and, in turn, further downscales the artificial vision systems. Also, the dimension of a multiple pixel prototype device in our study confirms the scalability and practical potentials of our developed device architecture toward the above applications.

Discovery of Graphene-Water Membrane Structure: Toward High-Quality Graphene Process.

It is widely accepted that solid-state membranes are indispensable media for the graphene process, particularly transfer procedures. But these membranes inevitably bring contaminations and residues to the transferred graphene and consequently compromise the material quality. This study reports a newly observed free-standing graphene-water membrane structure, which replaces the conventional solid-state supporting media with liquid film to sustain the graphene integrity and continuity. Experimental observation, theoretical model, and molecular dynamics simulations consistently indicate that the high surface tension of pure water and its large contact angle with graphene are essential factors for forming such a membrane structure. More interestingly, water surface tension ensures the flatness of graphene layers and renders high transfer quality on many types of target substrates. This report enriches the understanding of the interactions on reduced dimensional material while rendering an alternative approach for scalable layered material processing with ensured quality for advanced manufacturing.

Single-molecule photocatalytic dynamics at individual defects in two-dimensional layered materials.

The insightful comprehension of in situ catalytic dynamics at individual structural defects of two-dimensional (2D) layered material, which is crucial for the design of high-performance catalysts via defect engineering, is still missing. Here, we resolved single-molecule trajectories resulted from photocatalytic activities at individual structural features (i.e., basal plane, edge, wrinkle, and vacancy) in 2D layered indium selenide (InSe) in situ to quantitatively reveal heterogeneous photocatalytic dynamics and surface diffusion behaviors. The highest catalytic activity was found at vacancy in a four-layer InSe, up to ~30× higher than that on the basal plane. Moreover, lower adsorption strength of reactant and slower dissociation/diffusion rates of product were found at more photocatalytic active defects. These distinct dynamic properties are determined by lattice structures/electronic energy levels of defects and layer thickness of supported InSe. Our findings shed light on the fundamental understanding of photocatalysis at defects and guide the rational defect engineering.