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.

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.

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.

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.

Gate-Induced Metal-Insulator Transition in 2D van der Waals Layers of Copper Indium Selenide Based Field-Effect Transistors.

The existence of an exquisite phenomenon such as a metal-insulator transition (MIT) in two-dimensional (2D) systems, where completely different electronic functionalities in the same system can emerge simply by regulating parameters such as charge carrier density in them, is noteworthy. Such tunability in material properties can lead to several applications where precise tuning of function specific properties are desirable. Here, we report on our observation on the occurrence of MIT in the 2D material system of copper indium selenide (CuIn7Se11). Clear evidence of the metallic nature of conductivity (σ) under the influence of electrostatic doping via the gate, which crosses over to an insulating phase upon lowering the temperature, was observed by investigating the temperature and gate dependence of σ in CuIn7Se11 field-effect transistor devices. At higher charge carrier densities (n > 1012 cm-1), we found that σ ∼ (n)α with α ∼ 2, which suggests the presence of bare Coulomb impurity scattering within the studied range of temperature (280 K > T > 20 K). Our analysis of the conductivity data following the principles of percolation theory of transition where σ ∼ (n - nC)δ show that the critical percolation exponent δ(T) has average values ∼1.57 ± 0.27 and 1.02 ± 0.35 within the measured temperature range for the two devices and it is close to the 2D percolation exponent value of 1.33. We believe that the 2D MIT seen in our system is due to the charge density inhomogeneity caused by electrostatic doping and unscreened charge impurity scattering that leads to a percolation driven transition. The findings reported here for CuIn7Se11 system provide a different material platform to investigate MIT in 2D and are crucial in order to understand the fundamental basis of electronic interactions and charge-transport phenomenon in other unexplored 2D electron systems.

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.

Near-Field Coupled Integrable Two-Dimensional InSe Photosensor on Optical Fiber.

Two-dimensional (2D) van der Waals layered materials possess innate advantages as integrable sensors, due to their thinness, flexibility, and sensitivity. They can be seamlessly integrated onto surfaces with different geometries where detection for near-field signal is desired. In this study, we develop a device transfer technique to integrate device assemblies based on 2D materials onto an arbitrary smooth surface. Such technique utilizes a sacrificial polymer underlayer and achieves clean and nondestructive full device transfer. For demonstration, we transferred a complete 2D multilayer InSe photodetector device onto a stripped optical fiber. Due to the extreme vicinity of the 2D photodetector with the fiber core, the device can effectively couple with the evanescent field and accurately detect information transmitted inside the optical fiber. In addition, these super thin flexible device assemblies can be integrated onto the fibers themselves to non-invasively monitor the optical fiber performance. The demonstration of optically coupled, conformal 2D devices on substrates of different form factors can enable a variety of near-field optical and sensing applications.

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.

Atomic-Monolayer Two-Dimensional Lateral Quasi-Heterojunction Bipolar Transistors with Resonant Tunneling Phenomenon.

High-frequency operation with ultrathin, lightweight, and extremely flexible semiconducting electronics is highly desirable for the development of mobile devices, wearable electronic systems, and defense technologies. In this work, the experimental observation of quasi-heterojunction bipolar transistors utilizing a monolayer of the lateral WSe2-MoS2 junctions as the conducting p-n channel is demonstrated. Both lateral n-p-n and p-n-p heterojunction bipolar transistors are fabricated to exhibit the output characteristics and current gain. A maximum common-emitter current gain of around 3 is obtained in our prototype two-dimensional quasi-heterojunction bipolar transistors. Interestingly, we also observe the negative differential resistance in the electrical characteristics. A potential mechanism is that the negative differential resistance is induced by resonant tunneling phenomenon due to the formation of quantum well under applying high bias voltages. Our results open the door to two-dimensional materials for high-frequency, high-speed, high-density, and flexible electronics.

Imaging the motion of electrons across semiconductor heterojunctions.

Technological progress since the late twentieth century has centred on semiconductor devices, such as transistors, diodes and solar cells. At the heart of these devices is the internal motion of electrons through semiconductor materials due to applied electric fields or by the excitation of photocarriers. Imaging the motion of these electrons would provide unprecedented insight into this important phenomenon, but requires high spatial and temporal resolution. Current studies of electron dynamics in semiconductors are generally limited by the spatial resolution of optical probes, or by the temporal resolution of electronic probes. Here, by combining femtosecond pump-probe techniques with spectroscopic photoemission electron microscopy, we imaged the motion of photoexcited electrons from high-energy to low-energy states in a type-II 2D InSe/GaAs heterostructure. At the instant of photoexcitation, energy-resolved photoelectron images revealed a highly non-equilibrium distribution of photocarriers in space and energy. Thereafter, in response to the out-of-equilibrium photocarriers, we observed the spatial redistribution of charges, thus forming internal electric fields, bending the semiconductor bands, and finally impeding further charge transfer. By assembling images taken at different time-delays, we produced a movie lasting a few trillionths of a second of the electron-transfer process in the photoexcited type-II heterostructure-a fundamental phenomenon in semiconductor devices such as solar cells. Quantitative analysis and theoretical modelling of spatial variations in the movie provide insight into future solar cells, 2D materials and other semiconductor devices.

Enabling Ultrasensitive Photo-detection Through Control of Interface Properties in Molybdenum Disulfide Atomic Layers.

The interfaces in devices made of two-dimensional materials such as MoS2 can effectively control their optoelectronic performance. However, the extent and nature of these deterministic interactions are not fully understood. Here, we investigate the role of substrate interfaces on the photodetector properties of MoS2 devices by studying its photocurrent properties on both SiO2 and self-assembled monolayer-modified substrates. Results indicate that while the photoresponsivity of the devices can be enhanced through control of device interfaces, response times are moderately compromised. We attribute this trade-off to the changes in the electrical contact resistance at the device metal-semiconductor interface. We demonstrate that the formation of charge carrier traps at the interface can dominate the device photoresponse properties. The capture and emission rates of deeply trapped charge carriers in the substrate-semiconductor-metal regions are strongly influenced by exposure to light and can dynamically dope the contact regions and thus perturb the photodetector properties. As a result, interface-modified photodetectors have significantly lower dark-currents and higher on-currents. Through appropriate interfacial design, a record high device responsivity of 4.5 × 103 A/W at 7 V is achieved, indicative of the large signal gain in the devices and exemplifying an important design strategy that enables highly responsive two-dimensional photodetectors.

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.

Layer Engineering of 2D Semiconductor Junctions.

A new concept for junction fabrication by connecting multiple regions with varying layer thicknesses, based on the thickness dependence, is demonstrated. This type of junction is only possible in super-thin-layered 2D materials, and exhibits similar characteristics as p-n junctions. Rectification and photovoltaic effects are observed in chemically homogeneous MoSe2 junctions between domains of different thicknesses.

Low-Cost, Large-Area, Facile, and Rapid Fabrication of Aligned ZnO Nanowire Device Arrays.

Well aligned nanowires of ZnO have been made with an electrospinning technique using zinc acetate precursor solutions. Employment of two connected parallel collector plates with a separating gap of 4 cm resulted in a very high degree of nanowire alignment. By adjusting the process parameters, the deposition density of the wires could be controlled. Field effect transistors were prepared by depositing wires between two gold electrodes on top of a heavily doped Si substrate covered with a 300 nm oxide layer. These devices showed good FET characteristics and photosensitivity under UV-illumination. The method provides a fast and scalable fabrication route for functional nanowire arrays with a high degree of alignment and control over nanowire spacing.

Wafer-scale monodomain films of spontaneously aligned single-walled carbon nanotubes.

The one-dimensional character of electrons, phonons and excitons in individual single-walled carbon nanotubes leads to extremely anisotropic electronic, thermal and optical properties. However, despite significant efforts to develop ways to produce large-scale architectures of aligned nanotubes, macroscopic manifestations of such properties remain limited. Here, we show that large (>cm(2)) monodomain films of aligned single-walled carbon nanotubes can be prepared using slow vacuum filtration. The produced films are globally aligned within ±1.5° (a nematic order parameter of ∼1) and are highly packed, containing 1 × 10(6) nanotubes in a cross-sectional area of 1 µm(2). The method works for nanotubes synthesized by various methods, and film thickness is controllable from a few nanometres to ∼100 nm. We use the approach to create ideal polarizers in the terahertz frequency range and, by combining the method with recently developed sorting techniques, highly aligned and chirality-enriched nanotube thin-film devices. Semiconductor-enriched devices exhibit polarized light emission and polarization-dependent photocurrent, as well as anisotropic conductivities and transistor action with high on/off ratios.

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.

Observing the interplay between surface and bulk optical nonlinearities in thin van der Waals crystals.

Van der Waals materials, existing in a range of thicknesses from monolayer to bulk, allow for interplay between surface and bulk nonlinearities, which otherwise dominate only at atomically-thin or bulk extremes, respectively. Here, we observe an unexpected peak in intensity of the generated second harmonic signal versus the thickness of Indium Selenide crystals, in contrast to the quadratic increase expected from thin crystals. We explain this by interference effects between surface and bulk nonlinearities, which offer a new handle on engineering the nonlinear optical response of 2D materials and their heterostructures.

Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry.

Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti(4+) to form planar p-type [Ti(4+)n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B(3+), Al(3+) and Sn(4+)) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

Solid-Liquid Self-Adaptive Polymeric Composite.

A solid-liquid self-adaptive composite (SAC) is synthesized using a simple mixing-evaporation protocol, with poly(dimethylsiloxane) (PDMS) and poly(vinylidene fluoride) (PVDF) as active constituents. SAC exists as a porous solid containing a near equivalent distribution of the solid (PVDF)-liquid (PDMS) phases, with the liquid encapsulated and stabilized within a continuous solid network percolating throughout the structure. The pores, liquid, and solid phases form a complex hierarchical structure, which offers both mechanical robustness and a significant structural adaptability under external forces. SAC exhibits attractive self-healing properties during tension, and demonstrates reversible self-stiffening properties under compression with a maximum of 7-fold increase seen in the storage modulus. In a comparison to existing self-healing and self-stiffening materials, SAC offers distinct advantages in the ease of fabrication, high achievable storage modulus, and reversibility. Such materials could provide a new class of adaptive materials system with multifunctionality, tunability, and scale-up potentials.

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.