Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures.

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides-which represent one- and three-atom-thick two-dimensional building blocks, respectively-have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Ultraefficient Electrocatalytic Hydrogen Evolution from Strain-Engineered, Multilayer MoS2.

This paper reports an approach to repurpose low-cost, bulk multilayer MoS2 for development of ultraefficient hydrogen evolution reaction (HER) catalysts over large areas (>cm2). We create working electrodes for use in HER by dry transfer of MoS2 nano- and microflakes to gold thin films deposited on prestrained thermoplastic substrates. By relieving the prestrain at a macroscopic scale, a tunable level of tensile strain is developed in the MoS2 and consequently results in a local phase transition as a result of spontaneously formed surface wrinkles. Using electrochemical impedance spectroscopy, we verified that electrochemical activation of the strained MoS2 lowered the charge transfer resistance within the materials system, achieving HER activity comparable to platinum (Pt). Raman and X-ray photoelectron spectroscopy show that desulfurization in the multilayer MoS2 was promoted by the phase transition; the combined effect of desulfurization and the lower charge resistance induced superior HER performance.

Gas-Phase Alkali Metal-Assisted MOCVD Growth of 2D Transition Metal Dichalcogenides for Large-Scale Precise Nucleation Control.

Advances in large-area and high-quality 2D transition metal dichalcogenides (TMDCs) growth are essential for semiconductor applications. Here, the gas-phase alkali metal-assisted metal-organic chemical vapor deposition (GAA-MOCVD) of 2D TMDCs is reported. It is determined that sodium propionate (SP) is an ideal gas-phase alkali-metal additive for nucleation control in the MOCVD of 2D TMDCs. The grain size of MoS2 in the GAA-MOCVD process is larger than that in the conventional MOCVD process. This method can be applied to the growth of various TMDCs (MoS2 , MoSe2 , WSe2 , and WSe2 ) and the generation of large-scale continuous films. Furthermore, the growth behaviors of MoS2 under different SP and oxygen injection time conditions are systematically investigated to determine the effects of SP and oxygen on nucleation control in the GAA-MOCVD process. It is found that the combination of SP and oxygen increases the grain size and nucleation suppression of MoS2 . Thus, the GAA-MOCVD with a precise and controllable supply of a gas-phase alkali metal and oxygen allows achievement of optimum growth conditions that maximizes the grain size of MoS2 . It is expected that GAA-MOCVD can provide a way for batch fabrication of large-scale atomically thin electronic devices based on 2D semiconductors.

Fabrication of heterogeneous chemical patterns on stretchable hydrogels using single-photon lithography.

Curved hydrogel surfaces bearing chemical patterns are highly desirable in various applications, including artificial blood vessels, wearable electronics, and soft robotics. However, previous studies on the fabrication of chemical patterns on hydrogels employed two-photon lithography, which is still not widely accessible to most laboratories. This work demonstrates a new patterning technique for fabricating curved hydrogels with chemical patterns on their surfaces without two-photon microscopy. In this work, we show that exposing hydrogels in fluorophore solutions to single photons via confocal microscopy enables the patterning of fluorophores on hydrogels. By applying this technique to highly stretchable hydrogels, we demonstrate three applications: (1) improving pattern resolution by fabricating patterns on stretched hydrogels and then returning the hydrogels to their initial, unstretched length; (2) modifying the local stretchability of hydrogels at a microscale resolution; and (3) fabricating perfusable microchannels with chemical patterns by winding chemically patterned hydrogels around a template, embedding the hydrogels in a second hydrogel, and then removing the template. The patterning method demonstrated in this work may facilitate a better mimicking of the physicochemical properties of organs in tissue engineering and may be used to make hydrogel robots with specific chemical functionalities.

Switchable, Tunable, and Directable Exciton Funneling in Periodically Wrinkled WS2.

The extreme elastic strain of monolayer transition metal dichalcogenides provides an ideal platform to achieve efficient exciton funneling via local strain modulation; however, studies conducted thus far have focused on the use of substrates with fixed strain profiles. We prepared 1L-WS2 on a flexible substrate such that the formation of topographic wrinkles could be switched on or off, and the depth or the direction of the wrinkle could be modified by external strain, thereby providing full control of the periodic undulation of the band gap profile of 1L-WS2 in the range 0-57 meV. Nanoscale photoluminescence (PL) imaging unambiguously evinced that the photoexcited excitons of 1L-WS2 were accumulated at the top regions of the wrinkles with less band gap than the valley region. Our results of broad tunability of the two-dimensional (2D) exciton funneling suggest a promising route to control exciton drift for enhanced optoelectronic performances and future 2D exciton devices.

Electric-Field-Induced Reversible Phase Transitions in a Spontaneously Ion-Intercalated 2D Metal Oxide.

Electric field driven reversible phase transitions in two-dimensional (2D) materials are appealing for their potential in switching applications. Here, we introduce potassium intercalated MnO2 as an exemplary case. We demonstrate the synthesis of large-area single-crystal layered MnO2 via chemical vapor deposition as thin as 5 nm. These crystals are spontaneously intercalated by potassium ions during the synthesis. We showed that the charge transport in 2D K-MnO2 is dominated by motion of hydrated potassium ions in the interlayer space. Under a few volts bias, separation of potassium and the structural water leads to formation of different phases at the opposite terminals, and at larger biases K-MnO2 crystals exhibit reversible layered-to-spinel phase transition. These phase transitions are accompanied by electrical and optical changes in the material. We used the electric field driven ionic motion in K-MnO2 based devices to demonstrate the memristive capabilities of two terminal devices.

Arrayed MoS2 -In0.53 Ga0.47 As van der Waals Heterostructure for High-Speed and Broadband Detection from Visible to Shortwave-Infrared Light.

A high-speed and broadband 5 × 5 photodetector array based on MoS2 /In0.53 Ga0.47 As heterojunction is successfully demonstrated to take full advantage of the type-II band-aligned multilayer MoS2 /In0.53 Ga0.47 As. The fabricated devices exhibit good uniformity in the Raman spectrum and clear rectifying characteristics. The fabricated MoS2 /In0.53 Ga0.47 As photodetectors show good optical performances at a broad wavelength range showing high responsivities corresponding to the detectivity of ≈1010 Jones at -3 V for the incident broadband light from 400 to 1550 nm. A very fast photoresponse is also obtained with a small rise/fall time in the order of microseconds both for visible (638 nm) and shortwave infrared (1310 nm). Finally, the image scanning properties of MoS2 /In0.53 Ga0.47 As devices are demonstrated for visible and infrared light, indicating that the suggested device is one of the promising options for future broadband imager, which can be integrated on the focal plane arrays (FPAs).

High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity.

The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal-organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm(2) V(-1) s(-1) at room temperature and 114 cm(2) V(-1) s(-1) at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three-dimensional circuitry. Our work is a step towards the realization of atomically thin integrated circuitry.

Tuning Electrical Conductance of MoS2 Monolayers through Substitutional Doping.

Tuning electrical conductivity of semiconducting materials through substitutional doping is crucial for fabricating functional devices. This, however, has not been fully realized in two-dimensional (2D) materials due to the difficulty of homogeneously controlling the dopant concentrations and the lack of systematic study of the net impact of substitutional dopants separate from that of the unintentional doping from the device fabrication processes. Here, we grow wafer-scale, continuous MoS2 monolayers with tunable concentrations of Nb and Re and fabricate devices using a polymer-free approach to study the direct electrical impact of substitutional dopants in MoS2 monolayers. In particular, the electrical conductivity of Nb doped MoS2 in the absence of electrostatic gating is reproducibly tuned over 7 orders of magnitude by controlling the Nb concentration. Our study further indicates that the dopant carriers do not fully ionize in the 2D limit, unlike in their three-dimensional analogues, which is explained by weaker charge screening and impurity band conduction. Moreover, we show that the dopants are stable, which enables the doped films to be processed as independent building blocks that can be used as electrodes for functional circuitry.

Mechanoluminescent, Air-Dielectric MoS2 Transistors as Active-Matrix Pressure Sensors for Wide Detection Ranges from Footsteps to Cellular Motions.

Tactile pressure sensors as flexible bioelectronic devices have been regarded as the key component for recently emerging applications in electronic skins, health-monitoring devices, or human-machine interfaces. However, their narrow range of sensible pressure and their difficulty in forming high integrations represent major limitations for various potential applications. Herein, we report fully integrated, active-matrix arrays of pressure-sensitive MoS2 transistors with mechanoluminescent layers and air dielectrics for wide detectable range from footsteps to cellular motions. The inclusion of mechanoluminescent materials as well as air spaces can increase the sensitivity significantly over entire pressure regimes. In addition, the high integration capability of these active-matrix sensory circuitries can enhance their spatial resolution to the level sufficient to analyze the pressure distribution in a single cardiomyocyte. We envision that these wide-range pressure sensors will provide a new strategy toward next-generation electronics at biomachine interfaces to monitor various mechanical and biological phenomena at single-cell resolution.

Capillary Origami with Atomically Thin Membranes.

Small-scale optical and mechanical components and machines require control over three-dimensional structure at the microscale. Inspired by the analogy between paper and two-dimensional materials, origami-style folding of atomically thin materials offers a promising approach for making microscale structures from the thinnest possible sheets. In this Letter, we show that a monolayer of molybdenum disulfide (MoS2) can be folded into three-dimensional shapes by a technique called capillary origami, in which the surface tension of a droplet drives the folding of a thin sheet. We define shape nets by patterning rigid metal panels connected by MoS2 hinges, allowing us to fold micron-scale polyhedrons. Finally, we demonstrate that these shapes can be folded in parallel without the use of micropipettes or microfluidics by means of a microemulsion of droplets that dissolves into the bulk solution to drive folding. These results demonstrate controllable folding of the thinnest possible materials using capillary origami and indicate a route forward for design and parallel fabrication of more complex three-dimensional micron-scale structures and machines.

Reversible MoS2 Origami with Spatially Resolved and Reconfigurable Photosensitivity.

Two-dimensional layered materials (2DLMs) have been extensively studied in a variety of planar optoelectronic devices. Three-dimensional (3D) optoelectronic structures offer unique advantages including omnidirectional responses, multipolar detection, and enhanced light-matter interactions. However, there has been limited success in transforming monolayer 2DLMs into reconfigurable 3D optoelectronic devices due to challenges in microfabrication and integration of these materials in truly 3D geometries. Here, we report an origami-inspired self-folding approach to reversibly transform monolayer molybdenum disulfide (MoS2) into functional 3D optoelectronic devices. We pattern and integrate monolayer MoS2 and gold (Au) onto differentially photo-cross-linked thin polymer (SU8) films. The devices reversibly self-fold due to swelling gradients in the SU8 films upon solvent exchange. We fabricate a wide variety of optically active 3D MoS2 microstructures including pyramids, cubes, flowers, dodecahedra, and Miura-oris, and we simulate the self-folding mechanism using a coarse-grained mechanics model. Using finite-difference time-domain (FDTD) simulation and optoelectronic characterization, we demonstrate that the 3D self-folded MoS2 structures show enhanced light interaction and are capable of angle-resolved photodetection. Importantly, the structures are also reversibly reconfigurable upon solvent exchange with high tunability in the optical detection area. Our approach provides a versatile strategy to reversibly configure 2D materials in 3D optoelectronic devices of broad relevance to flexible and wearable electronics, biosensing, and robotics.

Absence of a Band Gap at the Interface of a Metal and Highly Doped Monolayer MoS2.

High quality electrical contact to semiconducting transition metal dichalcogenides (TMDCs) such as MoS2 is key to unlocking their unique electronic and optoelectronic properties for fundamental research and device applications. Despite extensive experimental and theoretical efforts reliable ohmic contact to doped TMDCs remains elusive and would benefit from a better understanding of the underlying physics of the metal-TMDC interface. Here we present measurements of the atomic-scale energy band diagram of junctions between various metals and heavily doped monolayer MoS2 using ultrahigh vacuum scanning tunneling microscopy (UHV-STM). Our measurements reveal that the electronic properties of these junctions are dominated by two-dimensional metal-induced gap states (MIGS). These MIGS are characterized by a spatially growing measured gap in the local density of states (L-DOS) of the MoS2 within 2 nm of the metal-semiconductor interface. Their decay lengths extend from a minimum of ∼0.55 nm near midgap to as long as 2 nm near the band edges and are nearly identical for Au, Pd, and graphite contacts, indicating that it is a universal property of the monolayer semiconductor. Our findings indicate that even in heavily doped semiconductors, the presence of MIGS sets the ultimate limit for electrical contact.

Long-Lived Hole Spin/Valley Polarization Probed by Kerr Rotation in Monolayer WSe2.

Time-resolved Kerr rotation and photoluminescence measurements are performed on MOCVD-grown monolayer tungsten diselenide (WSe2). We observe a surprisingly long-lived Kerr rotation signal (∼80 ns) at 10 K, which is attributed to spin/valley polarization of the resident holes. This polarization is robust to transverse magnetic field (up to 0.3 T). Wavelength-dependent measurements reveal that only excitation near the free exciton energy generates this long-lived spin/valley polarization.

Atomic-Scale Spectroscopy of Gated Monolayer MoS2.

The electronic properties of semiconducting monolayer transition-metal dichalcogenides can be tuned by electrostatic gate potentials. Here we report gate-tunable imaging and spectroscopy of monolayer MoS2 by atomic-resolution scanning tunneling microscopy/spectroscopy (STM/STS). Our measurements are performed on large-area samples grown by metal-organic chemical vapor deposition (MOCVD) techniques on a silicon oxide substrate. Topographic measurements of defect density indicate a sample quality comparable to single-crystal MoS2. From gate voltage dependent spectroscopic measurements, we determine that in-gap states exist in or near the MoS2 film at a density of 1.3 × 10(12) eV(-1) cm(-2). By combining the single-particle band gap measured by STS with optical measurements, we estimate an exciton binding energy of 230 meV on this substrate, in qualitative agreement with numerical simulation. Grain boundaries are observed in these polycrystalline samples, which are seen to not have strong electronic signatures in STM imaging.

Atomic layer-by-layer thermoelectric conversion in topological insulator bismuth/antimony tellurides.

Material design for direct heat-to-electricity conversion with substantial efficiency essentially requires cooperative control of electrical and thermal transport. Bismuth telluride (Bi2Te3) and antimony telluride (Sb2Te3), displaying the highest thermoelectric power at room temperature, are also known as topological insulators (TIs) whose electronic structures are modified by electronic confinements and strong spin-orbit interaction in a-few-monolayers thickness regime, thus possibly providing another degree of freedom for electron and phonon transport at surfaces. Here, we explore novel thermoelectric conversion in the atomic monolayer steps of a-few-layer topological insulating Bi2Te3 (n-type) and Sb2Te3 (p-type). Specifically, by scanning photoinduced thermoelectric current imaging at the monolayer steps, we show that efficient thermoelectric conversion is accomplished by optothermal motion of hot electrons (Bi2Te3) and holes (Sb2Te3) through 2D subbands and topologically protected surface states in a geometrically deterministic manner. Our discovery suggests that the thermoelectric conversion can be interiorly achieved at the atomic steps of a homogeneous medium by direct exploiting of quantum nature of TIs, thus providing a new design rule for the compact thermoelectric circuitry at the ultimate size limit.

Growth of straight one-dimensional Ge/ZnSe heterojunctions with atomically sharp interfaces by catalytic residue controls.

One-dimensional (1D) heteroepitaxy with an abrupt interface is essential to construct the 1D heterojunctions required for photonic and electronic devices. During catalytic 1D heteroepitaxial growth, however, the heterojunctions are generically kinked and composition-diffused across the interfaces. Here, we report a simple synthetic route for straight 1D heteroepitaxy with atomically sharp interfaces of group IV(Ge)/group II-VI(ZnSe) nanowires (NWs) during Au-catalytic growth. Specifically, it is discovered that eliminating residues in Au catalysts by Se vapour treatments lowers the energy barrier for the Ge NW axial heteroepitaxy on ZnSe NWs, and forms atomically abrupt heterointerfaces. We verified such 1D variation in the local electronic band structure of the grown Ge/ZnSe NW heterojunctions with spatially resolved photocurrent measurements.

Ion transport induced room-temperature insulator-metal transition in single-crystalline Cu2Se.

Cu2Se is a superionic conductor above 414 K, with ionic conductivities reaching that of molten salts. The superionic behavior results from hopping Cu ions between different crystallographic sites within the Se scaffold. However, the properties of Cu2Se below 414 K are far less known due to experimental limitations imposed by the bulk or polycrystalline samples that have been available so far. Here, we report the synthesis of ultra-thin, large-area single crystalline Cu2Se samples using a chemical vapor deposition method. The as-synthesized Cu2Se crystals exhibit optically and electrically detectable and controllable robust phases at room temperature and above. We demonstrate that Cu ion vacancies can be manipulated to induce an insulator-metal transition, which exhibits 6 orders of magnitude change in the electrical resistance of two terminal devices, accompanied by an optical change in the phase configuration. Our experiments show that the high mobility of the liquid-like Cu ion vacancies in Cu2Se causes macroscopic ordering in the Cu vacancies. Consequently, phase distribution over the crystals is not dictated by the diffusive motion of the ions but by the local energy minima formed due to the phase transition. As a result, long-range vacancy ordering of the crystal below 414 K becomes optically observable at a micrometer scale. This work demonstrates that Cu2Se could be a prototypical system where long-range ordering properties can be studied via electrical and optical methods.

Structural alignment of ZnO columns across multiple monolayer MoS2 layers as compliant substrates.

Understanding the behavior of materials in multi-dimensional architectures composed of atomically thin two-dimensional (2D) materials and three-dimensional (3D) materials has become mandatory for progress in materials preparation via various epitaxy techniques, such as van der Waals and remote epitaxy methods. We investigated the growth behavior of ZnO on monolayer MoS2 as a model system to study the growth of a 3D material on a 2D material, which is beyond the scope of remote and van der Waals epitaxy. The study revealed column-to-column alignment and inversion of crystallinity, which can be explained by combinatorial epitaxy, grain alignment across an atomically sharp interface, and a compliant substrate. The growth study enabled the formation of a ZnO/MoS2 heterostructure with type-I band alignment. Our findings will have a scientific impact on realizing 2D/3D heterostructures for practical device applications.