Cascaded compression of size distribution of nanopores in monolayer graphene.

Monolayer graphene with nanometre-scale pores, atomically thin thickness and remarkable mechanical properties provides wide-ranging opportunities for applications in ion and molecular separations1, energy storage2 and electronics3. Because the performance of these applications relies heavily on the size of the nanopores, it is desirable to design and engineer with precision a suitable nanopore size with narrow size distributions. However, conventional top-down processes often yield log-normal distributions with long tails, particularly at the sub-nanometre scale4. Moreover, the size distribution and density of the nanopores are often intrinsically intercorrelated, leading to a trade-off between the two that substantially limits their applications5-9. Here we report a cascaded compression approach to narrowing the size distribution of nanopores with left skewness and ultrasmall tail deviation, while keeping the density of nanopores increasing at each compression cycle. The formation of nanopores is split into many small steps, in each of which the size distribution of all the existing nanopores is compressed by a combination of shrinkage and expansion and, at the same time as expansion, a new batch of nanopores is created, leading to increased nanopore density by each cycle. As a result, high-density nanopores in monolayer graphene with a left-skewed, short-tail size distribution are obtained that show ultrafast and ångström-size-tunable selective transport of ions and molecules, breaking the limitation of the conventional log-normal size distribution9,10. This method allows for independent control of several metrics of the generated nanopores, including the density, mean diameter, standard deviation and skewness of the size distribution, which will lead to the next leap in nanotechnology.

Tailoring the aluminum nanocrystal surface oxide for all-aluminum-based antenna-reactor plasmonic photocatalysts.

Aluminum nanocrystals (AlNCs) are of increasing interest as sustainable, earth-abundant nanoparticles for visible wavelength plasmonics and as versatile nanoantennas for energy-efficient plasmonic photocatalysis. Here, we show that annealing AlNCs under various gases and thermal conditions induces substantial, systematic changes in their surface oxide, modifying crystalline phase, surface morphology, density, and defect type and concentration. Tailoring the surface oxide properties enables AlNCs to function as all-aluminum-based antenna-reactor plasmonic photocatalysts, with the modified surface oxides providing varying reactivities and selectivities for several chemical reactions.

Structure and mechanism of human diacylglycerol O-acyltransferase 1.

Diacylglycerol O-acyltransferase 1 (DGAT1) synthesizes triacylglycerides and is required for dietary fat absorption and fat storage in humans1. DGAT1 belongs to the membrane-bound O-acyltransferase (MBOAT) superfamily, members of which are found in all kingdoms of life and are involved in the acylation of lipids and proteins2,3. How human DGAT1 and other mammalian members of the MBOAT family recognize their substrates and catalyse their reactions is unknown. The absence of three-dimensional structures also hampers rational targeting of DGAT1 for therapeutic purposes. Here we present the cryo-electron microscopy structure of human DGAT1 in complex with an oleoyl-CoA substrate. Each DGAT1 protomer has nine transmembrane helices, eight of which form a conserved structural fold that we name the MBOAT fold. The MBOAT fold in DGAT1 forms a hollow chamber in the membrane that encloses highly conserved catalytic residues. The chamber has separate entrances for each of the two substrates, fatty acyl-CoA and diacylglycerol. DGAT1 can exist as either a homodimer or a homotetramer and the two forms have similar enzymatic activity. The N terminus of DGAT1 interacts with the neighbouring protomer and these interactions are required for enzymatic activity.

Precise Fabrication and Manipulation of Individual Polymer Nanofibers.

Polymer nanofibers hold promise in a wide range of applications owing to their diverse properties, flexibility, and cost effectiveness. In this study, we introduce a polymer nanofiber drawing process in a scanning electron microscope and focused ion beam (SEM/FIB) instrument with in situ observation. We employed a nanometer-sharp tungsten needle and prepolymer microcapsules to enable nanofiber drawing in a vacuum environment. This method produces individual polymer nanofibers with diameters as small as ∼500 nm and lengths extending to millimeters, yielding nanofibers with an aspect ratio of 2000:1. The attachment to the tungsten manipulator ensures accurate transfer of the polymer nanofiber to diverse substrate types as well as fabrication of assembled structures. Our findings provide valuable insights into ultrafine polymer fiber drawing, paving the way for high-precision manipulation and assembly of polymer nanofibers.

Double Layer SiO2-Coated Water-Stable Halide Perovskite as a Promising Antimicrobial Photocatalyst under Visible Light.

Halide perovskite nanocrystals (HPNCs) have emerged as promising materials for various light harvesting applications due to their exceptional optical and electronic properties. However, their inherent instability in water and biological fluids has limited their use as photocatalysts in the aqueous phase. In this study, we present highly water-stable SiO2-coated HPNCs as efficient photocatalysts for antimicrobial applications. The double SiO2 layer coating method confers long-term structural and optical stability to HPNCs in water, while the in situ synthesis of lead- and bismuth-based perovskite NCs into the SiO2 shell enhances their versatility and tunability. We demonstrate that the substantial generation of singlet oxygen via energy transfer from HPNCs enables efficient photoinduced antibacterial efficacy under aqueous conditions. More than 90% of Escherichia coli was inactivated under mild visible light irradiation for 6 h. The excellent photocatalytic antibacterial performance suggests that SiO2-coated HPNCs hold great potential for various aqueous phase photocatalytic applications.

Dynamic Evolution of Copper Nanowires during CO2 Reduction Probed by Operando Electrochemical 4D-STEM and X-ray Spectroscopy.

Nanowires have emerged as an important family of one-dimensional (1D) nanomaterials owing to their exceptional optical, electrical, and chemical properties. In particular, Cu nanowires (NWs) show promising applications in catalyzing the challenging electrochemical CO2 reduction reaction (CO2RR) to valuable chemical fuels. Despite early reports showing morphological changes of Cu NWs after CO2RR processes, their structural evolution and the resulting exact nature of active Cu sites remain largely elusive, which calls for the development of multimodal operando time-resolved nm-scale methods. Here, we report that well-defined 1D copper nanowires, with a diameter of around 30 nm, have a metallic 5-fold twinned Cu core and around 4 nm Cu2O shell. Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) showed that as-synthesized Cu@Cu2O NWs experienced electroreduction of surface Cu2O to disordered (spongy) metallic Cu shell (Cu@CuS NWs) under CO2RR relevant conditions. Cu@CuS NWs further underwent a CO-driven Cu migration leading to a complete evolution to polycrystalline metallic Cu nanograins. Operando electrochemical four-dimensional (4D) STEM in liquid, assisted by machine learning, interrogates the complex structures of Cu nanograin boundaries. Correlative operando synchrotron-based high-energy-resolution X-ray absorption spectroscopy unambiguously probes the electroreduction of Cu@Cu2O to fully metallic Cu nanograins followed by partial reoxidation of surface Cu during postelectrolysis air exposure. This study shows that Cu nanowires evolve into completely different metallic Cu nanograin structures supporting the operando (operating) active sites for the CO2RR.

Electric Field Effects in Flash Joule Heating Synthesis.

Flash Joule heating has emerged as an ultrafast, scalable, and versatile synthesis method for nanomaterials, such as graphene. Here, we experimentally and theoretically deconvolute the contributions of thermal and electrical processes to the synthesis of graphene by flash Joule heating. While traditional methods of graphene synthesis involve purely chemical or thermal driving forces, our results show that the presence of charge and the resulting electric field in a graphene precursor catalyze the formation of graphene. Furthermore, modulation of the current or the pulse width affords the ability to control the three-step phase transition of the material from amorphous carbon to turbostratic graphene and finally to ordered (AB and ABC-stacked) graphene and graphite. Finally, density functional theory simulations reveal that the presence of a charge- and current-induced electric field inside the graphene precursor facilitates phase transition by lowering the activation energy of the reaction. These results demonstrate that the passage of electrical current through a solid sample can directly drive nanocrystal nucleation in flash Joule heating, an insight that may inform future Joule heating or other electrical synthesis strategies.

Electron ptychography of 2D materials to deep sub-ångström resolution.

Aberration-corrected optics have made electron microscopy at atomic resolution a widespread and often essential tool for characterizing nanoscale structures. Image resolution has traditionally been improved by increasing the numerical aperture of the lens (α) and the beam energy, with the state-of-the-art at 300 kiloelectronvolts just entering the deep sub-ångström (that is, less than 0.5 ångström) regime. Two-dimensional (2D) materials are imaged at lower beam energies to avoid displacement damage from large momenta transfers, limiting spatial resolution to about 1 ångström. Here, by combining an electron microscope pixel-array detector with the dynamic range necessary to record the complete distribution of transmitted electrons and full-field ptychography to recover phase information from the full phase space, we increase the spatial resolution well beyond the traditional numerical-aperture-limited resolution. At a beam energy of 80 kiloelectronvolts, our ptychographic reconstruction improves the image contrast of single-atom defects in MoS2 substantially, reaching an information limit close to 5α, which corresponds to an Abbe diffraction-limited resolution of 0.39 ångström, at the electron dose and imaging conditions for which conventional imaging methods reach only 0.98 ångström.

GaN/NbN epitaxial semiconductor/superconductor heterostructures.

Epitaxy is a process by which a thin layer of one crystal is deposited in an ordered fashion onto a substrate crystal. The direct epitaxial growth of semiconductor heterostructures on top of crystalline superconductors has proved challenging. Here, however, we report the successful use of molecular beam epitaxy to grow and integrate niobium nitride (NbN)-based superconductors with the wide-bandgap family of semiconductors-silicon carbide, gallium nitride (GaN) and aluminium gallium nitride (AlGaN). We apply molecular beam epitaxy to grow an AlGaN/GaN quantum-well heterostructure directly on top of an ultrathin crystalline NbN superconductor. The resulting high-mobility, two-dimensional electron gas in the semiconductor exhibits quantum oscillations, and thus enables a semiconductor transistor-an electronic gain element-to be grown and fabricated directly on a crystalline superconductor. Using the epitaxial superconductor as the source load of the transistor, we observe in the transistor output characteristics a negative differential resistance-a feature often used in amplifiers and oscillators. Our demonstration of the direct epitaxial growth of high-quality semiconductor heterostructures and devices on crystalline nitride superconductors opens up the possibility of combining the macroscopic quantum effects of superconductors with the electronic, photonic and piezoelectric properties of the group III/nitride semiconductor family.

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.

High-yield monolayer graphene grids for near-atomic resolution cryoelectron microscopy.

Cryogenic electron microscopy (cryo-EM) has become one of the most powerful techniques to reveal the atomic structures and working mechanisms of biological macromolecules. New designs of the cryo-EM grids-aimed at preserving thin, uniform vitrified ice and improving protein adsorption-have been considered a promising approach to achieving higher resolution with the minimal amount of materials and data. Here, we describe a method for preparing graphene cryo-EM grids with up to 99% monolayer graphene coverage that allows for more than 70% grid squares for effective data acquisition with improved image quality and protein density. Using our graphene grids, we have achieved 2.6-Å resolution for streptavidin, with a molecular weight of 52 kDa, from 11,000 particles. Our graphene grids increase the density of examined soluble, membrane, and lipoproteins by at least 5-fold, affording the opportunity for structural investigation of challenging proteins which cannot be produced in large quantity. In addition, our method employs only simple tools that most structural biology laboratories can access. Moreover, this approach supports customized grid designs targeting specific proteins, owing to its broad compatibility with a variety of nanomaterials.

Additive manufacturing of patterned 2D semiconductor through recyclable masked growth.

The 2D van der Waals crystals have shown great promise as potential future electronic materials due to their atomically thin and smooth nature, highly tailorable electronic structure, and mass production compatibility through chemical synthesis. Electronic devices, such as field effect transistors (FETs), from these materials require patterning and fabrication into desired structures. Specifically, the scale up and future development of "2D"-based electronics will inevitably require large numbers of fabrication steps in the patterning of 2D semiconductors, such as transition metal dichalcogenides (TMDs). This is currently carried out via multiple steps of lithography, etching, and transfer. As 2D devices become more complex (e.g., numerous 2D materials, more layers, specific shapes, etc.), the patterning steps can become economically costly and time consuming. Here, we developed a method to directly synthesize a 2D semiconductor, monolayer molybdenum disulfide (MoS2), in arbitrary patterns on insulating SiO2/Si via seed-promoted chemical vapor deposition (CVD) and substrate engineering. This method shows the potential of using the prepatterned substrates as a master template for the repeated growth of monolayer MoS2 patterns. Our technique currently produces arbitrary monolayer MoS2 patterns at a spatial resolution of 2 µm with excellent homogeneity and transistor performance (room temperature electron mobility of 30 cm2 V-1 s-1 and on-off current ratio of 107). Extending this patterning method to other 2D materials can provide a facile method for the repeatable direct synthesis of 2D materials for future electronics and optoelectronics.

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.

Graphene-based bimorphs for micron-sized, autonomous origami machines.

Origami-inspired fabrication presents an attractive platform for miniaturizing machines: thinner layers of folding material lead to smaller devices, provided that key functional aspects, such as conductivity, stiffness, and flexibility, are persevered. Here, we show origami fabrication at its ultimate limit by using 2D atomic membranes as a folding material. As a prototype, we bond graphene sheets to nanometer-thick layers of glass to make ultrathin bimorph actuators that bend to micrometer radii of curvature in response to small strain differentials. These strains are two orders of magnitude lower than the fracture threshold for the device, thus maintaining conductivity across the structure. By patterning 2-[Formula: see text]m-thick rigid panels on top of bimorphs, we localize bending to the unpatterned regions to produce folds. Although the graphene bimorphs are only nanometers thick, they can lift these panels, the weight equivalent of a 500-nm-thick silicon chip. Using panels and bimorphs, we can scale down existing origami patterns to produce a wide range of machines. These machines change shape in fractions of a second when crossing a tunable pH threshold, showing that they sense their environments, respond, and perform useful functions on time and length scales comparable with microscale biological organisms. With the incorporation of electronic, photonic, and chemical payloads, these basic elements will become a powerful platform for robotics at the micrometer scale.

Scaling-up Atomically Thin Coplanar Semiconductor-Metal Circuitry via Phase Engineered Chemical Assembly.

Two-dimensional (2D) layered semiconductors, with their ultimate atomic thickness, have shown promise to scale down transistors for modern integrated circuitry. However, the electrical contacts that connect these materials with external bulky metals are usually unsatisfactory, which limits the transistor performance. Recently, contacting 2D semiconductors using coplanar 2D conductors has shown promise in reducing the problematic high contact resistance. However, many of these methods are not ideal for scaled production. Here, we report on the large-scale, spatially controlled chemical assembly of the integrated 2H-MoTe2 field-effect transistors (FETs) with coplanar metallic 1T'-MoTe2 contacts via phase engineered approaches. We demonstrate that the heterophase FETs exhibit ohmic contact behavior with low contact resistance, resulting from the coplanar seamless contact between 2H and 1T'-MoTe2 confirmed by transmission electron microscopy characterizations. The average mobility of the heterophase FETs was measured to be as high as 23 cm2 V-1 s-1 (comparable with those of exfoliated single crystals), due to the large 2H-MoTe2 single-crystalline domain size (486 ± 187 µm). By developing a patterned growth method, we realize the 1T'-MoTe2 gated heterophase FET array whose components of the channel, gate, and contacts are all 2D materials. Finally, we transfer the heterophase device array onto a flexible substrate and demonstrate the near-infrared photoresponse with high photoresponsivity (∼1.02 A/W). Our study provides a basis for the large-scale application of phase-engineered coplanar MoTe2 semiconductor-metal structure in advanced electronics and optoelectronics.

Sub-nanometre channels embedded in two-dimensional materials.

Two-dimensional (2D) materials are among the most promising candidates for next-generation electronics due to their atomic thinness, allowing for flexible transparent electronics and ultimate length scaling. Thus far, atomically thin p-n junctions, metal-semiconductor contacts, and metal-insulator barriers have been demonstrated. Although 2D materials achieve the thinnest possible devices, precise nanoscale control over the lateral dimensions is also necessary. Here, we report the direct synthesis of sub-nanometre-wide one-dimensional (1D) MoS2 channels embedded within WSe2 monolayers, using a dislocation-catalysed approach. The 1D channels have edges free of misfit dislocations and dangling bonds, forming a coherent interface with the embedding 2D matrix. Periodic dislocation arrays produce 2D superlattices of coherent MoS2 1D channels in WSe2. Using molecular dynamics simulations, we have identified other combinations of 2D materials where 1D channels can also be formed. The electronic band structure of these 1D channels offers the promise of carrier confinement in a direct-gap material and the charge separation needed to access the ultimate length scales necessary for future electronic applications.

Strain Mapping of Two-Dimensional Heterostructures with Subpicometer Precision.

Next-generation, atomically thin devices require in-plane, one-dimensional heterojunctions to electrically connect different two-dimensional (2D) materials. However, the lattice mismatch between most 2D materials leads to unavoidable strain, dislocations, or ripples, which can strongly affect their mechanical, optical, and electronic properties. We have developed an approach to map 2D heterojunction lattice and strain profiles with subpicometer precision and the ability to identify dislocations and out-of-plane ripples. We collected diffraction patterns from a focused electron beam for each real-space scan position with a high-speed, high dynamic range, momentum-resolved detector-the electron microscope pixel array detector (EMPAD). The resulting four-dimensional (4D) phase space data sets contain the full spatially resolved lattice information on the sample. By using this technique on tungsten disulfide (WS2) and tungsten diselenide (WSe2) lateral heterostructures, we have mapped lattice distortions with 0.3 pm precision across multimicron fields of view and simultaneously observed the dislocations and ripples responsible for strain relaxation in 2D laterally epitaxial structures.

Synthetic Lateral Metal-Semiconductor Heterostructures of Transition Metal Disulfides.

Lateral heterostructures with planar integrity form the basis of two-dimensional (2D) electronics and optoelectronics. Here we report that, through a two-step chemical vapor deposition (CVD) process, high-quality lateral heterostructures can be constructed between metallic and semiconducting transition metal disulfide (TMD) layers. Instead of edge epitaxy, polycrystalline monolayer MoS2 in such junctions was revealed to nucleate from the vertices of multilayered VS2 crystals, creating one-dimensional junctions with ultralow contact resistance (0.5 kΩ·µm). This lateral contact contributes to 6-fold improved field-effect mobility for monolayer MoS2, compared to the conventional on-top nickel contacts. The all-CVD strategy presented here hence opens up a new avenue for all-2D-based synthetic electronics.

Intrinsic Two-Dimensional Ferroelectricity with Dipole Locking.

Out-of-plane ferroelectricity with a high transition temperature in ultrathin films is important for the exploration of new domain physics and scaling down of memory devices. However, depolarizing electrostatic fields and interfacial chemical bonds can destroy this long-range polar order at two-dimensional (2D) limit. Here we report the experimental discovery of the locking between out-of-plane dipoles and in-plane lattice asymmetry in atomically thin In_{2}Se_{3} crystals, a new stabilization mechanism leading to our observation of intrinsic 2D out-of-plane ferroelectricity. Through second harmonic generation spectroscopy and piezoresponse force microscopy, we found switching of out-of-plane electric polarization requires a flip of nonlinear optical polarization that corresponds to the inversion of in-plane lattice orientation. The polar order shows a very high transition temperature (∼700 K) without the assistance of extrinsic screening. This finding of intrinsic 2D ferroelectricity resulting from dipole locking opens up possibilities to explore 2D multiferroic physics and develop ultrahigh density memory devices.