Fast water transport and molecular sieving through ultrathin ordered conjugated-polymer-framework membranes.

The development of membranes that block solutes while allowing rapid water transport is of great importance. The microstructure of the membrane needs to be rationally designed at the molecular level to achieve precise molecular sieving and high water flux simultaneously. We report the design and fabrication of ultrathin, ordered conjugated-polymer-framework (CPF) films with thicknesses down to 1 nm via chemical vapour deposition and their performance as separation membranes. Our CPF membranes inherently have regular rhombic sub-nanometre (10.3 × 3.7 Å) channels, unlike membranes made of carbon nanotubes or graphene, whose separation performance depends on the alignment or stacking of materials. The optimized membrane exhibited a high water/NaCl selectivity of ∼6,900 and water permeance of ∼112 mol m-2 h-1 bar-1, and salt rejection >99.5% in high-salinity mixed-ion separations driven by osmotic pressure. Molecular dynamics simulations revealed that water molecules quickly and collectively pass through the membrane by forming a continuous three-dimensional network within the hydrophobic channels. The advent of ordered CPF provides a route towards developing carbon-based membranes for precise molecular separation.

Wafer-scale single-orientation 2D layers by atomic edge-guided epitaxial growth.

Two-dimensional (2D) layered materials hold tremendous promise for post-Si nanoelectronics due to their unique optical and electrical properties. Significant advances have been achieved in device fabrication and synthesis routes for 2D nanoelectronics over the past decade; however, one major bottleneck preventing their immediate applications has been the lack of a reproducible approach for growing wafer-scale single-crystal films despite tremendous progress in recent experimental demonstrations. In this tutorial review, we provide a systematic summary of the critical factors-including crystal/substrate symmetry and energy consideration-necessary for synthesizing single-orientation 2D layers. In particular, we focus on the discussions of the atomic edge-guided epitaxial growth, which assists in unidirectional nucleation for the wafer-scale growth of single-crystal 2D layers.

Ledge-directed epitaxy of continuously self-aligned single-crystalline nanoribbons of transition metal dichalcogenides.

Two-dimensional transition metal dichalcogenide nanoribbons are touted as the future extreme device downscaling for advanced logic and memory devices but remain a formidable synthetic challenge. Here, we demonstrate a ledge-directed epitaxy (LDE) of dense arrays of continuous, self-aligned, monolayer and single-crystalline MoS2 nanoribbons on ß-gallium (III) oxide (ß-Ga2O3) (100) substrates. LDE MoS2 nanoribbons have spatial uniformity over a long range and transport characteristics on par with those seen in exfoliated benchmarks. Prototype MoS2-nanoribbon-based field-effect transistors exhibit high on/off ratios of 108 and an averaged room temperature electron mobility of 65 cm2 V-1 s-1. The MoS2 nanoribbons can be readily transferred to arbitrary substrates while the underlying ß-Ga2O3 can be reused after mechanical exfoliation. We further demonstrate LDE as a versatile epitaxy platform for the growth of p-type WSe2 nanoribbons and lateral heterostructures made of p-WSe2 and n-MoS2 nanoribbons for futuristic electronics applications.

Finite-Area Membrane Metasurfaces for Enhancing Light-Matter Coupling in Monolayer Transition Metal Dichalcogenides.

Transition metal dichalcogenides (TMDCs) are at the forefront of nanophotonics because of their exceptional optical characteristics. The 2D architecture of TMDCs facilitates efficient light absorption and emission, holding tantalizing potential for next-generation nanophotonic and quantum devices. Yet, the atomic thinness limits their interaction volume with light, affecting light-matter interaction and quantum efficiency. The light coupling in the 2D layered TMDCs can be enhanced by integration with photonic structure, and the metasurfaces supporting bound states in the continuum (BICs) offer strong confinement of optical fields, ideal for coupling with 2D TMDCs. Here, we demonstrate enhanced light-matter coupling by integrating TMDC monolayers, including WSe2 and MoS2, with a finite-area membrane metasurface, leading to amplified and high-quality-factor (Q-factor) spontaneous emission from quasi-BIC-coupled TMDC monolayers. The high-Q-factor emission extends over an area with a scale of a few micrometers while maintaining the high-Q factor across the emission area. Notably, the suspended finite-area membrane metasurface, which is freestanding in air rather than positioned atop a substrate, minimizes radiation loss while enhancing light-matter interaction in the TMDC monolayer. Furthermore, the predominantly in-plane dipole orientation of excitons within TMDC monolayers results in distinctive enhancement behaviors for emission, contingent on the excitation power, when coupled with quasi-BIC modes exhibiting TE and TM resonances. This work introduces a nanophotonic platform for robust coupling of membrane metasurfaces with 2D materials, offering possibilities for developing 2D material-based nanophotonic and quantum devices.

Enhanced Photogating Gain in Scalable MoS2 Plasmonic Photodetectors via Resonant Plasmonic Metasurfaces.

Absorption of photons in atomically thin materials has become a challenge in the realization of ultrathin, high-performance optoelectronics. While numerous schemes have been used to enhance absorption in 2D semiconductors, such enhanced device performance in scalable monolayer photodetectors remains unattained. Here, we demonstrate wafer-scale integration of monolayer single-crystal MoS2 photodetectors with a nitride-based resonant plasmonic metasurface to achieve a high detectivity of 2.58 × 1012 Jones with a record-low dark current of 8 pA and long-term stability over 40 days. Upon comparison with control devices, we observe an overall enhancement factor of >100; this can be attributed to the local strong EM field enhanced photogating effect by the resonant plasmonic metasurface. Considering the compatibility of 2D semiconductors and hafnium nitride with the Si CMOS process and their scalability across wafer sizes, our results facilitate the smooth incorporation of 2D semiconductor-based photodetectors into the fields of imaging, sensing, and optical communication applications.

Interfacial Reconstructed Layer Controls the Orientation of Monolayer Transition-Metal Dichalcogenides.

Growing continuous monolayer films of transition-metal dichalcogenides (TMDs) without the disruption of grain boundaries is essential to realize the full potential of these materials for future electronics and optoelectronics, but it remains a formidable challenge. It is generally believed that controlling the TMDs orientations on epitaxial substrates stems from matching the atomic registry, symmetry, and penetrable van der Waals forces. Interfacial reconstruction within the exceedingly narrow substrate-epilayer gap has been anticipated. However, its role in the growth mechanism has not been intensively investigated. Here, we report the experimental conformation of an interfacial reconstructed (IR) layer within the substrate-epilayer gap. Such an IR layer profoundly impacts the orientations of nucleating TMDs domains and, thus, affects the materials' properties. These findings provide deeper insights into the buried interface that could have profound implications for the development of TMD-based electronics and optoelectronics.

Oriented lateral growth of two-dimensional materials on c-plane sapphire.

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) represent the ultimate thickness for scaling down channel materials. They provide a tantalizing solution to push the limit of semiconductor technology nodes in the sub-1 nm range. One key challenge with 2D semiconducting TMD channel materials is to achieve large-scale batch growth on insulating substrates of single crystals with spatial homogeneity and compelling electrical properties. Recent studies have claimed the epitaxy growth of wafer-scale, single-crystal 2D TMDs on a c-plane sapphire substrate with deliberately engineered off-cut angles. It has been postulated that exposed step edges break the energy degeneracy of nucleation and thus drive the seamless stitching of mono-oriented flakes. Here we show that a more dominant factor should be considered: in particular, the interaction of 2D TMD grains with the exposed oxygen-aluminium atomic plane establishes an energy-minimized 2D TMD-sapphire configuration. Reconstructing the surfaces of c-plane sapphire substrates to only a single type of atomic plane (plane symmetry) already guarantees the single-crystal epitaxy of monolayer TMDs without the aid of step edges. Electrical results evidence the structural uniformity of the monolayers. Our findings elucidate a long-standing question that curbs the wafer-scale batch epitaxy of 2D TMD single crystals-an important step towards using 2D materials for future electronics. Experiments extended to perovskite materials also support the argument that the interaction with sapphire atomic surfaces is more dominant than step-edge docking.

Scalable CMOS back-end-of-line-compatible AlScN/two-dimensional channel ferroelectric field-effect transistors.

Three-dimensional monolithic integration of memory devices with logic transistors is a frontier challenge in computer hardware. This integration is essential for augmenting computational power concurrent with enhanced energy efficiency in big data applications such as artificial intelligence. Despite decades of efforts, there remains an urgent need for reliable, compact, fast, energy-efficient and scalable memory devices. Ferroelectric field-effect transistors (FE-FETs) are a promising candidate, but requisite scalability and performance in a back-end-of-line process have proven challenging. Here we present back-end-of-line-compatible FE-FETs using two-dimensional MoS2 channels and AlScN ferroelectric materials, all grown via wafer-scalable processes. A large array of FE-FETs with memory windows larger than 7.8 V, ON/OFF ratios greater than 107 and ON-current density greater than 250 µA um-1, all at ~80 nm channel length are demonstrated. The FE-FETs show stable retention up to 10 years by extension, and endurance greater than 104 cycles in addition to 4-bit pulse-programmable memory features, thereby opening a path towards the three-dimensional heterointegration of a two-dimensional semiconductor memory with silicon complementary metal-oxide-semiconductor logic.

Graphdiyne-Based Nanofilms for Compliant On-Skin Sensing.

Thin-film electronics pliably laminated onto the epidermis for noninvasive, specific, and multifunctional sensing are ideal wearable systems for health monitoring and information technologies. However, it remains a critical challenge to fabricate ultrathin and compliant skin-like sensors with high imperceptibility and sensitivities. Here we report a design of conductive hydrogen-substituted graphdiyne (HsGDY) nanofilms with conjugated porous structure and inherent softness for on-skin sensors that allow minimization of stress and discomfort with wear. Dominated by the subtle deformation-induced changes in the interdomain tunneling conductance, the engineered HsGDY sensors show continuous and accurate results. Real-time noninvasive spatial mapping of dynamic/static strains in both tensile/compressive directions monitors various body motions with high sensitivity (GF ∼22.6, under 2% strain), fast response (∼60 ms), and long-term durability (∼5000 cycles). Moreover, such devices can dynamically distinguish between the temperature difference and frequency of air inhaled and exhaled through the nostril, revealing a quantitative assessment of the movement/health of the human body. The proof-of-concept strategy provides an alternative route for the design of next-generation wearable organic bioelectronics with multiple electronic functionalities.

Three-dimensional hierarchically porous MoS2 foam as high-rate and stable lithium-ion battery anode.

Architected materials that actively respond to external stimuli hold tantalizing prospects for applications in energy storage, wearable electronics, and bioengineering. Molybdenum disulfide, an excellent two-dimensional building block, is a promising candidate for lithium-ion battery anode. However, the stacked and brittle two-dimensional layered structure limits its rate capability and electrochemical stability. Here we report the dewetting-induced manufacturing of two-dimensional molybdenum disulfide nanosheets into a three-dimensional foam with a structural hierarchy across seven orders of magnitude. Our molybdenum disulfide foam provides an interpenetrating network for efficient charge transport, rapid ion diffusion, and mechanically resilient and chemically stable support for electrochemical reactions. These features induce a pseudocapacitive energy storage mechanism involving molybdenum redox reactions, confirmed by in-situ X-ray absorption near edge structure. The extraordinary electrochemical performance of molybdenum disulfide foam outperforms most reported molybdenum disulfide-based Lithium-ion battery anodes and state-of-the-art materials. This work opens promising inroads for various applications where special properties arise from hierarchical architecture.

Low-defect-density WS2 by hydroxide vapor phase deposition.

Two-dimensional (2D) semiconducting monolayers such as transition metal dichalcogenides (TMDs) are promising channel materials to extend Moore's Law in advanced electronics. Synthetic TMD layers from chemical vapor deposition (CVD) are scalable for fabrication but notorious for their high defect densities. Therefore, innovative endeavors on growth reaction to enhance their quality are urgently needed. Here, we report that the hydroxide W species, an extremely pure vapor phase metal precursor form, is very efficient for sulfurization, leading to about one order of magnitude lower defect density compared to those from conventional CVD methods. The field-effect transistor (FET) devices based on the proposed growth reach a peak electron mobility ~200 cm2/Vs (~800 cm2/Vs) at room temperature (15 K), comparable to those from exfoliated flakes. The FET device with a channel length of 100 nm displays a high on-state current of ~400 µA/µm, encouraging the industrialization of 2D materials.

Aberration-corrected STEM imaging of 2D materials: Artifacts and practical applications of threefold astigmatism.

High-resolution scanning transmission electron microscopy (HR-STEM) with spherical aberration correction enables researchers to peer into two-dimensional (2D) materials and correlate the material properties with those of single atoms. The maximum intensity of corrected electron beam is confined in the area having sub-angstrom size. Meanwhile, the residual threefold astigmatism of the electron probe implies a triangular shape distribution of the intensity, whereas its tails overlap and thus interact with several atomic species simultaneously. The result is the resonant modulation of contrast that interferes the determination of phase transition of 2D materials. Here, we theoretically reveal and experimentally determine the origin of resonant modulation of contrast and its unintended impact on violating the power-law dependence of contrast on coordination modes between transition metal and chalcogenide atoms. The finding illuminates the correlation between atomic contrast, spatially inequivalent chalcogenide orientation, and residual threefold astigmatism on determining the atomic structure of emerging 2D materials.

3D Crumpled Ultrathin 1T MoS2 for Inkjet Printing of Mg-Ion Asymmetric Micro-supercapacitors.

Metallic molybdenum disulfide (MoS2), e.g., 1T phase, is touted as a highly promising material for energy storage that already displays a great capacitive performance. However, due to its tendency to aggregate and restack, it remains a formidable challenge to assemble a high-performance electrode without scrambling the intrinsic structure. Here, we report an electrohydrodynamic-assisted fabrication of 3D crumpled MoS2 (c-MoS2) and its formation of an additive-free stable ink for scalable inkjet printing. The 3D c-MoS2 powders exhibited a high concentration of metallic 1T phase and an ultrathin structure. The aggregation-resistant properties of the 3D crumpled particles endow the electrodes with open space for electrolyte ion transport. Importantly, we experimentally discovered and theoretically validated that 3D 1T c-MoS2 enables an extended electrochemical stable working potential range and enhanced capacitive performance in a bivalent magnesium-ion aqueous electrolyte. With reduced graphene oxide (rGO) as the positive electrode material, we inkjet-printed 96 rigid asymmetric micro-supercapacitors (AMSCs) on a 4-in. Si/SiO2 wafer and 100 flexible AMSCs on photo paper. These AMSCs exhibited a wide stable working voltage of 1.75 V and excellent capacitance retention of 96% over 20 000 cycles for a single device. Our work highlights the promise of 3D layered materials as well-dispersed functional materials for large-scale printed flexible energy storage devices.

Mixed-dimensional MXene-hydrogel heterostructures for electronic skin sensors with ultrabroad working range.

Skin-mountable microelectronics are garnering substantial interest for various promising applications including human-machine interfaces, biointegrated devices, and personalized medicine. However, it remains a critical challenge to develop e-skins to mimic the human somatosensory system in full working range. Here, we present a multifunctional e-skin system with a heterostructured configuration that couples vinyl-hybrid-silica nanoparticle (VSNP)-modified polyacrylamide (PAM) hydrogel with two-dimensional (2D) MXene through nano-bridging layers of polypyrrole nanowires (PpyNWs) at the interfaces, featuring high toughness and low hysteresis, in tandem with controlled crack generation and distribution. The multidimensional configurations endow the e-skin with an extraordinary working range (2800%), ultrafast responsiveness (90 ms) and resilience (240 ms), good linearity (800%), tunable sensing mechanisms, and excellent reproducibility. In parallel, this e-skin platform is capable of detecting, quantifying, and remotely monitoring stretching motions in multiple dimensions, tactile pressure, proximity sensing, and variations in temperature and light, establishing a promising platform for next-generation smart flexible electronics.

Metal-Guided Selective Growth of 2D Materials: Demonstration of a Bottom-Up CMOS Inverter.

2D transition metal dichalcogenide (TMD) layered materials are promising for future electronic and optoelectronic applications. The realization of large-area electronics and circuits strongly relies on wafer-scale, selective growth of quality 2D TMDs. Here, a scalable method, namely, metal-guided selective growth (MGSG), is reported. The success of control over the transition-metal-precursor vapor pressure, the first concurrent growth of two dissimilar monolayer TMDs, is demonstrated in conjunction with lateral or vertical TMD heterojunctions at precisely desired locations over the entire wafer in a single chemical vapor deposition (VCD) process. Owing to the location selectivity, MGSG allows the growth of p- and n-type TMDs with spatial homogeneity and uniform electrical performance for circuit applications. As a demonstration, the first bottom-up complementary metal-oxide-semiconductor inverter based on p-type WSe2 and n-type MoSe2 is achieved, which exhibits a high and reproducible voltage gain of 23 with little dependence on position.

Design and Mechanistic Study of Highly Durable Carbon-Coated Cobalt Diphosphide Core-Shell Nanostructure Electrocatalysts for the Efficient and Stable Oxygen Evolution Reaction.

The facile synthesis of hierarchically functional, catalytically active, and electrochemically stable nanostructures holds a tremendous promise for catalyzing the efficient and durable oxygen evolution reaction (OER) and yet remains a formidable challenge. Herein, we report the scalable production of core-shell nanostructures composed of carbon-coated cobalt diphosphide nanosheets, C@CoP2, via three simple steps: (i) electrochemical deposition of Co species, (ii) gas-phase phosphidation, and (iii) carbonization of CoP2 for catalytic durability enhancement. Electrochemical characterizations showed that C@CoP2 delivers an overpotential of 234 mV, retains its initial activity for over 80 h of continuous operation, and exhibits a fast OER rate of 63.8 mV dec-1 in base.