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.

Pressure tuning of minibands in MoS2/WSe2 heterostructures revealed by moiré phonons.

Moiré superlattices of two-dimensional heterostructures arose as a new platform to investigate emergent behaviour in quantum solids with unprecedented tunability. To glean insights into the physics of these systems, it is paramount to discover new probes of the moiré potential and moiré minibands, as well as their dependence on external tuning parameters. Hydrostatic pressure is a powerful control parameter, since it allows to continuously and reversibly enhance the moiré potential. Here we use high pressure to tune the minibands in a rotationally aligned MoS2/WSe2 moiré heterostructure, and show that their evolution can be probed via moiré phonons. The latter are Raman-inactive phonons from the individual layers that are activated by the moiré potential. Moiré phonons manifest themselves as satellite Raman peaks arising exclusively from the heterostructure region, increasing in intensity and frequency under applied pressure. Further theoretical analysis reveals that their scattering rate is directly connected to the moiré potential strength. By comparing the experimental and calculated pressure-induced enhancement, we obtain numerical estimates for the moiré potential amplitude and its pressure dependence. The present work establishes moiré phonons as a sensitive probe of the moiré potential as well as the electronic structures of moiré systems.

Revealing Variable Dependences in Hexagonal Boron Nitride Synthesis via Machine Learning.

Wafer-scale monolayer two-dimensional (2D) materials have been realized by epitaxial chemical vapor deposition (CVD) in recent years. To scale up the synthesis of 2D materials, a systematic analysis of how the growth dynamics depend on the growth parameters is essential to unravel its mechanisms. However, the studies of CVD-grown 2D materials mostly adopted the control variate method and considered each parameter as an independent variable, which is not comprehensive for 2D materials growth optimization. Herein, we synthesized a representative 2D material, monolayer hexagonal boron nitride (hBN), on single-crystalline Cu (111) by epitaxial chemical vapor deposition and varied the growth parameters to regulate the hBN domain sizes. Furthermore, we explored the correlation between two growth parameters and provided the growth windows for large flake sizes by the Gaussian process. This new analysis approach based on machine learning provides a more comprehensive understanding of the growth mechanism for 2D materials.

Electrical Control of Chemical Vapor Deposition of Graphene.

Chemical vapor deposition (CVD) is widely used for the efficient growth of low-dimensional materials. The growth mechanism comprises mass and heat transport, gas-phase and surface chemical reactions, and the interaction between the product and the substrate/catalyst. Correspondingly, the controllable parameter space is conventionally focused on the mass flow of each component, the temperature of the reaction chamber and the substrate, and the material and structure of the substrate/catalyst. Here, we report that applying an electric field between the copper substrate and a counter electrode has significant impacts on the growth of graphene. Electrochemical effect and ionic collision effect are observed in different conditions. With the assistance of negative and positive voltages applied on the growth substrate, selective growth and rapid growth of clean graphene films are achieved, respectively. We anticipate such electrical control will open up new ways to assist the synthesis of two-dimensional (2D) materials.

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.

Integrated biosensor platform based on graphene transistor arrays for real-time high-accuracy ion sensing.

Two-dimensional materials such as graphene have shown great promise as biosensors, but suffer from large device-to-device variation due to non-uniform material synthesis and device fabrication technologies. Here, we develop a robust bioelectronic sensing platform  composed of  more than 200 integrated sensing units, custom-built high-speed readout electronics, and machine learning inference that overcomes these challenges to achieve rapid, portable, and reliable measurements. The platform demonstrates reconfigurable multi-ion electrolyte sensing capability and provides highly sensitive, reversible, and real-time response for potassium, sodium, and calcium ions in complex solutions despite variations in device performance. A calibration method leveraging the sensor redundancy and device-to-device variation is also proposed, while a machine learning model trained with multi-dimensional information collected through the multiplexed sensor array is used to enhance the sensing system's functionality and accuracy in ion classification.

Unraveling the Correlation between Raman and Photoluminescence in Monolayer MoS2 through Machine-Learning Models.

2D transition metal dichalcogenides (TMDCs) with intense and tunable photoluminescence (PL) have opened up new opportunities for optoelectronic and photonic applications such as light-emitting diodes, photodetectors, and single-photon emitters. Among the standard characterization tools for 2D materials, Raman spectroscopy stands out as a fast and non-destructive technique capable of probing material's crystallinity and perturbations such as doping and strain. However, a comprehensive understanding of the correlation between photoluminescence and Raman spectra in monolayer MoS2 remains elusive due to its highly nonlinear nature. Here, the connections between PL signatures and Raman modes are systematically explored, providing comprehensive insights into the physical mechanisms correlating PL and Raman features. This study's analysis further disentangles the strain and doping contributions from the Raman spectra through machine-learning models. First, a dense convolutional network (DenseNet) to predict PL maps by spatial Raman maps is deployed. Moreover, a gradient boosted trees model (XGBoost) with Shapley additive explanation (SHAP) to bridge the impact of individual Raman features in PL features is applied. Last, a support vector machine (SVM) to project PL features on Raman frequencies is adopted. This work may serve as a methodology for applying machine learning to characterizations of 2D materials.

Waveguide-integrated mid-infrared photodetection using graphene on a scalable chalcogenide glass platform.

The development of compact and fieldable mid-infrared (mid-IR) spectroscopy devices represents a critical challenge for distributed sensing with applications from gas leak detection to environmental monitoring. Recent work has focused on mid-IR photonic integrated circuit (PIC) sensing platforms and waveguide-integrated mid-IR light sources and detectors based on semiconductors such as PbTe, black phosphorus and tellurene. However, material bandgaps and reliance on SiO2 substrates limit operation to wavelengths λ ≲ 4 µm. Here we overcome these challenges with a chalcogenide glass-on-CaF2 PIC architecture incorporating split-gate photothermoelectric graphene photodetectors. Our design extends operation to λ = 5.2 µm with a Johnson noise-limited noise-equivalent power of 1.1 nW/Hz1/2, no fall-off in photoresponse up to f = 1 MHz, and a predicted 3-dB bandwidth of f3dB > 1 GHz. This mid-IR PIC platform readily extends to longer wavelengths and opens the door to applications from distributed gas sensing and portable dual comb spectroscopy to weather-resilient free space optical communications.

Soft-lock drawing of super-aligned carbon nanotube bundles for nanometre electrical contacts.

The assembly of single-walled carbon nanotubes (CNTs) into high-density horizontal arrays is strongly desired for practical applications, but challenges remain despite myriads of research efforts. Herein, we developed a non-destructive soft-lock drawing method to achieve ultraclean single-walled CNT arrays with a very high degree of alignment (angle standard deviation of ~0.03°). These arrays contained a large portion of nanometre-sized CNT bundles, yielding a high packing density (~400 µm-1) and high current carrying capacity (∼1.8 × 108 A cm-2). This alignment strategy can be generally extended to diverse substrates or sources of raw single-walled CNTs. Significantly, the assembled CNT bundles were used as nanometre electrical contacts of high-density monolayer molybdenum disulfide (MoS2) transistors, exhibiting high current density (~38 µA µm-1), low contact resistance (~1.6 kΩ µm), excellent device-to-device uniformity and highly reduced device areas (0.06 µm2 per device), demonstrating their potential for future electronic devices and advanced integration technologies.

Synthesis of High-Performance Monolayer Molybdenum Disulfide at Low Temperature.

The large-area synthesis of high-quality MoS2 plays an important role in realizing industrial applications of optoelectronics, nanoelectronics, and flexible devices. However, current techniques for chemical vapor deposition (CVD)-grown MoS2 require a high synthetic temperature and a transfer process, which limits its utilization in device fabrications. Here, the direct synthesis of high-quality monolayer MoS2 with the domain size up to 120 µm by metal-organic CVD (MOCVD) at a temperature of 320 °C is reported. Owing to the low-substrate temperature, the MOCVD-grown MoS2 exhibits low impurity doping and nearly unstrained properties on the growth substrate, demonstrating enhanced electronic performance with high electron mobility of 68.3 cm2 V-1 s-1 at room temperature. In addition, by tuning the precursor ratio, a better understanding of the MoS2 growth process via a geometric model of the MoS2 flake shape, is developed, which can provide further guidance for the synthesis of 2D materials.

Bottom-Up Synthesized All-Thermal-Catalyst Aerogels for Heat-Regenerative Air Filtration.

Airborne particular matter (PM) pollution is an increasing global issue and alternative sources of filter fibers are now an area of significant focus. Compared with relatively mature hazardous gas treatments, state of the art high-efficiency PM filters still lack thermal decomposition ability for organic PM pollutants, such as soot from coal-fired power plants and waste-combustion incinerators, resulting in frequent replacement, high cost, and second-hand pollution. In this manuscript, we propose a bottom-up synthesis method to make the first all-thermal-catalyst air filter (ATCAF). Self-assembled from ∼50 nm diameter TiO2 fibers, ATCAF could not only capture the combustion-generated PM pollutants with >99.999% efficiency but also catalyze the complete decomposition of the as-captured hydrocarbon pollutants at high temperature. It has the potential of in situ eliminating the PM pollutants from burning of hydrocarbon materials leveraging the burning heat.

Designing artificial two-dimensional landscapes via atomic-layer substitution.

Technology advancements in history have often been propelled by material innovations. In recent years, two-dimensional (2D) materials have attracted substantial interest as an ideal platform to construct atomic-level material architectures. In this work, we design a reaction pathway steered in a very different energy landscape, in contrast to typical thermal chemical vapor deposition method in high temperature, to enable room-temperature atomic-layer substitution (RT-ALS). First-principle calculations elucidate how the RT-ALS process is overall exothermic in energy and only has a small reaction barrier, facilitating the reaction to occur at room temperature. As a result, a variety of Janus monolayer transition metal dichalcogenides with vertical dipole could be universally realized. In particular, the RT-ALS strategy can be combined with lithography and flip-transfer to enable programmable in-plane multiheterostructures with different out-of-plane crystal symmetry and electric polarization. Various characterizations have confirmed the fidelity of the precise single atomic layer conversion. Our approach for designing an artificial 2D landscape at selective locations of a single layer of atoms can lead to unique electronic, photonic, and mechanical properties previously not found in nature. This opens a new paradigm for future material design, enabling structures and properties for unexplored territories.

Ultralow contact resistance between semimetal and monolayer semiconductors.

Advanced beyond-silicon electronic technology requires both channel materials and also ultralow-resistance contacts to be discovered1,2. Atomically thin two-dimensional semiconductors have great potential for realizing high-performance electronic devices1,3. However, owing to metal-induced gap states (MIGS)4-7, energy barriers at the metal-semiconductor interface-which fundamentally lead to high contact resistance and poor current-delivery capability-have constrained the improvement of two-dimensional semiconductor transistors so far2,8,9. Here we report ohmic contact between semimetallic bismuth and semiconducting monolayer transition metal dichalcogenides (TMDs) where the MIGS are sufficiently suppressed and degenerate states in the TMD are spontaneously formed in contact with bismuth. Through this approach, we achieve zero Schottky barrier height, a contact resistance of 123 ohm micrometres and an on-state current density of 1,135 microamps per micrometre on monolayer MoS2; these two values are, to the best of our knowledge, the lowest and highest yet recorded, respectively. We also demonstrate that excellent ohmic contacts can be formed on various monolayer semiconductors, including MoS2, WS2 and WSe2. Our reported contact resistances are a substantial improvement for two-dimensional semiconductors, and approach the quantum limit. This technology unveils the potential of high-performance monolayer transistors that are on par with state-of-the-art three-dimensional semiconductors, enabling further device downscaling and extending Moore's law.

Enhancement of van der Waals Interlayer Coupling through Polar Janus MoSSe.

Interlayer coupling plays essential roles in the quantum transport, polaritonic, and electrochemical properties of stacked van der Waals (vdW) materials. In this work, we report the unconventional interlayer coupling in vdW heterostructures (HSs) by utilizing an emerging 2D material, Janus transition metal dichalcogenides (TMDs). In contrast to conventional TMDs, monolayer Janus TMDs have two different chalcogen layers sandwiching the transition metal and thus exhibit broken mirror symmetry and an intrinsic vertical dipole moment. Such a broken symmetry is found to strongly enhance the vdW interlayer coupling by as much as 13.2% when forming MoSSe/MoS2 HS as compared to the pristine MoS2 counterparts. Our noncontact ultralow-frequency Raman probe, linear chain model, and density functional theory calculations confirm the enhancement and reveal the origins as charge redistribution in Janus MoSSe and reduced interlayer distance. Our results uncover the potential of tuning interlayer coupling strength through Janus heterostacking.

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.

Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction.

The emerging molybdenum disulfide (MoS2 ) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2 ) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.

Janus monolayers of transition metal dichalcogenides.

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

High-Sulfur-Vacancy Amorphous Molybdenum Sulfide as a High Current Electrocatalyst in Hydrogen Evolution.

The remote hydrogen plasma is able to create abundant S-vacancies on amorphous molybdenum sulfide (a-MoSx ) as active sites for hydrogen evolution. The results demonstrate that the plasma-treated a-MoSx exhibits superior performance and higher stability than Pt in a proton exchange membrane based electrolyzers measurement as a proof-of-concept of industrial application.