Bionic Design of Iron-Doped MoSe2 Catalyst for Efficient Nitrogen Fixation.

The catalytic system of biological nitrogen fixation in nature primarily relies on the "FeMo cofactor" within nitrogenase enzymes. Inspired by this natural structure, we have designed a bionic inorganic counterpart, iron-doped MoSe2, for the efficient electroreduction of dinitrogen to ammonia. The introduced Fe dopant significantly enhances nitrogen fixation activity of MoSe2. Furthermore, we constructed a heterostructure catalyst, the Fe-MoSe2/Mo2C with more versatile Mo valence states. The heterostructured electrocatalyst achieves an ammonia production rate of 3.38 µg cm-2 h-1, and a Faradaic efficiency of 30.8 %, which is ~5 fold higher than that of pristine MoSe2. This study presents a novel approach for designing bionic nitrogen fixation electrocatalysts.

Synthesis of Rhenium-Doped Copper Twin Boundary for High-Turnover-Frequency Electrochemical Nitrogen Reduction.

The precise design and synthesis of active sites to improve catalyst's performance has emerged as a promising tactic for electrochemistry. However, it is challenging to combine different types of active sites and manipulate them simultaneously at atomic resolution. Here, we present a strategy to synthesize Re atom-doped Cu twin boundaries (TBs), through pulsed electrodeposition and boundary segregation. The Re-doped Cu TBs demonstrate a highly efficient nitrogen reduction reaction (NRR) performance. Re-doped Cu TBs showed a turnover frequency of ∼5889 s-1, ∼800 times higher than the pure Cu TB active centers (∼7 s-1). In addition to the "acceptance-donation" activation of N2 molecules, theoretical calculations also reveal that the Re-Re dimer on TB can boost the NRR and impede the hydrogen evolution reaction synchronously, rendering Re-doped Cu TB catalysts with high NRR activity and selectivity.

Epitaxial Growth of Two-Dimensional MWW Zeolite.

Two-dimensional (2D) zeolite, with a high aspect ratio, has more open skeletons and accessible active sites than its three-dimensional (3D) counterpart. However, traditional methods of obtaining 2D zeolites often cause structural damage and widespread skeleton defects, hindering efficient selectivity in molecular separation. In this study, we present, for the first time, a direct epitaxial synthesis of 2D zeolite (Epi-MWW) guided by hexagonal boron nitride (h-BN) with a coincidence matching of site lattices to MWW zeolite. The as-grown Epi-MWW zeolite possesses a high crystallinity and intact hexagonal 2D morphology, with an average thickness of 10 nm and an aspect ratio of over 50. Thanks to its excellent molecular accessibility, the diffusion time constants of o-xylene (OX) and p-xylene (PX) are as 12 and 133 times higher than those of conventional MCM-22, respectively; the PX/OX selectivity of Epi-MWW is 7.4 times better than MCM-22 as calculated by the ideal adsorbed solution theory.

Long-Range Epitaxial MOF Electronics for Continuous Monitoring of Human Breath Ammonia.

As an important biomarker, ammonia exhibits a strong correlation with protein metabolism and specific organ dysfunction. Limited by the immobile instrumental structure, invasive and complicated procedures, and unsatisfactory online sensitivity and selectivity, current medical diagnosis fails to monitor this chemical in real time efficiently. Herein, we present the successful synthesis of a long-range epitaxial metal-organic framework on a millimeter domain-sized single-crystalline graphene substrate (LR-epi-MOF). With a perfect 30° epitaxial angle and a mere 2.8% coincidence site lattice mismatch between the MOF and graphene, this long-range-ordered epitaxial structure boosts the charge transfer from ammonia to the MOF and then to graphene, thereby promoting the overall charge delocalization and exhibiting extraordinary electrical global coupling properties. This unique characteristic imparts a remarkable sensitivity of 0.1 ppb toward ammonia. The sub-ppb detecting capability and high anti-interference ability enable continuous information recording of breath ammonia that is strongly correlated with the intriguing human lifestyle. Wearable electronics based on the LR-epi-MOF could accurately portray the active protein metabolism pattern in real time and provide personal assistance in health management.

12-inch growth of uniform MoS2 monolayer for integrated circuit manufacture.

Two-dimensional (2D) semiconductors, such as transition metal dichalcogenides, provide an opportunity for beyond-silicon exploration. However, the lab to fab transition of 2D semiconductors is still in its preliminary stages, and it has been challenging to meet manufacturing standards of stability and repeatability. Thus, there is a natural eagerness to grow wafer-level, high-quality films with industrially acceptable scale-cost-performance metrics. Here we report an improved chemical vapour deposition synthesis method in which the controlled release of precursors and substrates predeposited with amorphous Al2O3 ensure the uniform synthesis of monolayer MoS2 as large as 12 inches while also enabling fast and non-toxic growth to reduce manufacturing costs. Transistor arrays were fabricated to further confirm the high quality of the film and its integrated circuit application potential. This work achieves the co-optimization of scale-cost-performance metrics and lays the foundation for advancing the integration of 2D semiconductors in industry-standard pilot lines.

An artificial neural network chip based on two-dimensional semiconductor.

Recently, research on two-dimensional (2D) semiconductors has begun to translate from the fundamental investigation into rudimentary functional circuits. In this work, we unveil the first functional MoS2 artificial neural network (ANN) chip, including multiply-and-accumulate (MAC), memory and activation function circuits. Such MoS2 ANN chip is realized through fabricating 818 field-effect transistors (FETs) on a wafer-scale and high-homogeneity MoS2 film, with a gate-last process to realize top gate structured FETs. A 62-level simulation program with integrated circuit emphasis (SPICE) model is utilized to design and optimize our analog ANN circuits. To demonstrate a practical application, a tactile digit sensing recognition was demonstrated based on our ANN circuits. After training, the digit recognition rate exceeds 97%. Our work not only demonstrates the protentional of 2D semiconductors in wafer-scale integrated circuits, but also paves the way for its future application in AI computation.

Gate-Modulated High-Response Field-Effect Transistor-Type Gas Sensor Based on the MoS2/Metal-Organic Framework Heterostructure.

The high surface-to-volume ratio and decent material properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) make them advantageous as an active channel in field-effect transistor (FET)-type gas sensing devices. However, most existing TMD gas sensors are based on a two-terminal resistance-type structure and suffer from low responsivity and slow response, which has urged materials optimization as well as device engineering. Metal-organic frameworks (MOFs) have a large number of ordered binding sites in the pores that can specifically bind to gas molecules and can be decorated on TMD surfaces to enhance gas sensing capabilities. In this work, we successfully realize the FET-type gas sensor with MoS2-MOF as the channel. The fabricated gas sensor exhibits enhanced NH3 sensing performance (22.475 times higher in responsivity) as compared to the device with a bare MoS2 channel. In addition, the FET-type gas sensor geometry enables effective tuning of sensitivity through electrical gating based on the modulation over the channel carrier concentration. Furthermore, the dependence of responsivity on the MoS2 thickness is investigated as well to achieve an in-depth understanding of the electrical modulation mechanism of the MOF-decorated MoS2 gas sensors. The demonstrated results can pave an attractive pathway toward the realization of advanced high-response and tunable TMD-based gas sensing devices.

Pass-Transistor Logic Circuits Based on Wafer-Scale 2D Semiconductors.

2D semiconductors, such as molybdenum disulfide (MoS2 ), have attracted tremendous attention in constructing advanced monolithic integrated circuits (ICs) for future flexible and energy-efficient electronics. However, the development of large-scale ICs based on 2D materials is still in its early stage, mainly due to the non-uniformity of the individual devices and little investigation of device and circuit-level optimization. Herein, a 4-inch high-quality monolayer MoS2 film is successfully synthesized, which is then used to fabricate top-gated (TG) MoS2 field-effect transistors with wafer-scale uniformity. Some basic circuits such as static random access memory and ring oscillators are examined. A pass-transistor logic configuration based on pseudo-NMOS is then employed to design more complex MoS2 logic circuits, which are successfully fabricated with proper logic functions tested. These preliminary integration efforts show the promising potential of wafer-scale 2D semiconductors for application in complex ICs.

Precise CO2 Reduction for Bilayer Graphene.

It is of great significance to explore unique and diverse chemical pathways to convert CO2 into high-value-added products. Bilayer graphene (BLG), with a tunable twist angle and band structure, holds tremendous promise in both fundamental physics and next-generation high-performance devices. However, the π-conjugation and precise two-atom thickness are hindering the selective pathway, through an uncontrolled CO2 reduction and perplexing growth mechanism. Here, we developed a chemical vapor deposition method to catalytically convert CO2 into a high-quality BLG single crystal with a room temperature mobility of 2346 cm2 V-1 s-1. In a finely controlled growth window, the CO2 molecule works as both the carbon source and the oxygen etchant, helping to precisely define the BLG nucleus and set a record growth rate of 300 µm h-1.

Strain-Induced Nonlinear Frictional Behavior of Graphene Nanowall Films.

Graphene nanowall (GNW) films, a representation of three-dimensional (3D) carbon nanomaterial films, are emerging as promising candidates for applications in electric devices and composites, on account of their 3D structures and exceptional properties of graphene sheets. However, the frictional responses of GNW films, which exhibit significant influence on their performances, have seldom been reported. Herein, we reported a growth process of a GNW film by the chemical vapor deposition method and studied the frictional behavior of the GNW film for the first time. The results demonstrated the nonlinearity between the frictional force of the GNW film and normal load. Based on the structural evolution of the GNW film with normal load and frictional tests on precompressed GNW films, the influence of the strain property of the GNW film, namely, the strengthening effect, could be confirmed. The results of molecular dynamics simulations show that the bending force of GNWs in front of the tip plays a determinate role in the frictional force of the GNW film. Furthermore, the bending force is proportional to the bending contact area, which increases nonlinearly with the normal load due to the strengthening effect of the GNW film. The result suggests that the nonlinear increase of the bending contact area induced by the strengthening effect of the GNW film is the key factor that leads to its nonlinear frictional force. This study provides a novel insight into the frictional responses of GNW films, which would be beneficial for the design and application of electric devices and composites made of GNW and other 3D carbon nanomaterial films.

Wafer-scale functional circuits based on two dimensional semiconductors with fabrication optimized by machine learning.

Triggered by the pioneering research on graphene, the family of two-dimensional layered materials (2DLMs) has been investigated for more than a decade, and appealing functionalities have been demonstrated. However, there are still challenges inhibiting high-quality growth and circuit-level integration, and results from previous studies are still far from complying with industrial standards. Here, we overcome these challenges by utilizing machine-learning (ML) algorithms to evaluate key process parameters that impact the electrical characteristics of MoS2 top-gated field-effect transistors (FETs). The wafer-scale fabrication processes are then guided by ML combined with grid searching to co-optimize device performance, including mobility, threshold voltage and subthreshold swing. A 62-level SPICE modeling was implemented for MoS2 FETs and further used to construct functional digital, analog, and photodetection circuits. Finally, we present wafer-scale test FET arrays and a 4-bit full adder employing industry-standard design flows and processes. Taken together, these results experimentally validate the application potential of ML-assisted fabrication optimization for beyond-silicon electronic materials.

Reversing the Polarity of MoS2 with PTFE.

Pristine monolayer molybdenum disulfide (MoS2) demonstrates predominant and persistent n-type semiconducting polarity due to the natural sulfur vacancy, which hinders its electronic and optoelectronic applications in the rich bipolarity area of semiconductors. Current doping strategies in single-layer MoS2 are either too mild to reverse the heavily n-doped polarity or too volatile to create a robust electronic device meeting the requirements of both a long lifetime and compatibility for mass production. Herein, we demonstrate that MoS2 can be transferred onto polytetrafluoroethylene (PTFE), one of the most electronegative substrates. After transfer, the MoS2 photoluminescence exhibits an obvious blueshift from 1.83 to 1.89 eV and a prolonged lifetime, from 0.13 to 3.19 ns. The Fermi level of MoS2 experiences a remarkable 510 meV decrease, transforming its electronic structure into that of a hole-rich p-type semiconductor. Our work reveals a strong p-doping effect and charge transfer between MoS2 and PTFE, shedding light on a new nonvolatile strategy to fabricate p-type MoS2 devices.

An in-memory computing architecture based on two-dimensional semiconductors for multiply-accumulate operations.

In-memory computing may enable multiply-accumulate (MAC) operations, which are the primary calculations used in artificial intelligence (AI). Performing MAC operations with high capacity in a small area with high energy efficiency remains a challenge. In this work, we propose a circuit architecture that integrates monolayer MoS2 transistors in a two-transistor-one-capacitor (2T-1C) configuration. In this structure, the memory portion is similar to a 1T-1C Dynamic Random Access Memory (DRAM) so that theoretically the cycling endurance and erase/write speed inherit the merits of DRAM. Besides, the ultralow leakage current of the MoS2 transistor enables the storage of multi-level voltages on the capacitor with a long retention time. The electrical characteristics of a single MoS2 transistor also allow analog computation by multiplying the drain voltage by the stored voltage on the capacitor. The sum-of-product is then obtained by converging the currents from multiple 2T-1C units. Based on our experiment results, a neural network is ex-situ trained for image recognition with 90.3% accuracy. In the future, such 2T-1C units can potentially be integrated into three-dimensional (3D) circuits with dense logic and memory layers for low power in-situ training of neural networks in hardware.

Dichroic Photoelasticity in Black Phosphorus Revealed by Ultrafast Coherent Phonon Dynamics.

Coherent longitudinal lattice vibrations of black phosphorus provide unique access to the out-of-plane strain coupled in-plane optical properties. In this work, polarization-resolved femtosecond transient absorption microscopy is applied to study the anisotropic coherent phonon responses. Multiorder phonon harmonics were observed with thickness dependence well explained by the linear chain model, allowing rapid optical mapping of phonon frequency distributions. More interestingly, exotic coherent phonon oscillations occourred with a π-phase jump between the armchair and zigzag polarizations, which reveals opposite signs of photoelasticity under the longitudinal strain. Specifically, compressive strain reduces the imaginary refractive index in the armchair polarization but increases the real refractive index in the zigzag polarization, as confirmed by the ab initio calculations and thin film model. These fundamental properties of black phosphorus hold potential for applications in ultrafast and polarization-sensitive photoacoustic/photoelastic modulators.

Microscopic Mechanisms Behind the High Friction and Failure Initiation of Graphene Wrinkles.

Wrinkling occurs on the surfaces of large-area graphene ubiquitously. Despite that the wrinkled structures are found to degrade the lubricous property, the behind mechanisms remain less understood. Here, atomic force microscopy is adopted to characterize the friction and wear properties of graphene wrinkles (GWs) with different heights by nanoscratch tests. We verify the phenomena of high friction and reduced load-carrying capacity of wrinkles and report the observation of lubrication deterioration with increased heights. Using molecular dynamics simulations, we reveal that the contact quality at the interface is a dominant role in the friction evolution of wrinkles. The high friction of wrinkles is determined by the increased contact area and commensurability caused by the wrinkle deformation and topography changes. The wrinkle failure initiates near the root of the formed bilayer configuration due to the increased lateral stiffness and reduced atomic distance between the wrinkle layers. The increased interlocking effect results in a local shear stress of 91 GPa and induces the phase transitions of carbon atoms easily. As the wrinkle height decreases, the unstable local configuration weakens the interlocking effects and cannot fail even at a high load. This investigation sheds light on the microscopic frictional contact of GWs and provides guidance for tuning the tribological properties of graphene by controlling the wrinkle structures.

Direct electrosynthesis of 52% concentrated CO on silver's twin boundary.

The gaseous product concentration in direct electrochemical CO2 reduction is usually hurdled by the electrode's Faradaic efficiency, current density, and inevitable mixing with the unreacted CO2. A concentrated gaseous product with high purity will greatly lower the barrier for large-scale CO2 fixation and follow-up industrial usage. Here, we developed a pneumatic trough setup to collect the CO2 reduction product from a precisely engineered nanotwinned electrocatalyst, without using ion-exchange membrane. The silver catalyst's twin boundary density can be tuned from 0.3 to 1.5 × 104 cm-1. With the lengthy and winding twin boundaries, this catalyst exhibits a Faradaic efficiency up to 92% at -1.0 V and a turnover frequency of 127 s-1 in converting CO2 to CO. Through a tandem electrochemical-CVD system, we successfully produced CO with a volume percentage of up to 52%, and further transformed it into single layer graphene film.

Metal-Organic Framework for Transparent Electronics.

Electronics allowing for visible light to pass through are attractive, where a key challenge is to make the core functional units transparent. Here, it is shown that transparent electronics can be constructed by epitaxial growth of metal-organic frameworks (MOFs) on single-layer graphene (SLG) to give a desirable transparency of 95.7% to 550 nm visible light and an electrical conductivity of 4.0 × 104 S m-1. Through lattice and symmetry match, collective alignment of MOF pores and dense packing of MOFs vertically on SLG are achieved, as directly visualized by electron microscopy. These MOF-on-SLG constructs are capable of room-temperature recognition of gas molecules at the ppb level with a linear range from 10 to 108 ppb, providing real-time gas monitoring function in transparent electronics. The corresponding devices can be fabricated on flexible substrates with large size, 3 × 5 cm, and afford continuous folding for more than 200 times without losing conductivity or transparency.

FIB-Patterned Nano-Supercapacitors: Minimized Size with Ultrahigh Performances.

Advances in microelectronic system technology have necessitated the development and miniaturization of energy storage devices. Supercapacitors are an important complement to batteries in microelectronic systems; and further reduction of the size of micro-supercapacitors is challenging. Here, a novel strategy is demonstrated to break through the resolution limit of micro-supercapacitors by preparing nano-supercapacitors (NSCs) with interdigital nanosized electrodes using focused ion beam technology. The minimization of the size of the NSCs leads to a large increase in capacitance, with a high areal capacitance of 9.52 mF cm-2 and a volumetric capacitance of 18 700 F cm-3 , far superior to those of other reported works. Size reduction and the narrowing of the physical separation between nanoelectrodes are proved to be the most crucial factors in the enhancement of capacitive performances. New charge-storage mechanisms are discovered with a remarkable nonfaradaic double-layer capacitance that exists due to the considerable inner electric field force at the nanoscale. The developed strategy and the first set of data provided here shed light on the design and fabrication of flexible interdigitated NSCs that rival state-of-the-art supercapacitors in performance.

Vibrational Imaging and Quantification of Two-Dimensional Hexagonal Boron Nitride with Stimulated Raman Scattering.

Hexagonal boron nitride (h-BN) is an important member of two-dimensional (2D) materials with a large direct bandgap, and has attracted growing interest in ultraviolet optoelectronics and nanoelectronics. Compared with graphene and graphite, h-BN has weak Raman effect because of the far off-resonance excitation; hence, it is difficult to exploit Raman spectroscopy to characterize important properties of 2D h-BN, such as thickness, doping, and strain effects. Here, we applied stimulated Raman scattering (SRS) to enhance the sensitivity of the E2g Raman mode of h-BN. We showed that SRS microscopy achieves rapid high resolution imaging of h-BN with a pixel dwell time 4 orders of magnitude smaller than conventional spontaneous Raman microscopy. Moreover, the near-perfect linear dependence of signal intensity on h-BN thickness and isotropic polarization dependence allow convenient determination of the flake thickness with SRS imaging. Our results indicated that SRS microscopy provides a promising tool for high-speed quantification of h-BN and holds the potential for vibrational imaging of 2D materials.

Phase, Conductivity, and Surface Coordination Environment in Two-Dimensional Electrochemistry.

The booming frontier of electrochemistry is radically transforming the landscape of global chemical and energy industry. Most recent advancements in electrocatalysts have been built on trial and error, lacking model experiments to illuminate the fundamental factors hidden behind, such as phase, conductivity, and surface coordination environment. Here, we use phase-controllable, highly oriented two-dimensional MoTe2 as the model catalysts. The 2H phase MoTe2's conductivity can be engineered both extrinsically and intrinsically by single-layer graphene and lithiation, bringing down the sheet resistance from 0.95 MΩ/□ to 0.8 kΩ/□ and 0.6 kΩ/□. The corresponding electrocatalytic performance was unlocked from a silent state, catching up to its 1T' counterpart, with a parallel Tafel slope of 141 mV/dec. A focused ion beam further exposed the edge atoms, which exhibited a hydrogen evolution turnover frequency 104 times superior to that of basal plane atoms.