Sublimation-based wafer-scale monolayer WS2 formation via self-limited thinning of few-layer WS2.

Atomically-thin monolayer WS2 is a promising channel material for next-generation Moore's nanoelectronics owing to its high theoretical room temperature electron mobility and immunity to short channel effect. The high photoluminescence (PL) quantum yield of the monolayer WS2 also makes it highly promising for future high-performance optoelectronics. However, the difficulty in strictly growing monolayer WS2, due to its non-self-limiting growth mechanism, may hinder its industrial development because of the uncontrollable growth kinetics in attaining the high uniformity in thickness and property on the wafer-scale. In this study, we report a scalable process to achieve a 4 inch wafer-scale fully-covered strictly monolayer WS2 by applying the in situ self-limited thinning of multilayer WS2 formed by sulfurization of WOx films. Through a pulsed supply of sulfur precursor vapor under a continuous H2 flow, the self-limited thinning process can effectively trim down the overgrown multilayer WS2 to the monolayer limit without damaging the remaining bottom WS2 monolayer. Density functional theory (DFT) calculations reveal that the self-limited thinning arises from the thermodynamic instability of the WS2 top layers as opposed to a stable bottom monolayer WS2 on sapphire above a vacuum sublimation temperature of WS2. The self-limited thinning approach overcomes the intrinsic limitation of conventional vapor-based growth methods in preventing the 2nd layer WS2 domain nucleation/growth. It also offers additional advantages, such as scalability, simplicity, and possibility for batch processing, thus opening up a new avenue to develop a manufacturing-viable growth technology for the preparation of a strictly-monolayer WS2 on the wafer-scale.

In-Sensor Computing Realization Using Fully CMOS-Compatible TiN/HfOx-Based Neuristor Array.

With the evolution of artificial intelligence, the explosive growth of data from sensory terminals gives rise to severe energy-efficiency bottleneck issues due to cumbersome data interactions among sensory, memory, and computing modules. Heterogeneous integration methods such as chiplet technology can significantly reduce unnecessary data movement; however, they fail to address the fundamental issue of the substantial time and energy overheads resulting from the physical separation of computing and sensory components. Brain-inspired in-sensor neuromorphic computing (ISNC) has plenty of room for such data-intensive applications. However, one key obstacle in developing ISNC systems is the lack of compatibility between material systems and manufacturing processes deployed in sensors and computing units. This study successfully addresses this challenge by implementing fully CMOS-compatible TiN/HfOx-based neuristor array. The developed ISNC system demonstrates several advantageous features, including multilevel analogue modulation, minimal dispersion, and no significant degradation in conductance (@125 °C). These characteristics enable stable and reproducible neuromorphic computing. Additionally, the device exhibits modulatable sensory and multi-store memory processes. Furthermore, the system achieves information recognition with a high accuracy rate of 93%, along with frequency selectivity and notable activity-dependent plasticity. This work provides a promising route to affordable and highly efficient sensory neuromorphic systems.

Integration of Single-Atom Catalyst with Z-Scheme Heterojunction for Cascade Charge Transfer Enabling Highly Efficient Piezo-Photocatalysis.

Piezo-assisted photocatalysis (namely, piezo-photocatalysis), which utilizes mechanical energy to modulate spatial and energy distribution of photogenerated charge carriers, presents a promising strategy for molecule activation and reactive oxygen species (ROS) generation toward applications such as environmental remediation. However, similarly to photocatalysis, piezo-photocatalysis also suffers from inferior charge separation and utilization efficiency. Herein, a Z-scheme heterojunction composed of single Ag atoms-anchored polymeric carbon nitride (Ag-PCN) and SnO2- x is developed for efficient charge carrier transfer/separation both within the catalyst and between the catalyst and surface oxygen molecules (O2 ). As revealed by charge dynamics analysis and theoretical simulations, the synergy between the single Ag atoms and the Z-scheme heterojunction initiates a cascade electron transfer from SnO2- x to Ag-PCN and then to O2 adsorbed on Ag. With ultrasound irradiation, the polarization field generated within the piezoelectric hybrid further accelerates charge transfer and regulates the O2 activation pathway. As a result, the Ag-PCN/SnO2- x catalyst efficiently activates O2 into ·O2 - , ·OH, and H2 O2 under co-excitation of visible light and ultrasound, which are consequently utilized to trigger aerobic degradation of refractory antibiotic pollutants. This work provides a promising strategy to maneuver charge transfer dynamics for efficient piezo-photocatalysis by integrating single-atom catalysts (SACs) with Z-scheme heterojunction.

Homogeneous in-plane WSe2 P-N junctions for advanced optoelectronic devices.

Conventional doping schemes of silicon (Si) microelectronics are incompatible with atomically thick two-dimensional (2D) transition metal dichalcogenides (TMDCs), which makes it challenging to construct high-quality 2D homogeneous p-n junctions. Herein, we adopt a simple yet effective plasma-treated doping method to seamlessly construct a lateral 2D WSe2 p-n homojunction. WSe2 with ambipolar transport properties was exposed to O2 plasma to form WOx on the surface in a self-limiting process that induces hole doping in the underlying WSe2via electron transfer. Different electrical behaviors were observed between the as-exfoliated (ambipolar) region and the O2 plasma-treated (p-doped) region under electrostatic modulation of the back-gate bias (VBG), which produces a p-n in-plane homojunction. More importantly, a small contact resistance of 710 Ω µm with a p-doped region transistor mobility of ∼157 cm2 V-1 s-1 was achieved due to the transformation of Schottky contact into Ohmic contact after plasma treatment. This effectively avoids Fermi-level pinning and significantly improves the performance of photodetectors. The resultant WSe2 p-n junction device thus exhibits a high photoresponsivity of ∼7.1 × 104 mA W-1 and a superior external quantum efficiency of ∼228%. Also, the physical mechanism of charge transfer in the WSe2 p-n homojunction was analyzed. Our proposed strategy offers a powerful route to realize low contact resistance and high photoresponsivity in 2D TMDC-based optoelectronic devices, paving the way for next-generation atomic-thickness optoelectronics.

Van der Waals Layer Transfer of 2D Materials for Monolithic 3D Electronic System Integration: Review and Outlook.

Two-dimensional materials (2DMs) have attracted a great deal of interest due to their immense potential for scientific breakthroughs and technological innovations. While some 2D transition metal dichalcogenides (TMDC) such as MoS2 and WS2 are considered as the ultimate channel materials in unltrascaled transistors as replacements for Si, there has also been increasing interest in the monolithic 3D integration of 2DMs on the Si CMOS platform or in flexible electronics as back-end-of-line transistors, memory devices/selectors, and sensors, taking advantage of 2DM properties such as a high current driving capability with low leakage current, nonvolatile switching characteristics, a large surface-to-volume ratio, and a tunable bandgap. However, the realization of both of these scenarios critically depends on the development of manufacturing-viable high-yield 2DM layers transfer from the growth substrate to the Si, since the growth of high-quality 2DM layers often requires a high-temperature growth process on template substrates. Motivated by this, extensive efforts have been made by the 2DM research community to develop various 2DM layer transfer methods, leveraging the van der Waals transfer capability of the layer-structured 2DMs. These efforts have led to a number of successful demonstrations of wafer-scale 2D TMDC layer transfer, while 2DM-enabled template growth/transfer of some functional bulk materials such as III-V, Ge, and AlN has also been demonstrated. This review surveys and compares different 2DM transfer methods developed recently, with a focus on large-area 2D TMDC film transfer along with an introduction of 2DM template-assisted van der Waals growth/transfer of non-2D thin films. We will also briefly present an outlook of our envisioned multifunctionalities in 3D integrated electronic systems enabled by monolithic 3D integration of 2DMs and III-V via van der Waals transfer and discuss possible technology options for overcoming remaining challenges.

Anthracene Single-Crystal Scintillators for Computer Tomography Scanning.

X-ray imaging and computed tomography (CT) technology, as the important non-destructive measurements, can observe internal structures without destroying the detected sample, which are always used in biological diagnosis to detect tumors, pathologies, and bone damages. It is always a challenge to find materials with a low detection limit, a short exposure time, and high resolution to reduce X-ray damage and acquire high-contrast images. Here, we described a low-cost and high-efficient method to prepare centimeter-sized anthracene crystals, which exhibited intense X-ray radioluminescence with a detection limit of ∼0.108 µGy s-1, which is only one-fifth of the dose typically used for X-ray diagnostics. Additionally, the low absorption reduced the damage in radiation and ensured superior cycle performance. X-ray detectors based on anthracene crystals also exhibited an extremely high resolution of 40 lp mm-1. The CT scanning and reconstruction of a foam sample were then achieved, and the detailed internal structure could be clearly observed. These indicated that organic crystals are expecting to be leading candidate low-cost materials for low-dose and highly sensitive X-ray detection and CT scanning.

Celebrating 25 Years of IMRE: Research Highlights on Nanomaterials and Nanotechnologies.

The Institute of Materials Research and Engineering (IMRE) is a research institute of the Science and Engineering Research Council (SERC), Agency for Science, Technology and Research (A*STAR). IMRE was established in September 1997. Over the past 25 years, IMRE has developed core competencies and interdisciplinary teams for material development from fundamental discoveries to industrial translation. Currently, with over 400 researchers and state-of-the-art research facilities, IMRE conducts world class research in important material and material technology fields, including polymer composites, optical materials, electronic materials, soft materials, structural materials, energy materials, biomaterials, quantum technologies, as well as advanced characterization. As a material-centered research institute in Singapore, IMRE has played important roles in pushing science boundaries and developing cutting-edge technologies. One of the key strategies is to partner international organizations, research institutes, and industry to fulfill its vision to be a leading research institute to accelerate materials research, moving from "Made in Singapore" toward "Created in Singapore".

Wafer-Scale 2D Hafnium Diselenide Based Memristor Crossbar Array for Energy-Efficient Neural Network Hardware.

Memristor crossbar with programmable conductance could overcome the energy consumption and speed limitations of neural networks when executing core computing tasks in image processing. However, the implementation of crossbar array (CBA) based on ultrathin 2D materials is hindered by challenges associated with large-scale material synthesis and device integration. Here, a memristor CBA is demonstrated using wafer-scale (2-inch) polycrystalline hafnium diselenide (HfSe2 ) grown by molecular beam epitaxy, and a metal-assisted van der Waals transfer technique. The memristor exhibits small switching voltage (0.6 V), low switching energy (0.82 pJ), and simultaneously achieves emulation of synaptic weight plasticity. Furthermore, the CBA enables artificial neural network with a high recognition accuracy of 93.34%. Hardware multiply-and-accumulate (MAC) operation with a narrow error distribution of 0.29% is also demonstrated, and a high power efficiency of greater than 8-trillion operations per second per Watt is achieved. Based on the MAC results, hardware convolution image processing can be performed using programmable kernels (i.e., soft, horizontal, and vertical edge enhancement), which constitutes a vital function for neural network hardware.

Suspended MoS2 Photodetector Using Patterned Sapphire Substrate.

The introduction of patterned sapphire substrates (PSS) has been regarded as an effective method to improve the photoelectric performance of 2D layered materials in recent years. Molybdenum disulfide (MoS2 ), an intriguing transition metal 2D materials with splendid photoresponse owing to a direct-indirect bandgap transition at monolayer, shows promising optoelectronics applications. Here, a large-scale, continuous multilayer MoS2 film is prepared on a SiO2 /Si substrate and transferred to flat sapphire substrate and PSS, respectively. An enhanced dynamic distribution of local electric field and concentrated photon excitons across the interface between MoS2 and patterned sapphire substrates are revealed by the finite-difference time-domain simulation. The photoelectric performance of the MoS2 /PSS photodetector is improved under the three lasers of 365, 460, and 660 nm. Under the 365 nm laser, the photocurrent increased by 3 times, noise equivalent power (NEP) decreases to 1.77 × 10-14 W/Hz1/2 and specific detectivity (D*) increases to 1.2 × 1010 Jones. Meanwhile, the responsivity is increased by 7 times at 460 nm, and the response time of the MoS2 /PSS photodetector is also shortened under three wavelengths. The work demonstrates an effective method for enhancing the optical properties of photodetectors and enabling simultaneous detection of broad-spectrum emissions.

Self-Selective Multi-Terminal Memtransistor Crossbar Array for In-Memory Computing.

Two-terminal resistive switching devices are commonly plagued with longstanding scientific issues including interdevice variability and sneak current that lead to computational errors and high-power consumption. This necessitates the integration of a separate selector in a one-transistor-one-RRAM (1T-1R) configuration to mitigate crosstalk issue, which compromises circuit footprint. Here, we demonstrate a multi-terminal memtransistor crossbar array with increased parallelism in programming via independent gate control, which allows in situ computation at a dense cell size of 3-4.5 F2 and a minimal sneak current of 0.1 nA. Moreover, a low switching energy of 20 fJ/bit is achieved at a voltage of merely 0.42 V. The architecture is capable of performing multiply-and-accumulate operation, a core computing task for pattern classification. A high MNIST recognition accuracy of 96.87% is simulated owing to the linear synaptic plasticity. Such computing paradigm is deemed revolutionary toward enabling data-centric applications in artificial intelligence and Internet-of-things.

Gate-Tunable Polar Optical Phonon to Piezoelectric Scattering in Few-Layer Bi2 O2 Se for High-Performance Thermoelectrics.

Atomically thin Bi2 O2 Se has emerged as a new member in 2D materials with ultrahigh carrier mobility and excellent air-stability, showing great potential for electronics and optoelectronics. In addition, its ferroelectric nature renders an ultralow thermal conductivity, making it a perfect candidate for thermoelectrics. In this work, the thermoelectric performance of 2D Bi2 O2 Se is investigated over a wide temperature range (20-300 K). A gate-tunable transition from polar optical phonon (POP) scattering to piezoelectric scattering is observed, which facilitates the capacity of drastic mobility engineering in 2D Bi2 O2 Se. Consequently, a high power factor of more than 400 µW m-1  K-2 over an unprecedented temperature range (80-200 K) is achieved, corresponding to the persistently high mobility arising from the highly gate-tunable scattering mechanism. This finding provides a new avenue for maximizing thermoelectric performance by changing the scattering mechanism and carrier mobility over a wide temperature range.

Exciton-Enabled Meta-Optics in Two-Dimensional Transition Metal Dichalcogenides.

Optical wavefront engineering has been rapidly developing in fundamentals from phase accumulation in the optical path to the electromagnetic resonances of confined nanomodes in optical metasurfaces. However, the amplitude modulation of light has limited approaches that usually originate from the ohmic loss and absorptive dissipation of materials. Here, an atomically thin photon-sieve platform made of MoS2 multilayers is demonstrated for high-quality optical nanodevices, assisted fundamentally by strong excitonic resonances at the band-nesting region of MoS2. The atomic thin MoS2 significantly facilitates high transmission of the sieved photons and high-fidelity nanofabrication. A proof-of-concept two-dimensional (2D) nanosieve hologram exhibits 10-fold enhanced efficiency compared with its non-2D counterparts. Furthermore, a supercritical 2D lens with its focal spot breaking diffraction limit is developed to exhibit experimentally far-field label-free aberrationless imaging with a resolution of ∼0.44λ at λ = 450 nm in air. This transition-metal-dichalcogenide (TMDC) photonic platform opens new opportunities toward future 2D meta-optics and nanophotonics.

MoS2 /Polymer Heterostructures Enabling Stable Resistive Switching and Multistate Randomness.

Resistive random-access memories (ReRAMs) based on transition metal dichalcogenide layers are promising physical sources for random number generation (RNG). However, most ReRAM devices undergo performance degradation from cycle to cycle, which makes preserving a normal probability distribution during operation a challenging task. Here, ReRAM devices with excellent stability are reported by using a MoS2 /polymer heterostructure as active layer. The stability enhancement manifests in outstanding cumulative probabilities for both high- and low-resistivity states of the memory cells. Moreover, the intrinsic values of the high-resistivity state are found to be an excellent source of randomness as suggested by a Chi-square test. It is demonstrated that one of these cells alone can generate ten distinct random states, in contrast to the four conventional binary cells that would be required for an equivalent number of states. This work unravels a scalable interface engineering process for the production of high-performance ReRAM devices, and sheds light on their promising application as reliable RNGs for enhanced cybersecurity in the big data era.

Large enhancement of thermoelectric performance in MoS2/h-BN heterostructure due to vacancy-induced band hybridization.

Local impurity states arising from atomic vacancies in two-dimensional (2D) nanosheets are predicted to have a profound effect on charge transport due to resonant scattering and can be used to manipulate thermoelectric properties. However, the effects of these impurities are often masked by external fluctuations and turbostratic interfaces; therefore, it is challenging to probe the correlation between vacancy impurities and thermoelectric parameters experimentally. In this work, we demonstrate that n-type molybdenum disulfide (MoS2) supported on hexagonal boron nitride (h-BN) substrate reveals a large anomalous positive Seebeck coefficient with strong band hybridization. The presence of vacancies on MoS2 with a large conduction subband splitting of 50.0 ± 5.0 meV may contribute to Kondo insulator-like properties. Furthermore, by tuning the chemical potential, the thermoelectric power factor can be enhanced by up to two orders of magnitude to 50 mW m-1 K-2 Our work shows that defect engineering in 2D materials provides an effective strategy for controlling band structure and tuning thermoelectric transport.

Anisotropic Collective Charge Excitations in Quasimetallic 2D Transition-Metal Dichalcogenides.

The quasimetallic 1T' phase 2D transition-metal dichalcogenides (TMDs) consist of 1D zigzag metal chains stacked periodically along a single axis. This gives rise to its prominent physical properties which promises the onset of novel physical phenomena and applications. Here, the in-plane electronic correlations are explored, and new mid-infrared plasmon excitations in 1T' phase monolayer WSe2 and MoS2 are observed using optical spectroscopies. Based on an extensive first-principles study which analyzes the charge dynamics across multiple axes of the atomic-layered systems, the collective charge excitations are found to disperse only along the direction perpendicular to the chains. Further analysis reveals that the interchain long-range coupling is responsible for the coherent 1D charge dynamics and the spin-orbit coupling affects the plasmon frequency. Detailed investigation of these charge collective modes in 2D-chained systems offers opportunities for novel device applications and has implications for the underlying mechanism that governs superconductivity in 2D TMD systems.

Three-Dimensional Resonant Exciton in Monolayer Tungsten Diselenide Actuated by Spin-Orbit Coupling.

The intricate features of many-body interactions and spin-orbit coupling play a significant role in numerous physical phenomena. Particularly in two-dimensional transition metal dichalcogenides (2D-TMDs), excitonic dynamics are a key phenomenon that promises opportunities for diverse range of device applications. Here, we report the direct observation of a visible-range three-dimensional resonant exciton and its associated charged exciton in monolayer tungsten diselenide, as compared to monolayer molybdenum disulfide. A comprehensive experimental study that includes high-resolution TEM, Raman, high-resolution spectroscopic ellipsometry over a wide temperature range down to 4 K, high-energy temperature, and excitation power-dependent photoluminescence spectroscopy has been conducted. It is supported by first-principles calculations to unravel the influence of spin-orbit coupling in the formation of the resonant exciton and to identify its in-plane and out-of-plane features. Furthermore, we study the impact of temperature and thickness on the spin-orbit coupling strength in 2D-TMDs. This work is crucial in creating a platform in the fundamental understanding of high-energy resonant exciton in layered two-dimensional systems and that such high-energy optoelectronic features make them an increasingly attractive candidate for novel electronic and optoelectronic applications particularly in the aspects of solar cells and light-emitting diodes via the manipulation of excitonic states.

Revealing the Grain Boundary Formation Mechanism and Kinetics during Polycrystalline MoS2 Growth.

Controllable synthesis of MoS2 with desired grain morphology via chemical vapor deposition (CVD) or physical vapor deposition (PVD) remains a challenge. Hence, it is important to understand polycrystalline growth of MoS2 and further provide guidelines for its CVD/PVD growth. Here, we formulate a kinetic Monte Carlo (kMC) model aiming at predicting the grain boundary (GB) formation in the CVD/PVD growth of polycrystalline MoS2. In the kMC model, the grain growth is via kink nucleation and propagation, whose energetic parameters and initial nucleus details are either from first-principles calculations or from experiments. Using the kMC model, we perform extensive simulations to predict the GB formation by using two, three, four, and five initial nuclei and compare the simulation results with previous experimental results. The obtained GB morphologies are in an excellent agreement with those experimental results. These agreements suggest that the proposed kMC model can correctly capture the mechanism and kinetics of GB formation. In particular, we reveal that the formation of smooth/rough GB is dictated by the two growth vectors for the kink propagation at the two associated grain edges, which is validated by our high-resolution scanning transmission electron microscopy images for PVD growth of MoS2 grains. Besides, we have made predictions beyond reproducing experimental observations, including the growth with artificially designed nuclei, the morphology transformation by tuning the Mo and S sources, and the formation of high-quality single-crystalline monolayer MoS2 by using single-crystalline substrates with vicinal steps. Our kMC model may serve as a powerful predictive tool for the CVD/PVD growth of monolayer MoS2 with desired GB configurations.

Layer Rotation-Angle-Dependent Excitonic Absorption in van der Waals Heterostructures Revealed by Electron Energy Loss Spectroscopy.

Heterostructures comprising van der Waals (vdW) stacked transition metal dichalcogenide (TMDC) monolayers are a fascinating class of two-dimensional (2D) materials. The presence of interlayer excitons, where the electron and the hole remain spatially separated in the two layers due to ultrafast charge transfer, is an intriguing feature of these heterostructures. The optoelectronic functionality of 2D heterostructure devices is critically dependent on the relative rotation angle of the layers. However, the role of the relative rotation angle of the constituent layers on intralayer absorption is not clear yet. Here, we investigate MoS2/WSe2 vdW heterostructures using monochromated low-loss electron energy loss (EEL) spectroscopy combined with aberration-corrected scanning transmission electron microscopy and report that momentum conservation is a critical factor in the intralayer absorption of TMDC vdW heterostructures. The evolution of the intralayer excitonic low-loss EEL spectroscopy peak broadenings as a function of the rotation angle reveals that the interlayer charge transfer rate can be about an order of magnitude faster in the aligned (or anti-aligned) case than in the misaligned cases. These results provide a deeper insight into the role of momentum conservation, one of the fundamental principles governing charge transfer dynamics in 2D vdW heterostructures.

Selective self-assembly of 2,3-diaminophenazine molecules on MoSe2 mirror twin boundaries.

The control of the density and type of line defects on two-dimensional (2D) materials enable the development of new methods to tailor their physical and chemical properties. In particular, mirror twin boundaries (MTBs) on transition metal dichacogenides have attracted much interest due to their metallic state with charge density wave transition and spin-charge separation property. In this work, we demonstrate the self-assembly of 2,3-diaminophenazine (DAP) molecule porous structure with alternate L-type and T-type aggregated configurations on the MoSe2 hexagonal wagon-wheel pattern surface. This site-specific molecular self-assembly is attributed to the more chemically reactive metallic MTBs compared to the pristine semiconducting MoSe2 domains. First-principles calculations reveal that the active MTBs couple with amino groups in the DAP molecules facilitating the DAP assembly. Our results demonstrate the site-dependent electronic and chemical properties of MoSe2 monolayers, which can be exploited as a natural template to create ordered nanostructures.

Employing a Bifunctional Molybdate Precursor To Grow the Highly Crystalline MoS2 for High-Performance Field-Effect Transistors.

Growth of the large-sized and high-quality MoS2 single crystals for high-performance low-power electronic applications is an important step to pursue. Despite the significant improvement made in minimizing extrinsic MoS2 contact resistance based on interfacial engineering of the devices, the electron mobility of field-effect transistors (FETs) made of a synthetic monolayer MoS2 is yet far below the expected theoretical values, implying that the MoS2 crystal quality needs to be further improved. Here, we demonstrate the high-performance two-terminal MoS2 FETs with room-temperature electron mobility up to ∼90 cm2 V-1 s-1 based on the sulfurization growth of the bifunctional precursor, sodium molybdate dihydrate. This unique transition-metal precursor, serving as both the crystalline Mo source and seed promotor (sodium), could facilitate the lateral growth of the highly crystalline monolayer MoS2 crystals (edge length up to ∼260 µm). Substrate surface treatment with oxygen plasma prior to the deposition of the Mo precursor is fundamental to increase the wettability between the Mo source and the substrate, promoting the thinning and coalescence of the source clusters during the growth of large-sized MoS2 single crystals. The control of growth temperature is also an essential step to grow a strictly monolayer MoS2 crystal. A proof-of-concept for thermoelectric device integration utilizing monolayer MoS2 sheds light on its potential in low-voltage and self-powered electronics.