Search

Two-dimensional (2D) semiconductors are promising candidates for optoelectronic application and quantum information processes due to their inherent out-of-plane 2D confinement. In addition, they offer the possibility of achieving low-dimensional in-plane exciton confinement, similar to zero-dimensional quantum dots, with intriguing optical and electronic properties via strain or composition engineering. However, realizing such laterally confined 2D monolayers and systematically controlling size-dependent optical properties remain significant challenges. Here, we report the observation of lateral confinement of excitons in epitaxially grown in-plane MoSe 2 quantum dots (~15-60 nm wide) inside a continuous matrix of WSe 2 monolayer film via a sequential epitaxial growth process. Various optical spectroscopy techniques reveal the size-dependent exciton confinement in the MoSe 2 monolayer quantum dots with exciton blue shift (12-40 meV) at a low temperature as compared to continuous monolayer MoSe 2 . Finally, single-photon emission (g 2 (0) ~ 0.4) was also observed from the smallest dots at 1.6 K. Our study opens the door to compositionally engineered, tunable, in-plane quantum light sources in 2D semiconductors., (© 2024. The Author(s).)

Transition Metal Dichalcogenides (TMDs) are a unique class of materials that exhibit attractive electrical and optical properties which have generated significant interest for applications in microelectronics, optoelectronics, energy storage, and sensing. Considering the potential of these materials to impact such applications, it is crucial to develop a reliable and scalable synthesis process that is compatible with modern industrial manufacturing methods. Metal-organic chemical vapor deposition (MOCVD) offers an ideal solution to produce TMDs, due to its compatibility with large-scale production, precise layer control, and high material purity. Optimization of MOCVD protocols is necessary for effective TMD synthesis and integration into mainstream technologies. Additionally, improvements in metrology are necessary to measure the quality of the fabricated samples more accurately. In this work, we study MOCVD of wafer-scale molybdenum disulfide (MoS 2 ) utilizing two common chalcogen precursors, H 2 S and DTBS. We then develop a metrology platform for wafer scale samples quality assessment. For this, the coalesced films were characterized using Raman spectroscopy, atomic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Kelvin probe force microscopy. We then correlate the structural analysis of these grown films with electrical performance by using aerosol jet printing to fabricate van der Pauw test structures and assess sheet resistance., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Achieving robust and electrically controlled valley polarization in monolayer transition metal dichalcogenides (ML-TMDs) is a frontier challenge for realistic valleytronic applications. Theoretical investigations show that the integration of 2D materials with ferroelectrics is a promising strategy; however, an experimental demonstration has remained elusive. Here, we fabricate ferroelectric field-effect transistors using a ML-WSe 2 channel and an Al 0.68 Sc 0.32 N (AlScN) ferroelectric dielectric and experimentally demonstrate efficient tuning as well as non-volatile control of valley polarization. We measure a large array of transistors and obtain a maximum valley polarization of ∼27% at 80 K with stable retention up to 5400 s. The enhancement in the valley polarization is ascribed to the efficient exciton-to-trion (X-T) conversion and its coupling with an out-of-plane electric field, viz., the quantum-confined Stark effect. This changes the valley depolarization pathway from strong exchange interactions to slow spin-flip intervalley scattering. Our research demonstrates a promising approach for achieving non-volatile control over valley polarization for practical valleytronic device applications.

C-H bond activation enables the facile synthesis of new chemicals. While C-H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C-H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C-C coupling mediated by 2D TMDCs to promote C-H activation and carbon dots synthesis. Our results shed light on 2D materials for C-H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials., (© 2024. The Author(s).)

The semiconductor industry is transitioning to the 'More Moore' era, driven by the adoption of three-dimensional (3D) integration schemes surpassing the limitations of traditional two-dimensional scaling. Although innovative packaging solutions have made 3D integrated circuits (ICs) commercially viable, the inclusion of through-silicon vias and microbumps brings about increased area overhead and introduces parasitic capacitances that limit overall performance. Monolithic 3D integration (M3D) is regarded as the future of 3D ICs, yet its application faces hurdles in silicon ICs due to restricted thermal processing budgets in upper tiers, which can degrade device performance. To overcome these limitations, emerging materials like carbon nanotubes and two-dimensional semiconductors have been integrated into the back end of silicon ICs. Here we report the M3D integration of complementary WSe 2 FETs, in which n-type FETs are placed in tier 1 and p-type FETs are placed in tier 2. In particular, we achieve dense and scaled integration through 300 nm vias with a pitch of <1 µm, connecting more than 300 devices in tiers 1 and 2. Moreover, we have effectively implemented vertically integrated logic gates, encompassing inverters, NAND gates and NOR gates. Our demonstration highlights the two-dimensional materials' role in advancing M3D integration in complementary metal-oxide-semiconductor circuits., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

Rational manipulation and assembly of discrete colloidal particles into architected superstructures have enabled several applications in materials science and nanotechnology. Optical manipulation techniques, typically operated in fluid media, facilitate the precise arrangement of colloidal particles into superstructures by using focused laser beams. However, as the optical energy is turned off, the inherent Brownian motion of the particles in fluid media impedes the retention and reconfiguration of such superstructures. Overcoming this fundamental limitation, we present on-demand, three-dimensional (3D) optical manipulation of colloidal particles in a phase-change solid medium made of surfactant bilayers. Unlike liquid crystal media, the lack of fluid flow within the bilayer media enables the assembly and retention of colloids for diverse spatial configurations. By utilizing the optically controlled temperature-dependent interactions between the particles and their surrounding media, we experimentally exhibit the holonomic microscale control of diverse particles for repeatable, reconfigurable, and controlled colloidal arrangements in 3D. Finally, we demonstrate tunable light-matter interactions between the particles and 2D materials by successfully manipulating and retaining these particles at fixed distances from the 2D material layers. Our experimental results demonstrate that the particles can be retained for over 120 days without any change in their relative positions or degradation in the bilayers. With the capability of arranging particles in 3D configurations with long-term stability, our platform pushes the frontiers of optical manipulation for distinct applications such as metamaterial fabrication, information storage, and security.

Recent advancements in ferroelectric field-effect transistors (FeFETs) using two-dimensional (2D) semiconductor channels and ferroelectric Al 0.68 Sc 0.32 N (AlScN) allow high-performance nonvolatile devices with exceptional ON-state currents, large ON/OFF current ratios, and large memory windows (MW). However, previous studies have solely focused on n-type FeFETs, leaving a crucial gap in the development of p-type and ambipolar FeFETs, which are essential for expanding their applicability to a wide range of circuit-level applications. Here, we present a comprehensive demonstration of n-type, p-type, and ambipolar FeFETs on an array scale using AlScN and multilayer/monolayer WSe 2 . The dominant injected carrier type is modulated through contact engineering at the metal-semiconductor junction, resulting in the realization of all three types of FeFETs. The effect of contact engineering on the carrier injection is further investigated through technology-computer-aided design simulations. Moreover, our 2D WSe 2 /AlScN FeFETs achieve high electron and hole current densities of ∼20 and ∼10 μA/μm, respectively, with a high ON/OFF ratio surpassing ∼10 7 and a large MW of >6 V (0.14 V/nm).

Monolayer transition metal dichalcogenides have strong intracovalent bonding. When stacked in multilayers, however, weak van der Waals interactions dominate interlayer mechanical coupling and, thus, influence their lattice vibrations. This study presents the frequency evolution of interlayer phonons in twisted WS 2 bilayers, highly subject to the twist angle. The twist angle between the layers is controlled to modulate the spacing between the layers, which, in turn, affects the interlayer coupling that is probed by Raman spectroscopy. The shifts of high-frequency E 2g 1 (Γ) and A 1g (Γ) phonon modes and their frequency separations are dependent on the twist angle, reflecting the correlation between the interlayer mechanical coupling and twist angle. In this work, we fabricated large-area, twisted bilayer WS 2 with a clean interface with controlled twist angles. Polarized Raman spectroscopy identified new interlayer modes, which were not previously reported, depending on the twist angle. The appearance of breathing modes in Raman phonon spectra provides evidence of strong interlayer coupling in bilayer structures. We confirm that the twist angle can alter the exciton and trion dynamics of bilayers as indicated by the photoluminescence peak shift. These large-area controlled twist angle samples have practical applications in optoelectronic device fabrication and twistronics.

In the field of semiconductors, three-dimensional (3D) integration not only enables packaging of more devices per unit area, referred to as 'More Moore' 1 but also introduces multifunctionalities for 'More than Moore' 2 technologies. Although silicon-based 3D integrated circuits are commercially available 3-5 , there is limited effort on 3D integration of emerging nanomaterials 6,7 such as two-dimensional (2D) materials despite their unique functionalities 7-10 . Here we demonstrate (1) wafer-scale and monolithic two-tier 3D integration based on MoS 2 with more than 10,000 field-effect transistors (FETs) in each tier; (2) three-tier 3D integration based on both MoS 2 and WSe 2 with about 500 FETs in each tier; and (3) two-tier 3D integration based on 200 scaled MoS 2 FETs (channel length, L CH  = 45 nm) in each tier. We also realize a 3D circuit and demonstrate multifunctional capabilities, including sensing and storage. We believe that our demonstrations will serve as the foundation for more sophisticated, highly dense and functionally divergent integrated circuits with a larger number of tiers integrated monolithically in the third dimension., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

As topological insulators (TIs) are becoming increasingly intriguing, the community is exploring transformative applications that require interfacing TIs with other materials such as ferromagnets or superconductors. Herein, we report on the manifestations of superconducting electrons carried by topological surface states (TSS) in Bi 2 Se 3 films. As key signatures of TSS-carried Cooper pairs, we uncover the hysteresis of magnetoresistance (MR) and the switching behavior of anisotropic magnetoresistance (AMR). For in-plane fields perpendicular to the injected current, AMR shows negative switching (resistance drop) when the contacts become superconducting, which is consistent with a cooperative Zeeman effect enabled by the spin-momentum locking of TSS. The MR and AMR behaviors are robust, occurring reliably in multiple samples, from different sources, and with different defect concentrations. Our findings can guide novel developments in superconductor/TI quantum devices relying on supercurrent detection as well as lead to more refined transport signatures of Majorana zero-modes in the future.

Epitaxial growth of two-dimensional transition metal dichalcogenides on sapphire has emerged as a promising route to wafer-scale single-crystal films. Steps on the sapphire act as sites for transition metal dichalcogenide nucleation and can impart a preferred domain orientation, resulting in a substantial reduction in mirror twins. Here we demonstrate control of both the nucleation site and unidirectional growth direction of WSe 2 on c-plane sapphire by metal-organic chemical vapour deposition. The unidirectional orientation is found to be intimately tied to growth conditions via changes in the sapphire surface chemistry that control the step edge location of WSe 2 nucleation, imparting either a 0° or 60° orientation relative to the underlying sapphire lattice. The results provide insight into the role of surface chemistry on transition metal dichalcogenide nucleation and domain alignment and demonstrate the ability to engineer domain orientation over wafer-scale substrates., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

n-type field effect transistors (FETs) based on two-dimensional (2D) transition-metal dichalcogenides (TMDs) such as MoS 2 and WS 2 have come close to meeting the requirements set forth in the International Roadmap for Devices and Systems (IRDS). However, p-type 2D FETs are dramatically lagging behind in meeting performance standards. Here, we adopt a three-pronged approach that includes contact engineering, channel length ( L ch ) scaling, and monolayer doping to achieve high performance p-type FETs based on synthetic WSe 2 . Using electrical measurements backed by atomistic imaging and rigorous analysis, Pd was identified as the favorable contact metal for WSe 2 owing to better epitaxy, larger grain size, and higher compressive strain, leading to a lower Schottky barrier height. While the ON-state performance of Pd-contacted WSe 2 FETs was improved by ∼10× by aggressively scaling L ch from 1 μm down to ∼20 nm, ultrascaled FETs were found to be contact limited. To reduce the contact resistance, monolayer tungsten oxyselenide (WO x Se y ) obtained using self-limiting oxidation of bilayer WSe 2 was used as a p-type dopant. This led to ∼5× improvement in the ON-state performance and ∼9× reduction in the contact resistance. We were able to achieve a median ON-state current as high as ∼10 μA/μm for ultrascaled and doped p-type WSe 2 FETs with Pd contacts. We also show the applicability of our monolayer doping strategy to other 2D materials such as MoS 2 , MoTe 2 , and MoSe 2 .

A true random number generator (TRNG) is essential to ensure information security for Internet of Things (IoT) edge devices. While pseudorandom number generators (PRNGs) have been instrumental, their deterministic nature limits their application in security-sensitive scenarios. In contrast, hardware-based TRNGs derived from physically unpredictable processes offer greater reliability. This study demonstrates a peripheral-free TRNG utilizing two cascaded three-stage inverters (TSIs) in conjunction with an XOR gate composed of monolayer molybdenum disulfide (MoS 2 ) field-effect transistors (FETs) by exploiting the stochastic charge trapping and detrapping phenomena at and/or near the MoS 2 /dielectric interface. The entropy source passes the NIST SP800-90B tests with a minimum normalized entropy of 0.8780, while the generated bits pass the NIST SP800-22 randomness tests without any postprocessing. Moreover, the keys generated using these random bits are uncorrelated with near-ideal entropy, bit uniformity, and Hamming distances, exhibiting resilience against machine learning (ML) attacks, temperature variations, and supply bias fluctuations with a frugal energy expenditure of 30 pJ/bit. This approach offers an advantageous alternative to conventional silicon, memristive, and nanomaterial-based TRNGs as it obviates the need for extensive peripherals while harnessing the potential of atomically thin 2D materials in developing low-power TRNGs.

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 MoS 2 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 10 7 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 10 4  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., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Over the past few years, graphene grown by chemical vapor deposition (CVD) has gained prominence as a template to grow transition metal dichalcogenide (TMD) overlayers. The resulting two-dimensional (2D) TMD/graphene vertical heterostructures are attractive for optoelectronic and energy applications. However, the effects of the microstructural heterogeneities of graphene grown by CVD on the growth of the TMD overlayers are relatively unknown. Here, we present a detailed investigation of how the stacking order and twist angle of CVD graphene influence the nucleation of WSe 2 triangular crystals. Through the combination of experiments and theory, we correlate the presence of interlayer dislocations in bilayer graphene with how WSe 2 nucleates, in agreement with the observation of a higher nucleation density of WSe 2 on top of Bernal-stacked bilayer graphene versus twisted bilayer graphene. Scanning/transmission electron microscopy (S/TEM) data show that interlayer dislocations are present only in Bernal-stacked bilayer graphene but not in twisted bilayer graphene. Atomistic ReaxFF reactive force field molecular dynamics simulations reveal that strain relaxation promotes the formation of these interlayer dislocations with localized buckling in Bernal-stacked bilayer graphene, whereas the strain becomes distributed in twisted bilayer graphene. Furthermore, these localized buckles in graphene are predicted to serve as thermodynamically favorable sites for binding WSe x molecules, leading to the higher nucleation density of WSe 2 on Bernal-stacked graphene. Overall, this study explores synthesis-structure correlations in the WSe 2 /graphene vertical heterostructure system toward the site-selective synthesis of TMDs by controlling the structural attributes of the graphene substrate.

Two-dimensional (2D) material research is rapidly evolving to broaden the spectrum of emergent 2D systems. Here, we review recent advances in the theory, synthesis, characterization, device, and quantum physics of 2D materials and their heterostructures. First, we shed insight into modeling of defects and intercalants, focusing on their formation pathways and strategic functionalities. We also review machine learning for synthesis and sensing applications of 2D materials. In addition, we highlight important development in the synthesis, processing, and characterization of various 2D materials (e.g., MXnenes, magnetic compounds, epitaxial layers, low-symmetry crystals, etc.) and discuss oxidation and strain gradient engineering in 2D materials. Next, we discuss the optical and phonon properties of 2D materials controlled by material inhomogeneity and give examples of multidimensional imaging and biosensing equipped with machine learning analysis based on 2D platforms. We then provide updates on mix-dimensional heterostructures using 2D building blocks for next-generation logic/memory devices and the quantum anomalous Hall devices of high-quality magnetic topological insulators, followed by advances in small twist-angle homojunctions and their exciting quantum transport. Finally, we provide the perspectives and future work on several topics mentioned in this review.

Limitations in cloud-based computing have prompted a paradigm shift toward all-in-one "edge" devices capable of independent data sensing, computing, and storage. Advanced defense and space applications stand to benefit immensely from this due to their need for continual operation in areas where maintaining remote oversight is difficult. However, the extreme environments relevant to these applications necessitate rigorous testing of technologies, with a common requirement being hardness to ionizing radiation. Two-dimensional (2D) molybdenum disulfide (MoS 2 ) has been noted to enable the sensing, storage, and logic capabilities necessary for all-in-one edge devices. Despite this, the investigation of ionizing radiation effects in MoS 2 -based devices remains incomplete. In particular, studies on gamma radiation effects in MoS 2 have been largely limited to standalone films, with few device investigations; to the best of our knowledge, no explorations have been made into gamma radiation effects on the sensing and memory capabilities of MoS 2 -based devices. In this work, we have used a statistical approach to study high-dose (1 Mrad) gamma radiation effects on photosensitive and programmable memtransistors fabricated from large-area monolayer MoS 2 . Memtransistors were divided into separate groups to ensure accurate extraction of device characteristics pertaining to baseline performance, sensing, and memory before and after irradiation. All-MoS 2 logic gates were also assessed to determine the gamma irradiation impact on logic implementation. Our findings show that the multiple functionalities of MoS 2 memtransistors are not severely impacted by gamma irradiation even without dedicated shielding/mitigation techniques. We believe that these results serve as a foundation for more application-oriented studies going forward.

Two-dimensional (2D) semiconductors possess promise for the development of field-effect transistors (FETs) at the ultimate scaling limit due to their strong gate electrostatics. However, proper FET scaling requires reduction of both channel length ( L CH ) and contact length ( L C ), the latter of which has remained a challenge due to increased current crowding at the nanoscale. Here, we investigate Au contacts to monolayer MoS 2 FETs with L C H down to 100 nm and L C down to 20 nm to evaluate the impact of contact scaling on FET performance. Au contacts are found to display a ∼2.5× reduction in the ON-current, from 519 to 206 μA/μm, when L C is scaled from 300 to 20 nm. It is our belief that this study is warranted to ensure an accurate representation of contact effects at and beyond the technology nodes currently occupied by silicon.

Ultrathin 2D-GaN x can be formed by Ga intercalation into epitaxial graphene (EG) on SiC followed by nitridation in ammonia. Defects in the graphene provide routes for intercalation, but the nature and role of the defects have remained elusive. Here we examine the influence of graphene layer thickness and chemical functionalization on Ga intercalation and 2D-GaN x formation using a combination of experimental and theoretical studies. Thin buffer layer regions of graphene near steps on SiC readily undergo oxygen functionalization when exposed to air or a He/O 2 plasma in contrast to thicker regions which are not chemically modified. Oxygen functionalization is found to inhibit Ga intercalation leading to accumulation of Ga droplets on the surface. In contrast, Ga readily intercalates between EG and SiC in the thicker graphene regions that do not contain oxygen. When NH 3 annealing is carried out immediately after Ga exposure, 2D-GaN x formation is observed only in the oxygen-functionalized regions, and Ga intercalated under thicker nonfunctionalized graphene does not convert to GaN x . Density functional theory calculations demonstrate that oxygen functionalization of graphene alters the binding energy of Ga and NH 3 species to the graphene surface. The presence of hydroxyl groups on graphene inhibits binding of Ga to the surface; however, it enhances the chemical reactivity of the graphene surface to NH 3 which, in turn, enhances Ga binding and facilitates the formation of 2D-GaN x . By modifying the EG process to produce oxygen-functionalized buffer layer graphene, uniformly intercalated 2D-GaN x is obtained across the entire substrate surface.

As the energy and hardware investments necessary for conventional high-precision digital computing continue to explode in the era of artificial intelligence (AI), a change in paradigm that can trade precision for energy and resource efficiency is being sought for many computing applications. Stochastic computing (SC) is an attractive alternative since, unlike digital computers, which require many logic gates and a high transistor volume to perform basic arithmetic operations such as addition, subtraction, multiplication, sorting, etc., SC can implement the same using simple logic gates. While it is possible to accelerate SC using traditional silicon complementary metal-oxide-semiconductor (CMOS) technology, the need for extensive hardware investment to generate stochastic bits (s-bits), the fundamental computing primitive for SC, makes it less attractive. Memristor and spin-based devices offer natural randomness but depend on hybrid designs involving CMOS peripherals for accelerating SC, which increases area and energy burden. Here, the limitations of existing and emerging technologies are overcome, and a standalone SC architecture embedded in memory and based on 2D memtransistors is experimentally demonstrated. The monolithic and non-von-Neumann SC architecture occupies a small hardware footprint and consumes a miniscule amount of energy (<1 nJ) for both s-bit generation and arithmetic operations, highlighting the benefits of SC., (© 2022 Wiley-VCH GmbH.)

Natural intelligence has many dimensions, with some of its most important manifestations being tied to learning about the environment and making behavioral changes. In primates, vision plays a critical role in learning. The underlying biological neural networks contain specialized neurons and synapses which not only sense and process visual stimuli but also learn and adapt with remarkable energy efficiency. Forgetting also plays an active role in learning. Mimicking the adaptive neurobiological mechanisms for seeing, learning, and forgetting can, therefore, accelerate the development of artificial intelligence (AI) and bridge the massive energy gap that exists between AI and biological intelligence. Here, we demonstrate a bioinspired machine vision system based on a 2D phototransistor array fabricated from large-area monolayer molybdenum disulfide (MoS 2 ) and integrated with an analog, nonvolatile, and programmable memory gate-stack; this architecture not only enables dynamic learning and relearning from visual stimuli but also offers learning adaptability under noisy illumination conditions at miniscule energy expenditure. In short, our demonstrated "all-in-one" hardware vision platform combines "sensing", "computing", and "storage" to not only overcome the von Neumann bottleneck of conventional complementary metal-oxide-semiconductor (CMOS) technology but also to eliminate the need for peripheral circuits and sensors.

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moiré pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moiré engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Atomically thin transition metal dichalcogenides (TMDs), like MoS 2 with high carrier mobilities and tunable electron dispersions, are unique active material candidates for next generation opto-electronic devices. Previous studies on ion irradiation show great potential applications when applied to two-dimensional (2D) materials, yet have been limited to micron size exfoliated flakes or smaller. To demonstrate the scalability of this method for industrial applications, we report the application of relatively low power (50 keV) 4 He + ion irradiation towards tuning the optoelectronic properties of an epitaxially grown continuous film of MoS 2 at the wafer scale, and demonstrate that precise manipulation of atomistic defects can be achieved in TMD films using ion implanters. The effect of 4 He + ion fluence on the PL and Raman signatures of the irradiated film provides new insights into the type and concentration of defects formed in the MoS 2 lattice, which are quantified through ion beam analysis. PL and Raman spectroscopy indicate that point defects are generated without causing disruption to the underlying lattice structure of the 2D films and hence, this technique can prove to be an effective way to achieve defect-mediated control over the opto-electronic properties of MoS 2 and other 2D materials., (Creative Commons Attribution license.)

In-sensor processing, which can reduce the energy and hardware burden for many machine vision applications, is currently lacking in state-of-the-art active pixel sensor (APS) technology. Photosensitive and semiconducting two-dimensional (2D) materials can bridge this technology gap by integrating image capture (sense) and image processing (compute) capabilities in a single device. Here, we introduce a 2D APS technology based on a monolayer MoS 2 phototransistor array, where each pixel uses a single programmable phototransistor, leading to a substantial reduction in footprint (900 pixels in ∼0.09 cm 2 ) and energy consumption (100s of fJ per pixel). By exploiting gate-tunable persistent photoconductivity, we achieve a responsivity of ∼3.6 × 10 7  A W -1 , specific detectivity of ∼5.6 × 10 13  Jones, spectral uniformity, a high dynamic range of ∼80 dB and in-sensor de-noising capabilities. Further, we demonstrate near-ideal yield and uniformity in photoresponse across the 2D APS array., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Artificial neural networks have demonstrated superiority over traditional computing architectures in tasks such as pattern classification and learning. However, they do not measure uncertainty in predictions, and hence they can make wrong predictions with high confidence, which can be detrimental for many mission-critical applications. In contrast, Bayesian neural networks (BNNs) naturally include such uncertainty in their model, as the weights are represented by probability distributions (e.g. Gaussian distribution). Here we introduce three-terminal memtransistors based on two-dimensional (2D) materials, which can emulate both probabilistic synapses as well as reconfigurable neurons. The cycle-to-cycle variation in the programming of the 2D memtransistor is exploited to achieve Gaussian random number generator-based synapses, whereas 2D memtransistor based integrated circuits are used to obtain neurons with hyperbolic tangent and sigmoid activation functions. Finally, memtransistor-based synapses and neurons are combined in a crossbar array architecture to realize a BNN accelerator for a data classification task., (© 2022. The Author(s).)

Bayesian networks (BNs) find widespread application in many real-world probabilistic problems including diagnostics, forecasting, computer vision, etc. The basic computing primitive for BNs is a stochastic bit (s-bit) generator that can control the probability of obtaining '1' in a binary bit-stream. While silicon-based complementary metal-oxide-semiconductor (CMOS) technology can be used for hardware implementation of BNs, the lack of inherent stochasticity makes it area and energy inefficient. On the other hand, memristors and spintronic devices offer inherent stochasticity but lack computing ability beyond simple vector matrix multiplication due to their two-terminal nature and rely on extensive CMOS peripherals for BN implementation, which limits area and energy efficiency. Here, we circumvent these challenges by introducing a hardware platform based on 2D memtransistors. First, we experimentally demonstrate a low-power and compact s-bit generator circuit that exploits cycle-to-cycle fluctuation in the post-programmed conductance state of 2D memtransistors. Next, the s-bit generators are monolithically integrated with 2D memtransistor-based logic gates to implement BNs. Our findings highlight the potential for 2D memtransistor-based integrated circuits for non-von Neumann computing applications., (© 2022. The Author(s).)

Atomically thin, 2D, and semiconducting transition metal dichalcogenides (TMDs) are seen as potential candidates for complementary metal oxide semiconductor (CMOS) technology in future nodes. While high-performance field effect transistors (FETs), logic gates, and integrated circuits (ICs) made from n-type TMDs such as MoS 2 and WS 2 grown at wafer scale have been demonstrated, realizing CMOS electronics necessitates integration of large area p-type semiconductors. Furthermore, the physical separation of memory and logic is a bottleneck of the existing CMOS technology and must be overcome to reduce the energy burden for computation. In this article, the existing limitations are overcome and for the first time, a heterogeneous integration of large area grown n-type MoS 2 and p-type vanadium doped WSe 2 FETs with non-volatile and analog memory storage capabilities to achieve a non-von Neumann 2D CMOS platform is introduced. This manufacturing process flow allows for precise positioning of n-type and p-type FETs, which is critical for any IC development. Inverters and a simplified 2-input-1-output multiplexers and neuromorphic computing primitives such as Gaussian, sigmoid, and tanh activation functions using this non-von Neumann 2D CMOS platform are also demonstrated. This demonstration shows the feasibility of heterogeneous integration of wafer scale 2D materials., (© 2022 Wiley-VCH GmbH.)

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect- and strain-induced single-photon emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach for creating large areas of localized emitters with high density (∼150 emitters/um 2 ) in a WSe 2 monolayer. We induce strain inside the WSe 2 monolayer with high spatial density by conformally placing the WSe 2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters will be applied to scalable, tunable, and versatile quantum light sources.

In the emerging era of the internet of things (IoT), ubiquitous sensors continuously collect, consume, store, and communicate a huge volume of information which is becoming increasingly vulnerable to theft and misuse. Modern software cryptosystems require extensive computational infrastructure for implementing ciphering algorithms, making them difficult to be adopted by IoT edge sensors that operate with limited hardware resources and at low energy budgets. Here we propose and experimentally demonstrate an "all-in-one" 8 × 8 array of robust, low-power, and bio-inspired crypto engines monolithically integrated with IoT edge sensors based on two-dimensional (2D) memtransistors. Each engine comprises five 2D memtransistors to accomplish sensing and encoding functionalities. The ciphered information is shown to be secure from an eavesdropper with finite resources and access to deep neural networks. Our hardware platform consists of a total of 320 fully integrated monolayer MoS 2 -based memtransistors and consumes energy in the range of hundreds of picojoules and offers near-sensor security., (© 2022. The Author(s).)

The electronic and optical properties of two-dimensional materials can be strongly influenced by defects, some of which can find significant implementations, such as controllable doping, prolonged valley lifetime, and single-photon emissions. In this work, we demonstrate that defects created by remote N 2 plasma exposure in single-layer WS 2 can induce a distinct low-energy photoluminescence (PL) peak at 1.59 eV, which is in sharp contrast to that caused by remote Ar plasma. This PL peak has a critical requirement on the N 2 plasma exposure dose, which is strongest for WS 2 with about 2.0% sulfur deficiencies (including substitutions and vacancies) and vanishes at 5.6% or higher sulfur deficiencies. Both experiments and first-principles calculations suggest that this 1.59 eV PL peak is caused by defects related to the sulfur substitutions by nitrogen, even though low-temperature PL measurements also reveal that not all the sulfur vacancies are remedied by the substitutional nitrogen. The distinct low-energy PL peak suggests that the substitutional nitrogen defect in single-layer WS 2 can potentially serve as an isolated artificial atom for creating single-photon emitters, and its intensity can also be used to monitor the doping concentrations of substitutional nitrogen.

Transition metal dichalcogenides (TMDCs) are versatile layered materials with potential applications ranging from optoelectronic devices to water splitting. Top-down fabrication methods such as exfoliation are not practical for a large-scale production of high-quality devices: a bottom-up approach such as sputtering, a low-temperature deposition method, is more suitable. However, due to its anisotropic nature, the growth mechanism of molybdenum disulfide (MoS 2 ) via sputtering is complex and remains to be investigated in detail. In this paper, we study the growth of MoS2 films co-deposited by using a sulfur (S) hot-lip cell and a molybdenum (Mo) sputtering target via reactive sputtering. The impact of S partial pressure on the structure and morphology of MoS 2 films was systematically characterized, and it was observed that the growth is dominated by vertically-oriented sheets with horizontal branches, resulting in a tree-like structure. The growth front of the structures is ascribed to the anisotropic incorporation of adatoms with regards to the orientation of MoS 2 ., (© 2022 IOP Publishing Ltd.)

Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light-matter coupling and exciton-polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

A comparison of hexagonal boron nitride (hBN) layers grown by chemical vapor deposition on C -plane (0001) versus A -plane (112̅0) sapphire (α-Al 2 O 3 ) substrate is reported. The high deposition temperature (>1200 °C) and hydrogen ambient used for hBN deposition on sapphire substantially alters the C -plane sapphire surface chemistry and leaves the top layer(s) oxygen deficient. The resulting surface morphology due to H 2 etching of C -plane sapphire is inhomogeneous with increased surface roughness which causes non-uniform residual stress in the deposited hBN film. In contrast to C -plane, the A -plane of sapphire does not alter substantially under a similar high temperature H 2 environment, thus providing a more stable alternative substrate for high quality hBN growth. The E 2g Raman mode full width at half-maximum (FWHM) for hBN deposited on C -plane sapphire is 24.5 ± 2.1 cm -1 while for hBN on A -plane sapphire is 24.5 ± 0.7 cm -1 . The lesser FWHM standard deviation on A -plane sapphire indicates uniform stress distribution across the film due to reduced undulations on the surface. The photoluminescence spectra of the hBN films at 300 and 3 K, obtained on C -plane and A -plane sapphire exhibit similar characteristics with peaks at 4.1 and 5.3 eV reported to be signature peaks associated with defects for hBN films deposited under lower V/III ratios. The dielectric breakdown field of hBN deposited on A -plane sapphire was measured to be 5 MV cm -1 , agreeing well with reports on mechanically exfoliated hBN flakes. Thus, under the typical growth conditions required for high crystalline quality hBN growth, A -plane sapphire provides a more chemically stable substrate.

Engineering atomic-scale defects is crucial for realizing wafer-scale, single-crystalline transition metal dichalcogenide monolayers for electronic devices. However, connecting atomic-scale defects to larger morphologies poses a significant challenge. Using electron microscopy and ReaxFF reactive force field-based molecular dynamics simulations, we provide insights into WS 2 crystal growth mechanisms, providing a direct link between synthetic conditions and microstructure. Dark-field TEM imaging of coalesced monolayer WS 2 films illuminates defect arrays that atomic-resolution STEM imaging identifies as translational grain boundaries. Electron diffraction and high-resolution imaging reveal that the films have nearly a single orientation with imperfectly stitched domains that tilt out-of-plane when released from the substrate. Imaging and ReaxFF simulations uncover two types of translational mismatch, and we discuss their origin related to relatively fast growth rates. Statistical analysis of >1300 facets demonstrates that microstructural features are constructed from nanometer-scale building blocks, describing the system across sub-Ångstrom to multimicrometer length scales.

Graphene shows great promise not only as a highly conductive flexible and transparent electrode for fabricating novel device architectures but also as an ideal synthesis platform for studying fundamental growth mechanisms of various materials. In particular, directly depositing metal phthalocyanines (MPc's) on graphene is viewed as a compelling approach to improve the performance of organic photovoltaics and light-emitting diodes. In this work, we systematically investigate the ZnPc physical vapor deposition (PVD) on graphene either as-grown on Cu or as-transferred on various substrates including Si(100), C-plane sapphire, SiO 2 /Si, and h-BN. To better understand the effect of the substrate on the ZnPc structure and morphology, we also compare the ZnPc growth on highly crystalline single- and multilayer graphene. The experiments show that, for identical deposition conditions, ZnPc exhibits various morphologies such as high-aspect-ratio nanowires or a continuous film when changing the substrate supporting graphene. ZnPc morphology is also found to transition from a thin film to a nanowire structure when increasing the number of graphene layers. Our observations suggest that substrate-induced changes in graphene affect the adsorption, surface diffusion, and arrangement of ZnPc molecules. This study provides clear guidelines to control MPc crystallinity, morphology, and molecular orientations which drastically influence the (opto)electronic properties., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The highest quality hexagonal boron nitride (hBN) crystals are grown from molten solutions. For hBN crystal growth at atmospheric pressure, typically the solvent is a combination of two metals, one with a high boron solubility and the other to promote nitrogen solubility. In this study, we demonstrate that high-quality hBN crystals can be grown at atmospheric pressure using pure iron as a flux. The ability to produce excellent-quality hBN crystals using pure iron as a solvent is unexpected, given its low solubility for nitrogen. The properties of crystals produced with this flux matched the best values ever reported for hBN: a narrow Raman E 2g vibration peak (7.6 cm -1 ) and strong phonon-assisted peaks in the photoluminescence spectra. To further test their quality, the hBN crytals were used as a substrate for WSe 2 epitaxy. WSe 2 was deposited with a low nucleation density, indicating the low defect density of the hBN. Lastly, the carrier tunneling through our hBN thin layers (3.5 nm) follows the Fowler-Nordheim model, with a barrier height of 3.7 eV, demonstrating hBN's superior electrical insulating properties. This ability to produce high-quality hBN crystals in such a simple, environmentally friendly and economical process will advance two-dimensional material research by enabling integrated devices.

Realization of wafer-scale single-crystal films of transition metal dichalcogenides (TMDs) such as WS 2 requires epitaxial growth and coalescence of oriented domains to form a continuous monolayer. The domains must be oriented in the same crystallographic direction on the substrate to inhibit the formation of inversion domain boundaries (IDBs), which are a common feature of layered chalcogenides. Here we demonstrate fully coalesced unidirectional WS 2 monolayers on 2 in. diameter c -plane sapphire by metalorganic chemical vapor deposition using a multistep growth process to achieve epitaxial WS 2 monolayers with low in-plane rotational twist (0.09°). Transmission electron microscopy analysis reveals that the WS 2 monolayers are largely free of IDBs but instead have translational boundaries that arise when WS 2 domains with slightly offset lattices merge together. By regulating the monolayer growth rate, the density of translational boundaries and bilayer coverage were significantly reduced. The unidirectional orientation of domains is attributed to the presence of steps on the sapphire surface coupled with growth conditions that promote surface diffusion, lateral domain growth, and coalescence while preserving the aligned domain structure. The transferred WS 2 monolayers show neutral and charged exciton emission at 80 K with negligible defect-related luminescence. Back-gated WS 2 field effect transistors exhibited an I ON / OFF of ∼10 7 and mobility of 16 cm 2 /(V s). The results demonstrate the potential of achieving wafer-scale TMD monolayers free of inversion domains with properties approaching those of exfoliated flakes.

Here we benchmark device-to-device variation in field-effect transistors (FETs) based on monolayer MoS 2 and WS 2 films grown using metal-organic chemical vapor deposition process. Our study involves 230 MoS 2 FETs and 160 WS 2 FETs with channel lengths ranging from 5 μm down to 100 nm. We use statistical measures to evaluate key FET performance indicators for benchmarking these two-dimensional (2D) transition metal dichalcogenide (TMD) monolayers against existing literature as well as ultra-thin body Si FETs. Our results show consistent performance of 2D FETs across 1 × 1 cm 2 chips owing to high quality and uniform growth of these TMDs followed by clean transfer onto device substrates. We are able to demonstrate record high carrier mobility of 33 cm 2  V -1  s -1 in WS 2 FETs, which is a 1.5X improvement compared to the best reported in the literature. Our experimental demonstrations confirm the technological viability of 2D FETs in future integrated circuits.

Reliable, controlled doping of 2D transition metal dichalcogenides will enable the realization of next-generation electronic, logic-memory, and magnetic devices based on these materials. However, to date, accurate control over dopant concentration and scalability of the process remains a challenge. Here, a systematic study of scalable in situ doping of fully coalesced 2D WSe 2 films with Re atoms via metal-organic chemical vapor deposition is reported. Dopant concentrations are uniformly distributed over the substrate surface, with precisely controlled concentrations down to <0.001% Re achieved by tuning the precursor partial pressure. Moreover, the impact of doping on morphological, chemical, optical, and electronic properties of WSe 2 is elucidated with detailed experimental and theoretical examinations, confirming that the substitutional doping of Re at the W site leads to n-type behavior of WSe 2 . Transport characteristics of fabricated back-gated field-effect-transistors are directly correlated to the dopant concentration, with degrading device performances for doping concentrations exceeding 1% of Re. The study demonstrates a viable approach to introducing true dopant-level impurities with high precision, which can be scaled up to batch production for applications beyond digital electronics., (© 2020 Wiley-VCH GmbH.)

In this article, we adopt a radical approach for next generation ultra-low-power sensor design by embracing the evolutionary success of animals with extraordinary sensory information processing capabilities that allow them to survive in extreme and resource constrained environments. Stochastic resonance (SR) is one of those astounding phenomena, where noise, which is considered detrimental for electronic circuits and communication systems, plays a constructive role in the detection of weak signals. Here, we show SR in a photodetector based on monolayer MoS 2 for detecting ultra-low-intensity subthreshold optical signals from a distant light emitting diode (LED). We demonstrate that weak periodic LED signals, which are otherwise undetectable, can be detected by a MoS 2 photodetector in the presence of a finite and optimum amount of white Gaussian noise at a frugal energy expenditure of few tens of nano-Joules. The concept of SR is generic in nature and can be extended beyond photodetector to any other sensors.

Defect engineering is important for tailoring the electronic and optical properties of two-dimensional materials, and the capability of generating defects of certain types at specific locations is meaningful for potential applications such as optoelectronics and quantum photonics. In this work, atomic defects are created in single-layer WSe2 using focused ion beam (FIB) irradiation, with defect densities spanning many orders of magnitude. The influences of defects are systematically characterized. Raman spectroscopy can only discern defects in WSe2 for a FIB dose higher than 1 × 1013 cm-2, which causes blue shifts of both A'1 and E' modes. Photoluminescence (PL) of WSe2 is more sensitive to defects. At cryogenic temperature, the low-energy PL induced by defects can be revealed, which shows redshifts and broadenings with increased FIB doses. Similar Raman shifts and PL spectrum changes are observed for the WSe2 film grown by chemical vapor deposition (CVD). A four microsecond-long lifetime is observed in the PL dynamics and is three orders of magnitude longer than the often observed delocalized exciton lifetime and becomes more dominant for WSe2 with increasing FIB doses. The ultra-long lifetime of PL in single-layer WSe2 is consistent with first-principles calculation results considering the creation of both chalcogen and metal vacancies by FIB, and can be valuable for photo-catalytic reactions, valleytronics and quantum light emissions owing to the longer carrier separation/manipulation time.

Spin-dependent contrasting phenomena at K and K' valleys in monolayer semiconductors have led to addressable valley degree of freedom, which is the cornerstone for emerging valleytronic applications in information storage and processing. Tunable and active modulation of valley dynamics in a monolayer WSe 2 is demonstrated at room temperature through controllable chiral Purcell effects in plasmonic chiral metamaterials. The strong spin-dependent modulation on the spontaneous decay of valley excitons leads to tunable handedness and spectral shift of valley-polarized emission, which is analyzed and predicted by an advanced theoretical model and further confirmed by experimental measurements. Moreover, large active spectral tuning (≈24 nm) and reversible ON/OFF switching of circular polarization of emission are achieved by the solvent-controllable thickness of the dielectric spacer in the metamaterials. With the on-demand and active tunability in valley-polarized emission, chiral Purcell effects can provide new strategies to harness valley excitons for applications in ultrathin valleytronic devices., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A defect-controlled approach for the nucleation and epitaxial growth of WSe 2 on hBN is demonstrated. The WSe 2 domains exhibit a preferred orientation of over 95%, leading to a reduced density of inversion domain boundaries (IDBs) upon coalescence. First-principles calculations and experimental studies as a function of growth conditions and substrate pretreatment confirm that WSe 2 nucleation density and orientation are controlled by the hBN surface defect density rather than thermodynamic factors. Detailed transmission electron microscopy analysis provides support for the role of single-atom vacancies on the hBN surface that trap W atoms and break surface symmetry leading to a reduced formation energy for one orientation of WSe 2 domains. Through careful control of nucleation and extended lateral growth time, fully coalesced WSe 2 monolayer films on hBN were achieved. Low-temperature photoluminescence (PL) measurements and transport measurements of back-gated field-effect transistor devices fabricated on WSe 2 /hBN films show improved optical and electrical properties compared to films grown on sapphire under similar conditions. Our results reveal an important nucleation mechanism for the epitaxial growth of van der Waals heterostructures and demonstrate hBN as a superior substrate for single-crystal transition-metal dichalcogenide (TMD) films, resulting in a reduced density of IDBs and improved properties. The results motivate further efforts focused on the development of single crystal hBN substrates and epilayers for synthesis of wafer-scale single crystal TMD films.

The utilization of alkali salts, such as NaCl and KI, has enabled the successful growth of large single domain and fully coalesced polycrystalline two-dimensional (2D) transition-metal dichalcogenide layers. However, the impact of alkali salts on photonic and electronic properties is not fully established. In this work, we report alkali-free epitaxy of MoS 2 on sapphire and benchmark the properties against alkali-assisted growth of MoS 2 . This study demonstrates that although NaCl can dramatically increase the domain size of monolayer MoS 2 by 20 times, it can also induce strong optical and electronic heterogeneities in as-grown, large-scale films. This work elucidates that utilization of NaCl can lead to variation in growth rates, loss of epitaxy, and high density of nanoscale MoS 2 particles (4 ± 0.7/μm 2 ). Such phenomena suggest that alkali atoms play an important role in Mo and S adatom mobility and strongly influence the 2D/sapphire interface during growth. Compared to alkali-free synthesis under the same growth conditions, MoS 2 growth assisted by NaCl results in >1% tensile strain in as-grown domains, which reduces photoluminescence by ∼20× and degrades transistor performance.