Non-epitaxial single-crystal 2D material growth by geometric confinement.

Two-dimensional (2D) materials and their heterostructures show a promising path for next-generation electronics1-3. Nevertheless, 2D-based electronics have not been commercialized, owing mainly to three critical challenges: i) precise kinetic control of layer-by-layer 2D material growth, ii) maintaining a single domain during the growth, and iii) wafer-scale controllability of layer numbers and crystallinity. Here we introduce a deterministic, confined-growth technique that can tackle these three issues simultaneously, thus obtaining wafer-scale single-domain 2D monolayer arrays and their heterostructures on arbitrary substrates. We geometrically confine the growth of the first set of nuclei by defining a selective growth area via patterning SiO2 masks on two-inch substrates. Owing to substantial reduction of the growth duration at the micrometre-scale SiO2 trenches, we obtain wafer-scale single-domain monolayer WSe2 arrays on the arbitrary substrates by filling the trenches via short growth of the first set of nuclei, before the second set of nuclei is introduced, thus without requiring epitaxial seeding. Further growth of transition metal dichalcogenides with the same principle yields the formation of single-domain MoS2/WSe2 heterostructures. Our achievement will lay a strong foundation for 2D materials to fit into industrial settings.

Vertical full-colour micro-LEDs via 2D materials-based layer transfer.

Micro-LEDs (µLEDs) have been explored for augmented and virtual reality display applications that require extremely high pixels per inch and luminance1,2. However, conventional manufacturing processes based on the lateral assembly of red, green and blue (RGB) µLEDs have limitations in enhancing pixel density3-6. Recent demonstrations of vertical µLED displays have attempted to address this issue by stacking freestanding RGB LED membranes and fabricating top-down7-14, but minimization of the lateral dimensions of stacked µLEDs has been difficult. Here we report full-colour, vertically stacked µLEDs that achieve, to our knowledge, the highest array density (5,100 pixels per inch) and the smallest size (4 µm) reported to date. This is enabled by a two-dimensional materials-based layer transfer technique15-18 that allows the growth of RGB LEDs of near-submicron thickness on two-dimensional material-coated substrates via remote or van der Waals epitaxy, mechanical release and stacking of LEDs, followed by top-down fabrication. The smallest-ever stack height of around 9 µm is the key enabler for record high µLED array density. We also demonstrate vertical integration of blue µLEDs with silicon membrane transistors for active matrix operation. These results establish routes to creating full-colour µLED displays for augmented and virtual reality, while also offering a generalizable platform for broader classes of three-dimensional integrated devices.

Mixed-Dimensional Integration of 3D-on-2D Heterostructures for Advanced Electronics.

Two-dimensional (2D) materials have garnered significant attention due to their exceptional properties requisite for next-generation electronics, including ultrahigh carrier mobility, superior mechanical flexibility, and unusual optical characteristics. Despite their great potential, one of the major technical difficulties toward lab-to-fab transition exists in the seamless integration of 2D materials with classic material systems, typically composed of three-dimensional (3D) materials. Owing to the self-passivated nature of 2D surfaces, it is particularly challenging to achieve well-defined interfaces when forming 3D materials on 2D materials (3D-on-2D) heterostructures. Here, we comprehensively review recent progress in 3D-on-2D incorporation strategies, ranging from direct-growth- to layer-transfer-based approaches and from non-epitaxial to epitaxial integration methods. Their technological advances and obstacles are rigorously discussed to explore optimal, yet viable, integration strategies of 3D-on-2D heterostructures. We conclude with an outlook on mixed-dimensional integration processes, identifying key challenges in state-of-the-art technology and suggesting potential opportunities for future innovation.

Remote Epitaxy: Fundamentals, Challenges, and Opportunities.

Advanced heterogeneous integration technologies are pivotal for next-generation electronics. Single-crystalline materials are one of the key building blocks for heterogeneous integration, although it is challenging to produce and integrate these materials. Remote epitaxy is recently introduced as a solution for growing single-crystalline thin films that can be exfoliated from host wafers and then transferred onto foreign platforms. This technology has quickly gained attention, as it can be applied to a wide variety of materials and can realize new functionalities and novel application platforms. Nevertheless, remote epitaxy is a delicate process, and thus, successful execution of remote epitaxy is often challenging. Here, we elucidate the mechanisms of remote epitaxy, summarize recent breakthroughs, and discuss the challenges and solutions in the remote epitaxy of various material systems. We also provide a vision for the future of remote epitaxy for studying fundamental materials science, as well as for functional applications.

Substantially Accelerated Response and Recovery in Pd-Decorated WO3 Nanorods Gasochromic Hydrogen Sensor.

The development of hydrogen (H2) gas sensors is essential for the safe and efficient adoption of H2 gas as a clean, renewable energy source in the challenges against climate change, given its flammability and associated safety risks. Among various H2 sensors, gasochromic sensors have attracted great interest due to their highly intuitive and low power operation, but slow kinetics, especially slow recovery rate limited its further practical application. This study introduces Pd-decorated amorphous WO3 nanorods (Pd-WO3 NRs) as an innovative gasochromic H2 sensor, demonstrating rapid and highly reversible color changes for H2 detection. In specific, the amorphous nanostructure exhibits notable porosity, enabling rapid detection and recovery by facilitating effective H2 gas interaction and efficient diffusion of hydrogen ions (H+) dissociated from the Pd nanoparticles (Pd NPs). The optimized Pd-WO3 NRs sensor achieves an impressive response time of 14 s and a recovery time of 1 s to 5% H2. The impressively fast recovery time of 1 s is observed under a wide range of H2 concentrations (0.2-5%), making this study a fundamental solution to the challenged slow recovery of gasochromic H2 sensors.

Monolithic 3D integration of 2D materials-based electronics towards ultimate edge computing solutions.

Three-dimensional (3D) hetero-integration technology is poised to revolutionize the field of electronics by stacking functional layers vertically, thereby creating novel 3D circuity architectures with high integration density and unparalleled multifunctionality. However, the conventional 3D integration technique involves complex wafer processing and intricate interlayer wiring. Here we demonstrate monolithic 3D integration of two-dimensional, material-based artificial intelligence (AI)-processing hardware with ultimate integrability and multifunctionality. A total of six layers of transistor and memristor arrays were vertically integrated into a 3D nanosystem to perform AI tasks, by peeling and stacking of AI processing layers made from bottom-up synthesized two-dimensional materials. This fully monolithic-3D-integrated AI system substantially reduces processing time, voltage drops, latency and footprint due to its densely packed AI processing layers with dense interlayer connectivity. The successful demonstration of this monolithic-3D-integrated AI system will not only provide a material-level solution for hetero-integration of electronics, but also pave the way for unprecedented multifunctional computing hardware with ultimate parallelism.

Visible Light Driven Ultrasensitive and Selective NO2 Detection in Tin Oxide Nanoparticles with Sulfur Doping Assisted by l-Cysteine.

In the pandemic era, the development of high-performance indoor air quality monitoring sensors has become more critical than ever. NO2 is one of the most toxic gases in daily life, which induces severe respiratory diseases. Thus, the real-time monitoring of low concentrations of NO2 is highly required. Herein, a visible light-driven ultrasensitive and selective chemoresistive NO2 sensor is presented based on sulfur-doped SnO2 nanoparticles. Sulfur-doped SnO2 nanoparticles are synthesized by incorporating l-cysteine as a sulfur doping agent, which also increases the surface area. The cationic and anionic doping of sulfur induces the formation of intermediate states in the band gap, highly contributing to the substantial enhancement of gas sensing performance under visible light illumination. Extraordinary gas sensing performances such as the gas response of 418 to 5 ppm of NO2 and a detection limit of 0.9 ppt are achieved under blue light illumination. Even under red light illumination, sulfur-doped SnO2 nanoparticles exhibit stable gas sensing. The endurance to humidity and long-term stability of the sensor are outstanding, which amplify the capability as an indoor air quality monitoring sensor. Overall, this study suggests an innovative strategy for developing the next generation of electronic noses.

Ionic-Activated Chemiresistive Gas Sensors for Room-Temperature Operation.

The development of high performance gas sensors that operate at room temperature has attracted considerable attention. Unfortunately, the conventional mechanism of chemiresistive sensors is restricted at room temperature by insufficient reaction energy with target molecules. Herein, novel strategy for room temperature gas sensors is reported using an ionic-activated sensing mechanism. The investigation reveals that a hydroxide layer is developed by the applied voltages on the SnO2 surface in the presence of humidity, leading to increased electrical conductivity. Surprisingly, the experimental results indicate ideal sensing behavior at room temperature for NO2 detection with sub-parts-per-trillion (132.3 ppt) detection and fast recovery (25.7 s) to 5 ppm NO2 under humid conditions. The ionic-activated sensing mechanism is proposed as a cascade process involving the formation of ionic conduction, reaction with a target gas, and demonstrates the novelty of the approach. It is believed that the results presented will open new pathways as a promising method for room temperature gas sensors.

Data-centric artificial olfactory system based on the eigengraph.

Recent studies of electronic nose system tend to waste significant amount of important data in odor identification. Until now, the sensitivity-oriented data composition has made it difficult to discover meaningful data to apply artificial intelligence in terms of in-depth analysis for odor attributes specifying the identities of gas molecules, ultimately resulting in hindering the advancement of the artificial olfactory technology. Here, we realize a data-centric approach to implement standardized artificial olfactory systems inspired by human olfactory mechanisms by formally defining and utilizing the concept of Eigengraph in electrochemisty. The implicit odor attributes of the eigengraphs were mathematically substantialized as the Fourier transform-based Mel-Frequency Cepstral Coefficient feature vectors. Their effectiveness and applicability in deep learning processes for gas classification have been clearly demonstrated through experiments on complex mixed gases and automobile exhaust gases. We suggest that our findings can be widely applied as source technologies to develop standardized artificial olfactory systems.

MAPbBr3 Halide Perovskite-Based Resistive Random-Access Memories Using Electron Transport Layers for Long Endurance Cycles and Retention Time.

Recent studies have focused on exploring the potential of resistive random-access memory (ReRAM) utilizing halide perovskites as novel data storage devices. This interest stems from its notable attributes, including a high ON/OFF ratio, low operating voltages, and exceptional mechanical properties. Nevertheless, there have been reports indicating that memory systems utilizing halide perovskites encounter certain obstacles pertaining to their stability and dependability, mostly assessed through endurance and retention time. Moreover, the presence of these problems can potentially restrict their practical applicability. This study explores a resistive switching memory device utilizing MAPbBr3 perovskite, which demonstrates bipolar switching characteristics. The device fabrication procedure involves a low-temperature, all-solution process. For the purpose of enhancing the device's reliability, the utilization of TPBI(2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) as an electron transfer material on the MAPbBr3 switching layer was implemented for the first time. The formation and rupture of Ag filaments in the MAPbBr3 perovskite switching layer are attributed to reduction-oxidation reactions. The TPBI is involved in the regulation of filaments during the SET and RESET processes. Hence, it can be shown that the MAPbBr3 device incorporating TPBI exhibited about 1000 endurance cycles when subjected to continuous voltage pulses. Moreover, the device consistently maintained ON/OFF ratios above 107. In contrast, the original MAPbBr3 device without TPBI demonstrated a significantly lower endurance with only 90 cycles observed. In addition, the MAPbBr3 device integrated with TPBI exhibited a retention time exceeding 3 × 103 s. The findings of this research provide compelling evidence to support the notion that electron transfer materials have promise for the development of halide perovskite memory systems owing to their favorable attributes of dependability and stability.

The future of two-dimensional semiconductors beyond Moore's law.

The primary challenge facing silicon-based electronics, crucial for modern technological progress, is difficulty in dimensional scaling. This stems from a severe deterioration of transistor performance due to carrier scattering when silicon thickness is reduced below a few nanometres. Atomically thin two-dimensional (2D) semiconductors still maintain their electrical characteristics even at sub-nanometre scales and offer the potential for monolithic three-dimensional (3D) integration. Here we explore a strategic shift aimed at addressing the scaling bottleneck of silicon by adopting 2D semiconductors as new channel materials. Examining both academic and industrial viewpoints, we delve into the latest trends in channel materials, the integration of metal contacts and gate dielectrics, and offer insights into the emerging landscape of industrializing 2D semiconductor-based transistors for monolithic 3D integration.

Real-Time Tunable Gas Sensing Platform Based on SnO2 Nanoparticles Activated by Blue Micro-Light-Emitting Diodes.

Micro-light-emitting diodes (µLEDs) have gained significant interest as an activation source for gas sensors owing to their advantages, including room temperature operation and low power consumption. However, despite these benefits, challenges still exist such as a limited range of detectable gases and slow response. In this study, we present a blue µLED-integrated light-activated gas sensor array based on SnO2 nanoparticles (NPs) that exhibit excellent sensitivity, tunable selectivity, and rapid detection with micro-watt level power consumption. The optimal power for µLED is observed at the highest gas response, supported by finite-difference time-domain simulation. Additionally, we first report the visible light-activated selective detection of reducing gases using noble metal-decorated SnO2 NPs. The noble metals induce catalytic interaction with reducing gases, clearly distinguishing NH3, H2, and C2H5OH. Real-time gas monitoring based on a fully hardware-implemented light-activated sensing array was demonstrated, opening up new avenues for advancements in light-activated electronic nose technologies.

Drastic Gas Sensing Selectivity in 2-Dimensional MoS2 Nanoflakes by Noble Metal Decoration.

Noble metal nanoparticle decoration is a representative strategy to enhance selectivity for fabricating chemical sensor arrays based on the 2-dimensional (2D) semiconductor material, represented by molybdenum disulfide (MoS2). However, the mechanism of selectivity tuning by noble metal decoration on 2D materials has not been fully elucidated. Here, we successfully decorated noble metal nanoparticles on MoS2 flakes by the solution process without using reducing agents. The MoS2 flakes showed drastic selectivity changes after surface decoration and distinguished ammonia, hydrogen, and ethanol gases clearly, which were not observed in general 3D metal oxide nanostructures. The role of noble metal nanoparticle decoration on the selectivity change is investigated by first-principles density functional theory (DFT) calculations. While the H2 sensitivity shows a similar tendency with the calculated binding energy, that of NH3 is strongly related to the binding site deactivation due to preferred noble metal particle decoration at the MoS2 edge. This finding is a specific phenomenon which originates from the distinguished structure of the 2D material, with highly active edge sites. We believe that our study will provide the fundamental comprehension for the strategy to devise the highly efficient sensor array based on 2D materials.

Remote epitaxial interaction through graphene.

The concept of remote epitaxy involves a two-dimensional van der Waals layer covering the substrate surface, which still enable adatoms to follow the atomic motif of the underlying substrate. The mode of growth must be carefully defined as defects, e.g., pinholes, in two-dimensional materials can allow direct epitaxy from the substrate, which, in combination with lateral epitaxial overgrowth, could also form an epilayer. Here, we show several unique cases that can only be observed for remote epitaxy, distinguishable from other two-dimensional material-based epitaxy mechanisms. We first grow BaTiO3 on patterned graphene to establish a condition for minimizing epitaxial lateral overgrowth. By observing entire nanometer-scale nuclei grown aligned to the substrate on pinhole-free graphene confirmed by high-resolution scanning transmission electron microscopy, we visually confirm that remote epitaxy is operative at the atomic scale. Macroscopically, we also show variations in the density of GaN microcrystal arrays that depend on the ionicity of substrates and the number of graphene layers.

High-throughput manufacturing of epitaxial membranes from a single wafer by 2D materials-based layer transfer process.

Layer transfer techniques have been extensively explored for semiconductor device fabrication as a path to reduce costs and to form heterogeneously integrated devices. These techniques entail isolating epitaxial layers from an expensive donor wafer to form freestanding membranes. However, current layer transfer processes are still low-throughput and too expensive to be commercially suitable. Here we report a high-throughput layer transfer technique that can produce multiple compound semiconductor membranes from a single wafer. We directly grow two-dimensional (2D) materials on III-N and III-V substrates using epitaxy tools, which enables a scheme comprised of multiple alternating layers of 2D materials and epilayers that can be formed by a single growth run. Each epilayer in the multistack structure is then harvested by layer-by-layer mechanical exfoliation, producing multiple freestanding membranes from a single wafer without involving time-consuming processes such as sacrificial layer etching or wafer polishing. Moreover, atomic-precision exfoliation at the 2D interface allows for the recycling of the wafers for subsequent membrane production, with the potential for greatly reducing the manufacturing cost.

Architecture engineering of nanostructured catalyst via layer-by-layer adornment of multiple nanocatalysts on silica nanorod arrays for hydrogenation of nitroarenes.

Direct consideration for both, the catalytically active species and the host materials provides highly efficient strategies for the architecture design of nanostructured catalysts. The conventional wet chemical methods have limitations in achieving such unique layer-by-layer design possessing one body framework with many catalyst parts. Herein, an innovative physical method is presented that allows the well-regulated architecture design for an array of functional nanocatalysts as exemplified by layer-by-layer adornment of Pd nanoparticles (NPs) on the highly arrayed silica nanorods. This spatially confined catalyst exhibits excellent efficiency for the hydrogenation of nitroarenes and widely deployed Suzuki cross-coupling reactions; their facile separation from the reaction mixtures is easily accomplished due to the monolithic structure. The generality of this method for the introduction of other metal source has also been demonstrated with Au NPs. This pioneering effort highlights the feasibility of physically controlled architecture design of nanostructured catalysts which may stimulate further studies in the general domain of the heterogeneous catalytic transformations.

Artificial Adaptive and Maladaptive Sensory Receptors Based on a Surface-Dominated Diffusive Memristor.

A biological receptor serves as sensory transduction from an external stimulus to an electrical signal. It allows humans to better match the environment by filtering out repetitive innocuous information and recognize potentially damaging stimuli through key features, including adaptive and maladaptive behaviors. Herein, for the first time, the authors develop substantial artificial receptors involving both adaptive and maladaptive behaviors using diffusive memristor. Metal-oxide nanorods (NR) as a switching matrix enable the electromigration of an active metal along the surface of the NRs under electrical stimulation, resulting in unique surface-dominated switching dynamics with the advantage of fast Ag migration and fine controllability of the conductive filament. To experimentally demonstrate its potential application, a thermoreceptor system is constructed using memristive artificial receptors. The proposed surface-dominated diffusive memristor allows the direct emulation of the biological receptors, which represents an advance in the bioinspired technology adopted in creating artificial intelligence systems.

Graphene nanopattern as a universal epitaxy platform for single-crystal membrane production and defect reduction.

Heterogeneous integration of single-crystal materials offers great opportunities for advanced device platforms and functional systems1. Although substantial efforts have been made to co-integrate active device layers by heteroepitaxy, the mismatch in lattice polarity and lattice constants has been limiting the quality of the grown materials2. Layer transfer methods as an alternative approach, on the other hand, suffer from the limited availability of transferrable materials and transfer-process-related obstacles3. Here, we introduce graphene nanopatterns as an advanced heterointegration platform that allows the creation of a broad spectrum of freestanding single-crystalline membranes with substantially reduced defects, ranging from non-polar materials to polar materials and from low-bandgap to high-bandgap semiconductors. Additionally, we unveil unique mechanisms to substantially reduce crystallographic defects such as misfit dislocations, threading dislocations and antiphase boundaries in lattice- and polarity-mismatched heteroepitaxial systems, owing to the flexibility and chemical inertness of graphene nanopatterns. More importantly, we develop a comprehensive mechanics theory to precisely guide cracks through the graphene layer, and demonstrate the successful exfoliation of any epitaxial overlayers grown on the graphene nanopatterns. Thus, this approach has the potential to revolutionize the heterogeneous integration of dissimilar materials by widening the choice of materials and offering flexibility in designing heterointegrated systems.

Chip-less wireless electronic skins by remote epitaxial freestanding compound semiconductors.

Recent advances in flexible and stretchable electronics have led to a surge of electronic skin (e-skin)-based health monitoring platforms. Conventional wireless e-skins rely on rigid integrated circuit chips that compromise the overall flexibility and consume considerable power. Chip-less wireless e-skins based on inductor-capacitor resonators are limited to mechanical sensors with low sensitivities. We report a chip-less wireless e-skin based on surface acoustic wave sensors made of freestanding ultrathin single-crystalline piezoelectric gallium nitride membranes. Surface acoustic wave-based e-skin offers highly sensitive, low-power, and long-term sensing of strain, ultraviolet light, and ion concentrations in sweat. We demonstrate weeklong monitoring of pulse. These results present routes to inexpensive and versatile low-power, high-sensitivity platforms for wireless health monitoring devices.

Microscopic evidence of strong interactions between chemical vapor deposited 2D MoS2 film and SiO2 growth template.

Two-dimensional MoS2 film can grow on oxide substrates including Al2O3 and SiO2. However, it cannot grow usually on non-oxide substrates such as a bare Si wafer using chemical vapor deposition. To address this issue, we prepared as-synthesized and transferred MoS2 (AS-MoS2 and TR-MoS2) films on SiO2/Si substrates and studied the effect of the SiO2 layer on the atomic and electronic structure of the MoS2 films using spherical aberration-corrected scanning transition electron microscopy (STEM) and electron energy loss spectroscopy (EELS). The interlayer distance between MoS2 layers film showed a change at the AS-MoS2/SiO2 interface, which is attributed to the formation of S-O chemical bonding at the interface, whereas the TR-MoS2/SiO2 interface showed only van der Waals interactions. Through STEM and EELS studies, we confirmed that there exists a bonding state in addition to the van der Waals force, which is the dominant interaction between MoS2 and SiO2. The formation of S-O bonding at the AS-MoS2/SiO2 interface layer suggests that the sulfur atoms at the termination layer in the MoS2 films are bonded to the oxygen atoms of the SiO2 layer during chemical vapor deposition. Our results indicate that the S-O bonding feature promotes the growth of MoS2 thin films on oxide growth templates.