Lateral Heterostructures of Graphene and h-BN with Atomic Lattice Coherence and Tunable Rotational Order.

In-plane heterostructures of graphene and hexagonal boron nitride (h-BN) exhibit exceptional properties, which are highly sensitive to the structure of the alternating domains. Nevertheless, achieving accurate control over their structural properties, while keeping a high perfection at the graphene-h-BN boundaries, still remains a challenge. Here, the growth of lateral heterostructures of graphene and h-BN on Rh(110) surfaces is reported. The choice of the 2D material, grown firstly, determines the structural properties of the whole heterostructure layer, allowing to have control over the rotational order of the domains. The atomic-scale observation of the boundaries demonstrates a perfect lateral matching. In-plane heterostructures floating over an oxygen layer have been successfully obtained, enabling to observe intervalley scattering processes in graphene regions. The high tuning capabilities of these heterostructures, along with their good structural quality, even around the boundaries, suggest their usage as test beds for fundamental studies aiming at the development of novel nanomaterials with tailored properties.

Photonics in Multimaterial Lateral Heterostructures Combining Group IV Chalcogenide van der Waals Semiconductors.

Lateral heterostructures combining two multilayer group IV chalcogenide van der Waals semiconductors have attracted interest for optoelectronics, twistronics, and valleytronics, owing to their structural anisotropy, bulk-like electronic properties, enhanced optical thickness, and vertical interfaces enabling in-plane charge manipulation/separation, perpendicular to the trajectory of incident light. Group IV monochalcogenides support propagating photonic waveguide modes, but their interference gives rise to complex light emission patterns throughout the visible/near-infrared range both in uniform flakes and single-interface lateral heterostructures. Here, this work demonstrates the judicious integration of pure and alloyed monochalcogenide crystals into multimaterial heterostructures with unique photonic properties, notably the ability to select photonic modes with targeted discrete energies through geometric factors rather than band engineering. SnS-GeS1-x Sex -GeSe-GeS1-x Sex heterostructures with a GeS1-x Sex active layer sandwiched laterally between GeSe and SnS, semiconductors with similar optical constants but smaller bandgaps, were designed and realized via sequential vapor transport synthesis. Raman spectroscopy, electron microscopy/diffraction, and energy-dispersive X-ray spectroscopy confirm a high crystal quality of the laterally stitched components with sharp interfaces. Nanometer-scale cathodoluminescence spectroscopy provides evidence for a facile transfer of electron-hole pairs across the lateral interfaces and demonstrates the selection of photon emission at discrete energies in the laterally embedded active (GeS1- x Sex ) part of the heterostructure.

Highly Effective Freshwater and Seawater Electrolysis Enabled by Atomic Rh-Modulated Co-CoO Lateral Heterostructures.

Atomic metal-modulated heterostructures have been evidenced as an exciting solution to develop high-performance multifunctional electrocatalyst toward water splitting. In this research, a catalyst of continuous cobalt-cobalt oxide (Co-CoO) lateral heterostructures implanted with well-dispersed rhodium (Rh) atoms and shelled over conductive porous 1D copper (Cu) nano-supports for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in both freshwater and seawater under alkaline condition is proposed. It is found that synergistic effects coming from uniform Rh atoms at doping level and Co-CoO heterostructures afford rich multi-integrated active sites and excellent charge transfer, thereby effectively promoting both HER and OER activities. The material requires overpotentials of 107.3 and 137.7 mV for HER and 277.7 and 260 mV for OER to reach an output of 10 mA cm-1 in freshwater and mimic seawater, respectively, surpassing earlier reported catalysts. Compared to a benchmark a Pt/C//RuO2 -based two-electrode electrolyzer, a device derived from the 1D-Cu@Co-CoO/Rh on copper foam delivers comparable cell voltages of 1.62, 1.60, and 1.70 V at 10 mA cm-2 in freshwater, mimic seawater, and natural seawater, respectively, together with robust stability. These results evidence that 1D-Cu@Co-CoO/Rh is a promising catalyst for green hydrogen generation via freshwater and seawater electrolysis applications.

Two-Dimensional TeB Structures with Anisotropic Carrier Mobility and Tunable Bandgap.

Two-dimensional (2D) semiconductors with desirable bandgaps and high carrier mobility have great potential in electronic and optoelectronic applications. In this work, we proposed α-TeB and ß-TeB monolayers using density functional theory (DFT) combined with the particle swarm-intelligent global structure search method. The high dynamical and thermal stabilities of two TeB structures indicate high feasibility for experimental synthesis. The electronic structure calculations show that the two structures are indirect bandgap semiconductors with bandgaps of 2.3 and 2.1 eV, respectively. The hole mobility of the ß-TeB sheet is up to 6.90 × 102 cm2 V-1 s-1. By reconstructing the two structures, we identified two new horizontal and lateral heterostructures, and the lateral heterostructure presents a direct band gap, indicating more probable applications could be further explored for TeB sheets.

Molecular Nanowire Bonding to Epitaxial Single-Layer MoS2 by an On-Surface Ullmann Coupling Reaction.

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self-assembled organic nanowire-TMDC system, a method to link and interconnect epitaxial single-layer MoS2 flakes with organic molecules is demonstrated. Whereas pristine epitaxial single-layer MoS2 has no affinity for molecular attachment, it is found that single-layer MoS2 will selectively bind the organic molecule 2,8-dibromodibenzothiophene (DBDBT) in a surface-assisted Ullmann coupling reaction when the MoS2 has been activated by pre-exposing it to hydrogen. Atom-resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig-zag edges available in a hexagonal single layer MoS2 sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic-TMDC hybrid materials.

Patterned Arrays of Functional Lateral Heterostructures via Sequential Template-Directed Printing.

The precise integration of microscale dots and lines with controllable interfacing connections is highly important for the fabrication of functional devices. To date, the solution-processible methods are used to fabricate the heterogeneous micropatterns for different materials. However, for increasingly miniaturized and multifunctional devices, it is extremely challenging to engineer the uncertain kinetics of a solution on the microstructures surfaces, resulting in uncontrollable interface connections and poor device performance. Here, a sequential template-directed printing process is demonstrated for the fabrication of arrayed microdots connected by microwires through the regulation of the Rayleigh-Taylor instability of material solution or suspension. Flexibility in the control of fluidic behaviors can realize precise interface connection between the micropatterns, including the microwires traversing, overlapping or connecting the microdots. Moreover, various morphologies such as circular, rhombic, or star-shaped microdots as well as straight, broken or curved microwires can be achieved. The lateral heterostructure printed with two different quantum dots displays bright dichromatic photoluminescence. The ammonia gas sensor printed by polyaniline and silver nanoparticles exhibits a rapid response time. This strategy can construct heterostructures in a facile manner by eliminating the uncertainty of the multimaterials interface connection, which will be promising for the development of novel lateral functional devices.

Lateral Heterostructures Fabricated via Artificial Pressure Gradient.

Hydrostatic conditions are generally pursued in high-pressure research, maintained to prevent the intrinsic pressure gradient on the culets of diamond anvil cells (DACs) from introducing heterogeneity to the structure and physical properties of the regulated materials. Here, a pioneering route to fabricate lateral heterostructures is proposed via artificial pressure gradients intentionally designed in DACs. Under the tailored pressure gradients, different structural phases emerge in distinct parts of the material, resulting in the formation of heterostructures. Harnessing the polymorphic transition nature of violet phosphorus under high pressure, violet/blue and violet/black phosphorus lateral heterostructures with different electrical properties have been successfully prepared by the pressure gradient method. This achievement highlights the potential of artificial pressure gradients as a portable and universal strategy for the fabrication of lateral heterostructures, shedding new light on the preparation and regulation of lateral heterostructures across a wider range of materials.

Lateral heterostructures of WS2 and MoS2 monolayers for photo-synaptic transistor.

Von Neumann architecture-based computing, while widely successful in personal computers and embedded systems, faces inherent challenges including the von Neumann bottleneck, particularly amidst the ongoing surge of data-intensive tasks. Neuromorphic computing, designed to integrate arithmetic, logic, and memory operations, has emerged as a promising solution for improving energy efficiency and performance. This approach requires the construction of an artificial synaptic device that can simultaneously perform signal processing, learning, and memory operations. We present a photo-synaptic device with 32 analog multi-states by exploiting field-effect transistors based on the lateral heterostructures of two-dimensional (2D) WS2 and MoS2 monolayers, formed through a two-step metal-organic chemical vapor deposition process. These lateral heterostructures offer high photoresponsivity and enhanced efficiency of charge trapping at the interface between the heterostructures and SiO2 due to the presence of the WS2 monolayer with large trap densities. As a result, it enables the photo-synaptic transistor to implement synaptic behaviors of long-term plasticity and high recognition accuracy. To confirm the feasibility of the photo-synapse, we investigated its synaptic characteristics under optical and electrical stimuli, including the retention of excitatory post-synaptic currents, potentiation, habituation, nonlinearity factor, and paired-pulse facilitation. Our findings suggest the potential of versatile 2D material-synapse with a high density of device integration.

Two-Dimensional Magnetic Semiconducting Heterostructures of Single-Layer CrI3-CrI2.

Single-layer heterostructures of magnetic materials are unique platforms for studying spin-related phenomena in two dimensions (2D) and have promising applications in spintronics and magnonics. Here, we report the fabrication of 2D magnetic lateral heterostructures consisting of single-layer chromium triiodide (CrI3) and chromium diiodide (CrI2). By carefully adjusting the abundance of iodine based on molecular beam epitaxy, single-layer CrI3-CrI2 heterostructures were grown on Au(111) surfaces with nearly atomic-level seamless boundaries. Two distinct types of interfaces, i.e., zigzag and armchair interfaces, have been identified by means of scanning tunneling microscopy. Our scanning tunneling spectroscopy study combined with density functional theory calculations indicates the existence of spin-polarized ground states below and above the Fermi energy localized at the boundary. Both the armchair and zigzag interfaces exhibit semiconducting nanowire behaviors with different spatial distributions of density of states. Our work presents a novel low-dimensional magnetic system for studying spin-related physics with reduced dimensions and designing advanced spintronic devices.

Enhanced Hydrogen Evolution Performance at the Lateral Interface between Two Layered Materials Predicted with Machine Learning.

While economical and effective catalysts are required for sustainable hydrogen production, low-dimensional interfacial engineering techniques have been developed to improve the catalytic activity in the hydrogen evolution reaction (HER). In this study, we used density functional theory (DFT) calculations to measure the Gibbs free energy change (ΔGH) in hydrogen adsorption in two-dimensional lateral heterostructures (LHSs) MX2/M'X'2 (MoS2/WS2, MoS2/WSe2, MoSe2/WS2, MoSe2/WSe2, MoTe2/WSe2, MoTe2/WTe2, and WS2/WSe2) and MX2/M'X' (NbS2/ZnO, NbSe2/ZnO, NbS2/GaN, MoS2/ZnO, MoSe2/ZnO, MoS2/AlN, MoS2/GaN, and MoSe2/GaN) at several different positions near the interface. Compared to the interfaces of LHS MX2/M'X'2 and the surfaces of the monolayer MX2 and MX, the interfaces of LHS MX2/M'X' display greater hydrogen evolution reactivity due to their metallic behavior. The hydrogen absorption is stronger at the interfaces of LHS MX2/M'X', and that facilitates proton accessibility and increases the usage of catalytically active sites. Here, we develop three types of descriptors that can be used universally in 2D materials and can explain changes in ΔGH for different adsorption sites in a single LHS using only the basic information of the LHSs (type and number of neighboring atoms to the adsorption points). Using the DFT results of the LHSs and the various experimental data of atomic information, we trained machine learning (ML) models with the chosen descriptors to predict promising combinations and adsorption sites for HER catalysts among the LHSs. Our ML model achieved an R2 score of 0.951 (regression) and an F1 score of 0.749 (classification). Furthermore, the developed surrogate model was implemented to predict the structures in the test set and was based on confirmation from the DFT calculations via ΔGH values. The LHS MoS2/ZnO is the best candidate for HER among 49 candidates considered using both DFT and ML models because it has a ΔGH of -0.02 eV on top of O at the interface position and requires only -171 mV of overpotential to obtain the standard current density (10 A/cm2).

One-Step Solution Patterning for Two-Dimensional Perovskite Nanoplate Arrays.

Two-dimensional perovskite crystals have attracted significant attention for their diverse optoelectronic characteristics, owing to their superior semiconducting properties. However, the majority of studies to date have focused on single crystals, which pose challenges for integration into device arrays due to their incompatibility with selective growth or conventional lithography techniques. Here, a facile one-step solution process for synthesizing 2D perovskite crystal arrays is proposed through meniscus-guided coating on patterned substrates. We further utilized this method for the synthesis of lateral heterostructure nanoplate arrays. Six different 2D perovskite nanoplate arrays, including epitaxial heterostructures, are successfully realized. Optical and crystallographic characterizations show the high optical performance and crystallinity of the nanoplates. Moreover, this method is further employed to prepare high-performance 2D perovskite nanoplate photosensor arrays. This strategy can be utilized as a guideline for the fundamental investigation of optical properties and the development of high-performance optoelectronics of perovskite materials including photosensors and displays.

Recent Progress in 1D Contacts for 2D-Material-Based Devices.

Recent studies have intensively examined 2D materials (2DMs) as promising materials for use in future quantum devices due to their atomic thinness. However, a major limitation occurs when 2DMs are in contact with metals: a van der Waals (vdW) gap is generated at the 2DM-metal interfaces, which induces metal-induced gap states that are responsible for an uncontrollable Schottky barrier (SB), Fermi-level pinning (FLP), and high contact resistance (RC ), thereby substantially lowering the electronic mobility of 2DM-based devices. Here, vdW-gap-free 1D edge contact is reviewed for use in 2D devices with substantially suppressed carrier scattering of 2DMs with hexagonal boron nitride (hBN) encapsulation. The 1D contact further enables uniform carrier transport across multilayered 2DM channels, high-density transistor integration independent of scaling, and the fabrication of double-gate transistors suitable for demonstrating unique quantum phenomena of 2DMs. The existing 1D contact methods are reviewed first. As a promising technology toward the large-scale production of 2D devices, seamless lateral contacts are reviewed in detail. The electronic, optoelectronic, and quantum devices developed via 1D contacts are subsequently discussed. Finally, the challenges regarding the reliability of 1D contacts are addressed, followed by an outlook of 1D contact methods.

Multilayer Lateral Heterostructures of Van Der Waals Crystals with Sharp, Carrier-Transparent Interfaces.

Research on engineered materials that integrate different 2D crystals has largely focused on two prototypical heterostructures: Vertical van der Waals stacks and lateral heterostructures of covalently stitched monolayers. Extending lateral integration to few layer or even multilayer van der Waals crystals could enable architectures that combine the superior light absorption and photonic properties of thicker crystals with close proximity to interfaces and efficient carrier separation within the layers, potentially benefiting applications such as photovoltaics. Here, the realization of multilayer heterstructures of the van der Waals semiconductors SnS and GeS with lateral interfaces spanning up to several hundred individual layers is demonstrated. Structural and chemical imaging identifies {110} interfaces that are perpendicular to the (001) layer plane and are laterally localized and sharp on a 10 nm scale across the entire thickness. Cathodoluminescence spectroscopy provides evidence for a facile transfer of electron-hole pairs across the lateral interfaces, indicating covalent stitching with high electronic quality and a low density of recombination centers.

Atomically Sharp Lateral Superlattice Heterojunctions Built-In Nitrogen-Doped Nanoporous Graphene.

Nanometer scale lateral heterostructures with atomically sharp band discontinuities can be conceived as the 2D analogues of vertical Van der Waals heterostructures, where pristine properties of each component coexist with interfacial phenomena that result in a variety of exotic quantum phenomena. However, despite considerable advances in the fabrication of lateral heterostructures, controlling their covalent interfaces and band discontinuities with atomic precision, scaling down components and producing periodic, lattice-coherent superlattices still represent major challenges. Here, a synthetic strategy to fabricate nanometer scale, coherent lateral superlattice heterojunctions with atomically sharp band discontinuity is reported. By merging interdigitated arrays of different types of graphene nanoribbons by means of a novel on-surface reaction, superlattices of 1D, and chemically heterogeneous nanoporous junctions are obtained. The latter host subnanometer quantum dipoles and tunneling in-gap states, altogether expected to promote interfacial phenomena such as interribbon excitons or selective photocatalysis.

Two-Dimensional Lateral Heterostructures Made by Selective Reaction on a Patterned Monolayer MoS2 Matrix.

Two-dimensional (2D) heterostructures have attracted widespread attention for their promising prospects in the fields of electronics and optoelectronics. However, in order to truly realize 2D-material-based integrated circuits, precisely controllable fabrication of 2D heterostructures is crucial and urgently needed. Here, we demonstrate an ex situ growth method of MoSe2/MoS2 lateral heterostructures by selective selenization of a laser-scanned, ultrathin oxidized region (MoOx) on a monolayer MoS2 matrix. In our method, monolayer MoS2 is scanned by a laser with a pre-designed pattern, where the laser-scanned MoS2 is totally oxidized into MoOx. The oxidized region is then selenized in a furnace, while the unoxidized MoS2 region remains unchanged, delivering a MoSe2/MoS2 heterostructure. Unlike in situ laser direct growth methods, our method separates the laser-scanned process from the selenization process, which avoids the long time of point-by-point selenization of MoS2 by laser, making the efficiency of the synthesis greatly improved. The formation process of the heterostructure is studied by Raman spectroscopy and Auger electron spectroscopy. This simple and controllable approach to lateral heterostructures with desired patterns paves the way for fast and mass integration of devices based on 2D heterostructures.

Vortex-Oriented Ferroelectric Domains in SnTe/PbTe Monolayer Lateral Heterostructures.

Heterostructures formed from interfaces between materials with complementary properties often display unconventional physics. Of especial interest are heterostructures formed with ferroelectric materials. These are mostly formed by combining thin layers in vertical stacks. Here the first in situ molecular beam epitaxial growth and scanning tunneling microscopy characterization of atomically sharp lateral heterostructures between a ferroelectric SnTe monolayer and a paraelectric PbTe monolayer are reported. The bias voltage dependence of the apparent heights of SnTe and PbTe monolayers, which are closely related to the type-II band alignment of the heterostructure, is investigated. Remarkably, it is discovered that the ferroelectric domains in the SnTe surrounding a PbTe core form either clockwise or counterclockwise vortex-oriented quadrant configurations. In addition, when there is a finite angle between the polarization and the interface, the perpendicular component of the polarization always points from SnTe to PbTe. Supported by first-principles calculation, the mechanism of vortex formation and preferred polarization direction is identified in the interaction between the polarization, the space charge, and the strain effect at the horizontal heterointerface. The studies bring the application of 2D group-IV monochalcogenides on in-plane ferroelectric heterostructures a step closer.

Spatially Controlled Preparation of Layered Metallic-Semiconducting Metal Chalcogenide Heterostructures.

Spatially controlled preparation of heterostructures composed of layered materials is important in achieving interesting properties. Although vapor-phased deposition methods can prepare vertical and lateral heterostructures, liquid-phased methods, which can enable scalable production and further solution processes, have shown limited controllability. Herein, we demonstrate by using wet chemical methods that metallic Sn0.5Mo0.5S2 nanosheets can be deposited epitaxially on the edges of semiconducting SnS2 nanoplates to form SnS2/Sn0.5Mo0.5S2 lateral heterostructures or coated on both the edges and basal surfaces of SnS2 to give SnS2@Sn0.5Mo0.5S2 core@shell heterostructures. They also showed good light-to-heat conversion ability due to the metallic property of Sn0.5Mo0.5S2. In particular, the core@shell heterostructure showed a higher photothermal conversion efficiency than the lateral counterpart, largely due to its randomly oriented and polycrystalline Sn0.5Mo0.5S2 layers with larger interfacing area for multiple internal light scattering.

Lateral Heterostructures of Multilayer GeS and SnS van der Waals Crystals.

Engineered heterostructures derive distinct properties from materials integration and interface formation. Two-dimensional crystals have been combined to form vertical stacks and lateral heterostuctures with covalent line interfaces. While thicker vertical stacks have been realized, lateral heterostructures from multilayer van der Waals crystals, which could bring the benefits of high-quality interfaces to bulk-like layered materials, have remained much less explored. Here, we demonstrate the integration of anisotropic layered Sn and Ge monosulfides into complex heterostructures with seamless lateral interfaces and tunable vertical design using a two-step growth process. The anisotropic lattice mismatch at the lateral interfaces between GeS and SnS is relaxed via dislocations and interfacial alloying. Nanoscale optoelectronic measurements by cathodoluminescence spectroscopy show the characteristic light emission of joined high-quality van der Waals crystals. Spectroscopy across the lateral interface indicates valley-selective luminescence in the bulk SnS component that arises due to anisotropic electron transfer across the interface. The results demonstrate the ability to realize high-quality lateral heterostructures of multilayer van der Waals crystals for diverse applications, e.g., in optoelectronics or valleytronics.

Promoted Photocharge Separation in 2D Lateral Epitaxial Heterostructure for Visible-Light-Driven CO2 Photoreduction.

Photocarrier recombination remains a big barrier for the improvement of solar energy conversion efficiency. For 2D materials, construction of heterostructures represents an efficient strategy to promote photoexcited carrier separation via an internal electric field at the heterointerface. However, due to the difficulty in seeking two components with suitable crystal lattice mismatch, most of the current 2D heterostructures are vertical heterostructures and the exploration of 2D lateral heterostructures is scarce and limited. Here, lateral epitaxial heterostructures of BiOCl @ Bi2 O3 at the atomic level are fabricated via sonicating-assisted etching of Cl in BiOCl. This unique lateral heterostructure expedites photoexcited charge separation and transportation through the internal electric field induced by chemical bonding at the lateral interface. As a result, the lateral BiOCl @ Bi2 O3 heterostructure demonstrates superior CO2 photoreduction properties with a CO yield rate of about 30 µmol g-1 h-1 under visible light illumination. The strategy to fabricate lateral epitaxial heterostructures in this work is expected to provide inspiration for preparing other 2D lateral heterostructures used in optoelectronic devices, energy conversion, and storage fields.

Two-Dimensional Lateral Heterostructures of Triphosphides: AlP3-GaP3 as a Promising Photocatalyst for Water Splitting.

Photocatalytic water splitting to produce hydrogen is a potential means of achieving scalable and economically feasible solar hydrogen production. Two-dimensional (2D) triphosphides are 2D materials with potential applications in photovoltaics and optoelectronics. Here, we theoretically investigated 56 systems in total, including seven monolayer XP3 (X = Al, Ga, Ge, As, In, Sn, and Sb) and their combined vertical and lateral heterostructures. We found that the lateral heterostructure AlP3-GaP3 should be a promising photocatalyst for water splitting, through a quadruple screening process combining free energy calculations. It is fascinating that AlP3-GaP3 ingeniously combines all the desired features for photocatalytic water-splitting reactions, including a nearly direct band gap (1.43 eV), perfect band edge position, high STH efficiency (16.89%), broad light absorption region of sunlight, ultrahigh carrier mobility (20,000 cm2 V-1 s-1), low exciton binding energy (0.33 eV), and excellent stability in a water environment. Moreover, through Gibbs free energy calculations, the active sites and possible reaction pathways of the overall water-splitting reaction by AlP3-GaP3 were also confirmed. Our work offers a strategy for the design and fabrication of novel lateral heterostructures for a high-performance photocatalyst in water-splitting reactions.