Atomic engineering of two-dimensional materials via liquid metals.

Two-dimensional (2D) materials, known for their distinctive electronic, mechanical, and thermal properties, have attracted considerable attention. The precise atomic-scale synthesis of 2D materials opens up new frontiers in nanotechnology, presenting novel opportunities for material design and property control but remains challenging due to the high expense of single-crystal solid metal catalysts. Liquid metals, with their fluidity, ductility, dynamic surface, and isotropy, have significantly enhanced the catalytic processes crucial for synthesizing 2D materials, including decomposition, diffusion, and nucleation, thus presenting an unprecedented precise control over material structures and properties. Besides, the emergence of liquid alloy makes the creation of diverse heterostructures possible, offering a new dimension for atomic engineering. Significant achievements have been made in this field encompassing defect-free preparation, large-area self-aligned array, phase engineering, heterostructures, etc. This review systematically summarizes these contributions from the aspects of fundamental synthesis methods, liquid catalyst selection, resulting 2D materials, and atomic engineering. Moreover, the review sheds light on the outlook and challenges in this evolving field, providing a valuable resource for deeply understanding this field. The emergence of liquid metals has undoubtedly revolutionized the traditional nanotechnology for preparing 2D materials on solid metal catalysts, offering flexible possibilities for the advancement of next-generation electronics.

Recent progress in emerging two-dimensional organic-inorganic van der Waals heterojunctions.

Two-dimensional (2D) materials have attracted significant attention in recent decades due to their exceptional optoelectronic properties. Among them, to meet the growing demand for multifunctional applications, 2D organic-inorganic van der Waals (vdW) heterojunctions have become increasingly popular in the development of optoelectronic devices. These heterojunctions demonstrate impressive capability to synergistically combine the favourable characteristics of organic and inorganic materials, thereby offering a wide range of advantages. Also, they enable the creation of innovative device structures and introduce novel functionalities in existing 2D materials, avoiding the need for lattice matching in different material systems. Presently, researchers are actively working on improving the performance of devices based on 2D organic-inorganic vdW heterojunctions by focusing on enhancing the quality of 2D materials, precise stacking methods, energy band regulation, and material selection. Therefore, this review presents a thorough examination of the emerging 2D organic-inorganic vdW heterojunctions, including their classification, fabrication, and corresponding devices. Additionally, this review offers profound and comprehensive insight into the challenges in this field to inspire future research directions. It is expected to propel researchers to harness the extraordinary capabilities of 2D organic-inorganic vdW heterojunctions for a wider range of applications by further advancing the understanding of their fundamental properties, expanding the range of available materials, and exploring novel device architectures. The ongoing research and development in this field hold potential to unlock captivating advancements and foster practical applications across diverse industries.

Additive-Assisted Growth of Scaled and Quality 2D Materials.

2D materials are increasingly becoming key components in modern electronics because of their prominent electronic and optoelectronic properties. The central and premise to the entire discipline of 2D materials lie in the high-quality and scaled preparations. The chemical vapor deposition (CVD) method offers compelling benefits in terms of scalability and controllability in shaping large-area and high-quality 2D materials. The past few years have witnessed development of numerous CVD growth strategies, with the use of additives attracting substantial attention in the production of scaled 2D crystals. This review provides an overview of different additives used in CVD growth of 2D materials, as well as a methodical demonstration of their vital roles. In addition, the intrinsic mechanisms of the production of scaled 2D crystals with additives are also discussed. Lastly, reliable guidance on the future design of optimal CVD synthesis routes is provided by analyzing the accessibility, pricing, by-products, controllability, universality, and commercialization of various additives.

Primary Nucleation-Dominated Chemical Vapor Deposition Growth for Uniform Graphene Monolayers on Dielectric Substrate.

Direct chemical vapor deposition growth of high quality graphene on dielectric substrates holds great promise for practical applications in electronics and optoelectronics. However, graphene growth on dielectrics always suffers from the issues of inhomogeneity and/or poor quality. Here, we first reveal that a novel precursor-modification strategy can successfully suppress the secondary nucleation of graphene to evolve ultrauniform graphene monolayer film on dielectric substrates. A mechanistic study indicates that the hydroxylation of silica substrate weakens the binding between graphene edges and substrate, thus realizing the primary nucleation-dominated growth. Field-effect transistors based on the graphene films show exceptional electrical performance with the charge carrier mobility up to 3800 cm2 V-1 s-1 in air, which is much higher than those reported results of graphene films grown on dielectrics.

Mo-Terminated Edge Reconstructions in Nanoporous Molybdenum Disulfide Film.

The catalytic and magnetic properties of molybdenum disulfide (MoS2) are significantly enhanced by the presence of edge sites. One way to obtain a high density of edge sites in a two-dimensional (2D) film is by introducing porosity. However, the large-scale bottom-up synthesis of a porous 2D MoS2 film remains challenging and the correlation of growth conditions to the atomic structures of the edges is not well understood. Here, using molecular beam epitaxy, we prepare wafer-scale nanoporous MoS2 films under conditions of high Mo flux and study their catalytic and magnetic properties. Atomic-resolution electron microscopy imaging of the pores reveals two new types of reconstructed Mo-terminated edges, namely, a distorted 1T (DT) edge and the Mo-Klein edge. Nanoporous MoS2 films are magnetic up to 400 K, which is attributed to the presence of Mo-terminated edges with unpaired electrons, as confirmed by density functional theory calculation. The small hydrogen adsorption free energy at these Mo-terminated edges leads to excellent activity for the hydrogen evolution reaction.

Formation of Twinned Graphene Polycrystals.

Liquid metals have been widely used as substrates to grow graphene and other 2D materials. On a homogeneous and isotropic liquid surface, a polycrystalline 2D material is formed by coalescence of many randomly nucleated single-crystal islands, and as a result, the domains in a polycrystal are expected to be randomly aligned. Here, we report the unexpected finding that only 30°-twinned graphene polycrystals are grown on a liquid Cu surface. Atomic simulations confirm that the unique domain alignment in graphene polycrystals is due to the free rotation of graphene islands on the liquid Cu surface and the highly stable 30°-grain boundaries in graphene. In-depth analysis predicts 30 types of possible 30°-twinned graphene polycrystals and 27 of them are observed. The revealed formation mechanism of graphene polycrystals on a liquid Cu surface deepens our fundamental understanding on polycrystal growth and could serve as a guideline for the controlled synthesis of 2D materials.

Chemical Vapor Deposition of Large-Size Monolayer MoSe2 Crystals on Molten Glass.

We report the fast growth of high-quality millimeter-size monolayer MoSe2 crystals on molten glass using an ambient pressure CVD system. We found that the isotropic surface of molten glass suppresses nucleation events and greatly improves the growth of large crystalline domains. Triangular monolayer MoSe2 crystals with sizes reaching ∼2.5 mm, and with a room-temperature carrier mobility up to ∼95 cm2/(V·s), can be synthesized in 5 min. The method can also be used to synthesize millimeter-size monolayer MoS2 crystals. Our results demonstrate that "liquid-state" glass is a highly promising substrate for the low-cost growth of high-quality large-size 2D transition metal dichalcogenides (TMDs).

Uniform hexagonal graphene flakes and films grown on liquid copper surface.

Unresolved problems associated with the production of graphene materials include the need for greater control over layer number, crystallinity, size, edge structure and spatial orientation, and a better understanding of the underlying mechanisms. Here we report a chemical vapor deposition approach that allows the direct synthesis of uniform single-layered, large-size (up to 10,000 µm(2)), spatially self-aligned, and single-crystalline hexagonal graphene flakes (HGFs) and their continuous films on liquid Cu surfaces. Employing a liquid Cu surface completely eliminates the grain boundaries in solid polycrystalline Cu, resulting in a uniform nucleation distribution and low graphene nucleation density, but also enables self-assembly of HGFs into compact and ordered structures. These HGFs show an average two-dimensional resistivity of 609 ± 200 Ω and saturation current density of 0.96 ± 0.15 mA/µm, demonstrating their good conductivity and capability for carrying high current density.

Phase and Composition Engineering of Self-Intercalated 2D Metallic Tantalum Sulfide for Second-Harmonic Generation.

Self-intercalation in two-dimensional (2D) materials is significant, as it offers a versatile approach to modify material properties, enabling the creation of interesting functional materials, which is essential in advancing applications across various fields. Here, we define ic-2D materials as covalently bonded compounds that result from the self-intercalation of a metal into layered 2D compounds. However, precisely growing ic-2D materials with controllable phases and self-intercalation concentrations to fully exploit the applications in the ic-2D family remains a great challenge. Herein, we demonstrated the controlled synthesis of self-intercalated H-phase and T-phase Ta1+xS2 via a temperature-driven chemical vapor deposition (CVD) approach with a viable intercalation concentration spanning from 10% to 58%. Atomic-resolution scanning transmission electron microscopy-annular dark field imaging demonstrated that the self-intercalated Ta atoms occupy the octahedral vacancies located at the van der Waals gap. The nonperiodic Ta atoms break the centrosymmetry structure and Fermi surface properties of intrinsic TaS2. Therefore, ic-2D T-phase Ta1+xS2 consistently exhibit a spontaneous nonlinear optical (NLO) effect regardless of the sample thickness and self-intercalation concentrations. Our results propose an approach to activate the NLO response of centrosymmetric 2D materials, achieving the modulation of a wide range of optoelectronic properties via nonperiodic self-intercalation in the ic-2D family.

Fractal etching of graphene.

An anisotropic etching mode is commonly known for perfect crystalline materials, generally leading to simple Euclidean geometric patterns. This principle has also proved to apply to the etching of the thinnest crystalline material, graphene, resulting in hexagonal holes with zigzag edge structures. Here we demonstrate for the first time that the graphene etching mode can deviate significantly from simple anisotropic etching. Using an as-grown graphene film on a liquid copper surface as a model system, we show that the etched graphene pattern can be modulated from a simple hexagonal pattern to complex fractal geometric patterns with sixfold symmetry by varying the Ar/H2 flow rate ratio. The etched fractal patterns are formed by the repeated construction of a basic identical motif, and the physical origin of the pattern formation is consistent with a diffusion-controlled process. The fractal etching mode of graphene presents an intriguing case for the fundamental study of material etching.

Gram-scale synthesis of graphene sheets by a catalytic arc-discharge method.

Flake graphite is used as carbon source and ZnO or ZnS as catalyst in the synthesis of high-quality graphene sheets. A catalytic growth mechanism for cathode-part graphene synthesis in the arc-discharge apparatus and an exfoliation mechanism for wall-part graphene synthesis are introduced. N-doped cathode-part graphene and undoped wall-part graphene are formed simultaneously.

Liquid metal catalyzed chemical vapor deposition towards morphology engineering of 2D epitaxial heterostructures.

The past decades have witnessed significant advancements in the growth of two-dimensional (2D) materials, offering a wide range of potential applications in the fields of electronics, optoelectronics, energy storage, sensors, catalysis, and biomedical treatments. Epitaxial heterostructures based on 2D materials, including vertical heterostructures, lateral structures, and superlattices, have emerged as novel material systems to manipulate the intrinsic properties and unlock new functionalities. Therefore, the development of controllable preparation methods for tailored epitaxial heterostructures serves as a fundamental basis for extensive property investigation and further application exploration. However, this pursuit presents formidable challenges due to the incomplete understanding of growth mechanisms and limited designable strategies. Chemical vapor deposition (CVD) is deemed as a promising and versatile platform for the controlled synthesis of 2D materials, especially with regard to achieving lattice matching, a critical factor in epitaxial growth. Consequently, CVD holds potential to overcome these hurdles. In this Feature Article, we present our recent breakthroughs in the controllable preparation of 2D epitaxial heterostructures using CVD. Our focus revolves around the processes of morphology engineering, interface engineering, size and density engineering, and striking the delicate balance between growth and etching. Using molten metals or alloys as primary catalysts, we have achieved remarkable control over the fabrication of graphene/hexagonal boron nitride (hBN) super-ordered arrays, enabled multistage etching of graphene/hBN heterostructures, and successfully realized the construction of graphene/MXene heterostructures. Furthermore, our research endeavors encompass both bottom-up and top-down fabrication methods, offering a novel perspective on the synthesis of 2D epitaxial heterostructures. The resulting products hold immense potential for enhancing the efficiency of critical reactions such as oxygen reduction, CO2 reduction, and hydrogen evolution reactions. By presenting our methodologies for obtaining 2D epitaxial heterostructures through CVD, we aspire to inspire fellow researchers in this field to devise more feasible and controllable fabrication techniques while also fostering the exploration of diverse heterostructure configurations. Together, these advancements will undoubtedly pave the way for further breakthroughs in atomic manufacturing and novel applications.

Ultralow-Power Vertical Transistors for Multilevel Decoding Modes.

Organic field-effect transistors with parallel transmission and learning functions are of interest in the development of brain-inspired neuromorphic computing. However, the poor performance and high power consumption are the two main issues limiting their practical applications. Herein, an ultralow-power vertical transistor is demonstrated based on transition-metal carbides/nitrides (MXene) and organic single crystal. The transistor exhibits a high JON of 16.6 mA cm-2 and a high JON /JOFF ratio of 9.12 × 105 under an ultralow working voltage of -1 mV. Furthermore, it can successfully simulate the functions of biological synapse under electrical modulation along with consuming only 8.7 aJ of power per spike. It also permits multilevel information decoding modes with a significant gap between the readable time of professionals and nonprofessionals, producing a high signal-to-noise ratio up to 114.15 dB. This work encourages the use of vertical transistors and organic single crystal in decoding information and advances the development of low-power neuromorphic systems.

Low temperature growth of highly nitrogen-doped single crystal graphene arrays by chemical vapor deposition.

The ability to dope graphene is highly important for modulating electrical properties of graphene. However, the current route for the synthesis of N-doped graphene by chemical vapor deposition (CVD) method mainly involves high growth temperature using ammonia gas or solid reagent melamine as nitrogen sources, leading to graphene with low doping level, polycrystalline nature, high defect density and low carrier mobility. Here, we demonstrate a self-assembly approach that allows the synthesis of single-layer, single crystal and highly nitrogen-doped graphene domain arrays by self-organization of pyridine molecules on Cu surface at temperature as low as 300 °C. These N-doped graphene domains have a dominated geometric structure of tetragonal-shape, reflecting the single crystal nature confirmed by electron-diffraction measurements. The electrical measurements of these graphene domains showed their high carrier mobility, high doping level, and reliable N-doped behavior in both air and vacuum.

Oxygen-aided synthesis of polycrystalline graphene on silicon dioxide substrates.

We report the metal-catalyst-free synthesis of high-quality polycrystalline graphene on dielectric substrates [silicon dioxide (SiO(2)) or quartz] using an oxygen-aided chemical vapor deposition (CVD) process. The growth was carried out using a CVD system at atmospheric pressure. After high-temperature activation of the growth substrates in air, high-quality polycrystalline graphene is subsequently grown on SiO(2) by utilizing the oxygen-based nucleation sites. The growth mechanism is analogous to that of growth for single-walled carbon nanotubes. Graphene-modified SiO(2) substrates can be directly used in transparent conducting films and field-effect devices. The carrier mobilities are about 531 cm(2) V(-1) s(-1) in air and 472 cm(2) V(-1) s(-1) in N(2), which are close to that of metal-catalyzed polycrystalline graphene. The method avoids the need for either a metal catalyst or a complicated and skilled postgrowth transfer process and is compatible with current silicon processing techniques.

Continuous orientated growth of scaled single-crystal 2D monolayer films.

Single-crystal 2D materials have attracted a boom of scientific and technological activities. Recently, chemical vapor deposition (CVD) shows great promise for the synthesis of high-quality 2D materials owing to high controllability, high scalability and ultra-low cost. Two types of strategies have been developed: one is single-seed method, which focuses on the ultimate control of the density of nucleation into only one nucleus and the other is a multi-seed approach, which concentrates on the precise engineering of orientation of nuclei into a uniform alignment. Currently, the latter is recognized as a more effective method to meet the demand of industrial production, whereas the oriented domains can seamlessly merge into a continuous single-crystal film in a short time. In this review, we present the detailed cases of growing the representative monocrystalline 2D materials via the single-seed CVD method as well as show its advantages and disadvantages in shaping 2D materials. Then, other typical 2D materials (including graphene, h-BN, and TMDs) are given in terms of the unique feature under the guideline of the multi-seed growth approach. Furthermore, the growth mechanism for the 2D single crystals is presented and the following application in electronics, optics and antioxidation coatings are also discussed. Finally, we outline the current challenges, and a bright development in the future of the continuous orientated growth of scaled 2D crystals should be envisioned.

Controlled growth of 2D ultrathin Ga2O3 crystals on liquid metal.

2D metal oxides (2DMOs) have drawn intensive interest in the past few years owing to their rich surface chemistry and unique electronic structures. Striving for large-scale and high-quality novel 2DMOs is of great significance for developing future nano-enabled technologies. In this work, we demonstrate for the first time controllable growth of highly crystalline 2D ultrathin Ga2O3 single crystals on liquid Ga by the chemical vapor deposition approach. With the introduction of oxygen into the growth process, large-area hexagonal α-Ga2O3 crystals with a uniform size distribution have been produced. At high temperature, fast diffusion of oxygen atoms onto the liquid surface facilitates reaction with Ga and thus leads to in situ formation of 2D ultrathin crystals. By precisely controlling the amount of oxygen, the vertical growth of the Ga2O3 single crystal has been realized. Furthermore, phase engineering can be achieved and thus 2D ß-Ga2O3 crystals were also prepared by precisely tuning the growth temperature. The controlled growth of 2D Ga2O3 crystals offers an applicable avenue for fabrication of other 2D metal oxides and can further open up possibilities for future electronics.

When graphene meets white graphene - recent advances in the construction of graphene and h-BN heterostructures.

2D heterostructures have very recently witnessed a boom in scientific and technological activities owing to the customized spatial orientation and tailored physical properties. A large amount of 2D heterostructures have been constructed on the basis of the combination of mechanical exfoliation and located transfer method, opening wide possibilities for designing novel hybrid systems with tuned structures, properties, and applications. Among the as-developed 2D heterostructures, in-plane graphene and h-BN heterostructures have drawn the most attention in the past few decades. The controllable synthesis, the investigation of properties, and the expansion of applications have been widely explored. Herein, the fabrication of graphene and h-BN heterostructures is mainly focused on. Then, the spatial configurations for the heterostructures are systematically probed to identify the highly related unique features. Moreover, as a most promising approach for the scaled production of 2D materials, the in situ CVD fabrication of the heterostructures is summarized, demonstrating a significant potential in the controllability of size, morphology, and quality. Further, the recent applications of the 2D heterostructures are discussed. Finally, the concerns and challenges are fully elucidated and a bright future has been envisioned.

Recent Advances in Growth of Large-Sized 2D Single Crystals on Cu Substrates.

Large-scale and high-quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large-sized and single-crystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large-sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h-BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in-depth growth dynamics and kinetics. Finally, relevant issues for industrial-scale mass production of 2D single crystals are discussed and a promising future is expected.

A minireview on chemical vapor deposition growth of wafer-scale monolayer h-BN single crystals.

Hexagonal boron nitride (h-BN), with its excellent stability, flat surface, and large bandgap, plays a role in a variety of fundamental science and technology fields. The past few years have witnessed significant development in the scaled growth of h-BN single crystals. Currently, the size of h-BN crystal can be reached up to wafer-scale, paving the way towards industrial production and commercial applications. In this minireview, recent academic breakthroughs regarding the controlled growth of large-sized h-BN single crystals via chemical vapor deposition (CVD) are presented. The as-developed technique in terms of growth parameters, choice of catalysts, and the mechanism is fully emphasized, offering a guideline in enhancing the size and quality of h-BN. Several typical metal catalysts have been used in shaping scaled h-BN single crystals, of which the metal Cu substrate has drawn the most intensive attention. The significant advances in expanding the size of h-BN single crystals will largely push forward the way to h-BN industrialization and commercialization. The past few years have witnessed significant development in the scaled growth of h-BN single crystals. Currently, the size of h-BN crystal can be reached up to wafer-scale, paving the way towards industrial production and commercial applications. In this minireview, recent academic breakthroughs regarding controlled growth of large-sized h-BN single crystals via chemical vapor deposition (CVD) are present. The as-developed technique in terms of growth parameters, choice of catalysts and mechanism is fully emphasized, offering a guideline in enhancing size and quality of h-BN. Several typical metal catalysts are exhibited in shaping scaled h-BN single crystals, of which the metal Cu substrate has drawn the most intensive attentions.