Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution.

In recent years, low-dimensional transition metal chalcogenide (TMC) materials have garnered growing research attention due to their superior electronic, optical, and catalytic properties compared to their bulk counterparts. The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications. In this context, the atomic substitution method has emerged as a favorable approach. It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely, crystal structures, and inherent properties of the resulting materials. In this review, we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional, one-dimensional and two-dimensional TMC materials. The effects of substituting elements, substitution ratios, and substitution positions on the structures and morphologies of resulting material are discussed. The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided, emphasizing the role of atomic substitution in achieving these advancements. Finally, challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Atomic Au3Cu Palisade Interlayer in Core@Shell Nanostructures for Efficient Kirkendall Effect Mediation.

Plasmonic Cu@semiconductor heteronanocrystals (HNCs) have many favorable properties, but the synthesis of solid structures is often hindered by the nanoscale Kirkendall effect. Herein, we present the use of an atomically thin Au3Cu palisade interlayer to reduce lattice mismatch and mediate the Kirkendall effect, enabling the successive topological synthesis of Cu@Au3Cu@Ag, Cu@Au3Cu@Ag2S, and further transformed solid Cu@Au3Cu@CdS core-shell HNCs via cation exchange. The atomically thin and intact Au3Cu palisade interlayer effectively modulates the diffusion kinetics of Cu atoms as demonstrated by experimental and theoretical investigations and simultaneously alleviates the lattice mismatch between Cu and Ag as well as Cu and CdS. The Cu@Au3Cu@CdS HNCs feature exceptional crystallinity and atomically organized heterointerfaces between the plasmonic metal and the semiconductor. This results in the efficient plasmon-induced injection of hot electrons from Cu@Au3Cu into the CdS shell, enabling the Cu@Au3Cu@CdS HNCs to achieve high activity and selectivity for the photocatalytic reduction of CO2 to CO.

Substrate Screening for the Epitaxial Growth of a Single-Crystal Graphene Wafer.

Epitaxial growth of a two-dimensional (2D) single crystal necessitates the symmetry group of the substrate being a subgroup of that of the 2D material. As a consequence of the theory of 2D material epitaxy, high-index surfaces, which own very low symmetry, have been successfully used to grow various 2D single crystals, while the rule of selecting the best substrates for 2D single crystal growth is still absent. Here, extensive density functional theory calculations were conducted to investigate the growth of graphene on abundant high-index Cu substrates. Although step edges are commonly regarded as the most active sites for graphene nucleation, our study reveals that, in some cases, graphene nucleation on terraces is superior than that near a step edge. To achieve parallel alignments of graphene islands, it is essential to either suppress terrace nucleation or ensure consistent orientations templated by both the terrace and step edge. In agreement with most experimental observations, we show that Cu substrates for the growth of single-crystalline graphene include vicinal Cu(111) surfaces, vicinal Cu(110) surfaces with Miller indices of (nn1) (n > 3), and vicinal Cu(100) surfaces with Miller indices of (n11) (n > 3).

A mechanism for thickness-controllable single crystalline 2D materials growth.

Recent efforts in growing two-dimensional (2D) multilayers have enabled the synthesis of single crystalline 2D multilayers in a wafer scale through the seamless stitching of multiple epitaxial 2D islands. Unlike previously observed wedding-cake or inverted-wedding-cake structures, these multilayer islands have the same size and shape in each layer with aligned edges. In this study, we investigated the underlying growth mechanisms of synchronic 2D multilayers growth and have showed that a heterogenous layer on a crystalline substrate is critical for maintaining the synchronic growth of 2D multilayers. During growth, the heterogenous layer passivates the edges of multilayer 2D island and thus prevents the coalescence of these active edges, while the high interfacial energy between the heterogenous surface layer and the substrate stabilizes the synchronic structure. Based on this model, we have successfully explained the previously observed synchronic growth of graphene and hexagonal boron nitride multilayers (Nat Nanotech 2020, 15: 861; Nature 2022, 606: 88). The deep understanding on the mechanism paves a way towards the synthesis of wafer-scale single-crystal 2D multilayers with a uniform thickness.

Epitaxial single-crystal hexagonal boron nitride multilayers on Ni (111).

Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene1-3, hexagonal boron nitride (hBN)4-6 and transition metal dichalcogenides7,8 have been grown. hBN is considered to be the 'ideal' dielectric for 2D-materials-based field-effect transistors (FETs), offering the potential for extending Moore's law9,10. Although hBN thicker than a monolayer is more desirable as substrate for 2D semiconductors11,12, highly uniform and single-crystal multilayer hBN growth has yet to be demonstrated. Here we report the epitaxial growth of wafer-scale single-crystal trilayer hBN by a chemical vapour deposition (CVD) method. Uniformly aligned hBN islands are found to grow on single-crystal Ni (111) at early stage and finally to coalesce into a single-crystal film. Cross-sectional transmission electron microscopy (TEM) results show that a Ni23B6 interlayer is formed (during cooling) between the single-crystal hBN film and Ni substrate by boron dissolution in Ni. There are epitaxial relationships between hBN and Ni23B6 and between Ni23B6 and Ni. We also find that the hBN film acts as a protective layer that remains intact during catalytic evolution of hydrogen, suggesting continuous single-crystal hBN. This hBN transferred onto the SiO2 (300 nm)/Si wafer acts as a dielectric layer to reduce electron doping from the SiO2 substrate in MoS2 FETs. Our results demonstrate high-quality single-crystal  multilayered hBN over large areas, which should open up new pathways for making it a ubiquitous substrate for 2D semiconductors.

Single-crystal two-dimensional material epitaxy on tailored non-single-crystal substrates.

The use of single-crystal substrates as templates for the epitaxial growth of single-crystal overlayers has been a primary principle of materials epitaxy for more than 70 years. Here we report our finding that, though counterintuitive, single-crystal 2D materials can be epitaxially grown on twinned crystals. By establishing a geometric principle to describe 2D materials alignment on high-index surfaces, we show that 2D material islands grown on the two sides of a twin boundary can be well aligned. To validate this prediction, wafer-scale Cu foils with abundant twin boundaries were synthesized, and on the surfaces of these polycrystalline Cu foils, we have successfully grown wafer-scale single-crystal graphene and hexagonal boron nitride films. In addition, to greatly increasing the availability of large area high-quality 2D single crystals, our discovery also extends the fundamental understanding of materials epitaxy.

Mechanism of Corrugated Graphene Moiré Superstructures on Transition-Metal Surfaces.

A graphene layer on a transition-metal (TM) surface can be either corrugated or flat, depending on the type of the substrate and its rotation angle with respect to the substrate. It was broadly observed that the degree of corrugation generally decreases with the increase of rotation angle or the decrease of Moiré pattern size. In contrast to a flat graphene on a TM surface, a corrugated graphene layer has an increased binding energy to the substrate and a concomitant elastic energy. Here, we developed a theoretical model about the competition between the binding energy increase and the elastic energy of corrugated graphene layers on TM surfaces in which all the parameters can be calculated by density functional theory (DFT) calculations. The agreement between the theoretical model and the experimental observations of graphene on various TM surfaces, for example, Ru(0001), Rh(111), Pt(111), and Ir(111), substantiated the applicability of this model for graphene on other TM surfaces. Moreover, the morphology of a graphene layer on an arbitrary TM surface can be theoretically predicted through simple DFT calculations based on the model. Our work thus provides a theoretical framework for the intelligent design of graphene/TM superstructures with the desired structure.

Theoretical Study of Chemical Vapor Deposition Synthesis of Graphene and Beyond: Challenges and Perspectives.

Two-dimensional (2D) materials have attracted great attention in recent years because of their unique dimensionality and related properties. Chemical vapor deposition (CVD), a crucial technique for thin-film epitaxial growth, has become the most promising method of synthesizing 2D materials. Different from traditional thin-film growth, where strong chemical bonds are involved in both thin films and substrates, the interaction in 2D materials and substrates involves the van der Waals force and is highly anisotropic, and therefore, traditional thin-film growth theories cannot be applied to 2D material CVD synthesis. During the last 15 years, extensive theoretical studies were devoted to the CVD synthesis of 2D materials. This Perspective attempts to present a theoretical framework for 2D material CVD synthesis as well as the challenges and opportunities in exploring CVD mechanisms. We hope that this Perspective can provide an in-depth understanding of 2D material CVD synthesis and can further stimulate 2D material synthesis.

Strategies, Status, and Challenges in Wafer Scale Single Crystalline Two-Dimensional Materials Synthesis.

The successful exfoliation of graphene has given a tremendous boost to research on various two-dimensional (2D) materials in the last 15 years. Different from traditional thin films, a 2D material is composed of one to a few atomic layers. While atoms within a layer are chemically bonded, interactions between layers are generally weak van der Waals (vdW) interactions. Due to their particular dimensionality, 2D materials exhibit special electronic, magnetic, mechanical, and thermal properties, not found in their 3D counterparts, and therefore they have great potential in various applications, such as 2D materials-based devices. To fully realize their large-scale practical applications, especially in devices, wafer scale single crystalline (WSSC) 2D materials are indispensable. In this review, we present a detailed overview on strategies toward the synthesis of WSSC 2D materials while highlighting the recent progress on WSSC graphene, hexagonal boron nitride (hBN), and transition metal dichalcogenide (TMDC) synthesis. The challenges that need to be addressed in future studies have also been described. In general, there have been two distinct routes to synthesize WSSC 2D materials: (i) allowing only one nucleus on a wafer scale substrate to be formed and developed into a large single crystal and (ii) seamlessly stitching a large number of unidirectionally aligned 2D islands on a wafer scale substrate, which is generally single crystalline. Currently, the synthesis of WSSC graphene has been realized by both routes, and WSSC hBN and MoS2 have been synthesized by route (ii). On the other hand, the growth of other WSSC 2D materials and WSSC multilayer 2D materials still remains a big challenge. In the last section, we wrap up this review by summarizing the future challenges and opportunities in the synthesis of various WSSC 2D materials.

The epitaxy of 2D materials growth.

Two dimensional (2D) materials consist of one to a few atomic layers, where the intra-layer atoms are chemically bonded and the atomic layers are weakly bonded. The high bonding anisotropicity in 2D materials make their growth on a substrate substantially different from the conventional thin film growth. Here, we proposed a general theoretical framework for the epitaxial growth of a 2D material on an arbitrary substrate. Our extensive density functional theory (DFT) calculations show that the propagating edge of a 2D material tends to align along a high symmetry direction of the substrate and, as a conclusion, the interplay between the symmetries of the 2D material and the substrate plays a critical role in the epitaxial growth of the 2D material. Based on our results, we have outlined that orientational uniformity of 2D material islands on a substrate can be realized only if the symmetry group of the substrate is a subgroup of that of the 2D material. Our predictions are in perfect agreement with most experimental observations on 2D materials' growth on various substrates known up to now. We believe that this general guideline will lead to the large-scale synthesis of wafer-scale single crystals of various 2D materials in the near future.

The alignment-dependent properties and applications of graphene moiré superstructures on the Ru(0001) surface.

The moiré superstructure of graphene on a lattice-mismatched metal substrate has profound effects on the electronic properties of graphene and can be used for many applications. Here, we propose to systematically tune the moiré superstructure of graphene on the Ru(0001) surface by rotating the graphene layer. Our study reveals two kinds of graphene moiré superstructures: (i) the ultra-flat graphene layers with height variations of less than 0.1 Å for rotation angles greater than 20° that have the same structural and electronic properties everywhere, and (ii) the highly corrugated graphene moiré superstructures with height variations from 0.4 to 1.6 Å for rotation angles less than 20°, whose electronic properties are highly modulated by the interaction with the substrate. Moreover, these rotated graphene moiré superstructures can serve as templates to produce matrices of size-tunable metal clusters from a few to ∼100 atoms. This study reveals the causes of the structural fluctuation of moiré superstructures of graphene on the transition metal surface and suggests a pathway to tune graphene's electronic properties for various applications.

Epitaxial growth of a 100-square-centimetre single-crystal hexagonal boron nitride monolayer on copper.

The development of two-dimensional (2D) materials has opened up possibilities for their application in electronics, optoelectronics and photovoltaics, because they can provide devices with smaller size, higher speed and additional functionalities compared with conventional silicon-based devices1. The ability to grow large, high-quality single crystals for 2D components-that is, conductors, semiconductors and insulators-is essential for the industrial application of 2D devices2-4. Atom-layered hexagonal boron nitride (hBN), with its excellent stability, flat surface and large bandgap, has been reported to be the best 2D insulator5-12. However, the size of 2D hBN single crystals is typically limited to less than one millimetre13-18, mainly because of difficulties in the growth of such crystals; these include excessive nucleation, which precludes growth from a single nucleus to large single crystals, and the threefold symmetry of the hBN lattice, which leads to antiparallel domains and twin boundaries on most substrates19. Here we report the epitaxial growth of a 100-square-centimetre single-crystal hBN monolayer on a low-symmetry Cu (110) vicinal surface, obtained by annealing an industrial copper foil. Structural characterizations and theoretical calculations indicate that epitaxial growth was achieved by the coupling of Cu <211> step edges with hBN zigzag edges, which breaks the equivalence of antiparallel hBN domains, enabling unidirectional domain alignment better than 99 per cent. The growth kinetics, unidirectional alignment and seamless stitching of the hBN domains are unambiguously demonstrated using centimetre- to atomic-scale characterization techniques. Our findings are expected to facilitate the wide application of 2D devices and lead to the epitaxial growth of broad non-centrosymmetric 2D materials, such as various transition-metal dichalcogenides20-23, to produce large single crystals.

Kinetics of Graphene and 2D Materials Growth.

During the last 10 years, remarkable achievements on the chemical vapor deposition (CVD) growth of 2D materials have been made, but the understanding of the underlying mechanisms is still relatively limited. Here, the current progress on the understanding of the growth kinetics of 2D materials, especially for their CVD synthesis, is reviewed. In order to present a complete picture of 2D materials' growth kinetics, the following factors are discussed: i) two types of growth modes, namely attachment-limited growth and diffusion-limited growth; ii) the etching of 2D materials, which offers an additional degree of freedom for growth control; iii) a number of experimental factors in graphene CVD synthesis, such as structure of the substrate, pressure of hydrogen or oxygen, temperature, etc., which are found to have profound effects on the growth kinetics; iv) double-layer and few-layer 2D materials' growth, which has distinct features different from the growth of single-layer 2D materials; and v) the growth of polycrystalline 2D materials by the coalescence of a few single crystalline domains. Finally, the current challenges and opportunities in future 2D materials' synthesis are summarized.

Colossal grain growth yields single-crystal metal foils by contact-free annealing.

Single-crystal metals have distinctive properties owing to the absence of grain boundaries and strong anisotropy. Commercial single-crystal metals are usually synthesized by bulk crystal growth or by deposition of thin films onto substrates, and they are expensive and small. We prepared extremely large single-crystal metal foils by "contact-free annealing" from commercial polycrystalline foils. The colossal grain growth (up to 32 square centimeters) is achieved by minimizing contact stresses, resulting in a preferred in-plane and out-of-plane crystal orientation, and is driven by surface energy minimization during the rotation of the crystal lattice followed by "consumption" of neighboring grains. Industrial-scale production of single-crystal metal foils is possible as a result of this discovery.

How graphene crosses a grain boundary on the catalyst surface during chemical vapour deposition growth.

The chemical vapour deposition (CVD) growth of graphene is normally an epitaxial process, where the atomic structure of the adlayer should copy the texture of the substrate. However, it has been widely observed that single crystalline graphene grown on metal foil may cross a grain boundary (GB) of the substrate without forming any line defect, a necessary condition to change its crystalline orientation and maintain the structure registry with the substrate on the other side of the GB. Here, we present a comprehensive theoretical study on graphene growth behavior on polycrystalline metal substrates. Our density functional theory (DFT) calculations reveal that for graphene growth on most metal surfaces, the binding energy difference between the epitaxial and non-epitaxial graphene on the substrate is not large enough to compensate for the formation energy of a GB in graphene and therefore, during the CVD process, the growing graphene can pass through a GB on the metal surface without changing its crystalline orientation. Hence, graphene CVD growth cannot be strictly regarded as an epitaxial process; this conclusion is further verified by atomic simulations. The present study shows that the growth of graphene on a metal catalyst surface should be regarded rather as a quasi-epitaxial process, where a graphene domain is aligned only on the single crystalline metal facet on which it nucleates, but this structural registry with the metal substrate may be lost when the graphene crosses a GB on the metal surface.

Distinctive electron transport on pyridine-linked molecular junctions with narrow monolayer graphene nanoribbon electrodes compared with metal electrodes and graphene electrodes.

The electrodes in the molecular devices are essential for creating functional organic electronic devices. We investigate theoretically the pyridine-terminated molecule - 4,4'-bipyridyl attached to the narrow monolayer zigzag graphene nanoribbon electrodes, compared to the metal (Au, Ag and Cu) and 2D graphene electrodes. Results show that this zigzag graphene nanoribbon-based junction shows excellent electron transport performances. It possesses great transmission at the fermi level due to the strongest delocalization of the electronic state. The coupling of the dominant molecular orbital to the ZGNR electrodes is much stronger than that to the metal electrodes due to a higher contributing proportion of PDOS on N atoms in the molecule at the fermi level. Also the molecular orbital couples more strongly to the ZGNR electrodes than the graphene electrodes because of a larger device density of state around the fermi level. Moreover, the different molecule-electrode coupling among these metal-based devices stems from the different proportion of density of d-states of the electrodes at the fermi level. In addition, the device with the narrow ZGNR electrodes exhibits the NDR effect unexpectedly.

Liquid-Liquid Phase Transition in Nanoconfined Silicon Carbide.

We report theoretical evidence of a liquid-liquid phase transition (LLPT) in liquid silicon carbide under nanoslit confinement. The LLPT is characterized by layering transitions induced by confinement and pressure, accompanying the rapid change in density. During the layering transition, the proportional distribution of tetracoordinated and pentacoordinated structures exhibits remarkable change. The tricoordinated structures lead to the microphase separation between silicon (with the dominant tricoordinated, tetracoordinated, and pentacoordinated structures) and carbon (with the dominant tricoordinated structures) in the layer close to the walls. A strong layer separation between silicon atoms and carbon atoms is induced by strong wall-liquid forces. Importantly, the pressure confinement phase diagram with negative slopes for LLPT lines indicates that, under high pressure, the LLPT is mainly confinement-induced, but under low pressure, it becomes dominantly pressure-induced.

Electronic transport properties of ultra-thin Ni and Ni-C nanowires.

The structures and electronic transport properties of ultra-thin Ni and Ni-C nanowires obtained from carbon nanotube (CNT) templates are theoretically investigated. C atoms tend to locate at the central positions of nanowires and are surrounded by Ni atoms. Spin polarization at the Fermi level is not responsible for the spin filtration of these nanowires. Increasing C concentration can improve the resistance of nanowires by abating the number of electronic transmission channels and the coupling of electron orbitals between Ni atoms. Moreover, with the increase of diameter, the conductance of these nanowires increases as well. This study is helpful for guiding the synthesis of nanowires with desired applications.

Interfacial structure and wetting properties of water droplets on graphene under a static electric field.

The behavior of water droplets located on graphene in the presence of various external electric fields (E-fields) is investigated using classical molecular dynamics (MD) simulations. We explore the effect of E-field on mass density distribution, water polarization as well as hydrogen bonds (H-bonds) to gain insight into the wetting properties of water droplets on graphene and their interfacial structure under uniform E-fields. The MD simulation results reveal that the equilibrium water droplets present a hemispherical, a conical and an ordered cylindrical shape with the increase of external E-field intensity. Accompanied by the shape variation of water droplets, the dipole orientation of water molecules experiences a remarkable change from a disordered state to an ordered state because of the polarization of water molecules induced by static E-field. The distinct two peaks in mass density and H-bond distribution profiles demonstrate that water has a layering structure in the interfacial region, which sensitively depends on the strong E-field (>0.8 V nm(-1)). In addition, when the external E-field is parallel to the substrate, the E-field would make the contact angle of the water droplets become small and increase its wettability. Our findings provide the possibility to control the structure and wetting properties of water on graphene by tuning the direction and intensity of external E-field which is of importance for relevant industrial processes on the solid surface.

Synergy and pinning effects in a monatomic liquid film in confined conditions.

The freezing behavior of a monatomic liquid film in confined conditions during rapid cooling was studied by molecular dynamics simulations. We illustrated the synergy and pinning effects of the local icosahedral order during freezing. Our results show that the icosahedron contributes to nucleation through the synergy with other short-range ordered structures and participates in crystal growth via assimilation, but the pinning effect should be overcome when crystals grow. Furthermore, a semi-ordered morphology with maze-like nano-patterns emerged due to the cooperation between the synergy effect and the pinning effect. Our findings shed light on the correlation between the local icosahedral order and the crystalline medium-range order, providing a better understanding of the rapid solidification.