On‐Surface Synthesis of Graphyne‐Based Nanostructures

The successful synthesis of stacking graphdiynes has stimulated numerous fascinating applications. However, it still remains challenging to prepare atomically precise 2D graphdiyne and other graphyne‐based structures. The development of on‐surface synthesis has contributed to many secondary graphyne‐based structures that are directive in fabricating extended graphyne networks. Herein, the recent progress concerning on‐surface synthesis of graphyne‐based nanostructures, especially atomically precise graphdiyne nanowires, is summarized.     

Graphene Nanoribbons: On-Surface Synthesis and Integration into Electronic Devices

Graphene nanoribbons (GNRs) are quasi-1D graphene strips, which have attracted attention as a novel class of semiconducting materials for various applications in electronics and optoelectronics. GNRs exhibit unique electronic and optical properties, which sensitively depend on their chemical structures, especially the width and edge configuration. Therefore, precision synthesis of GNRs with chemically defined structures is crucial for their fundamental studies as well as device applications. In contrast to top-down methods, bottom-up chemical synthesis using tailor-made molecular precursors can achieve atomically precise GNRs. Here, the synthesis of GNRs on metal surfaces under ultrahigh vacuum (UHV) and chemical vapor deposition (CVD) conditions is the main focus, and the recent progress in the field is summarized. The UHV method leads to successful unambiguous visualization of atomically precise structures of various GNRs with different edge configurations. The CVD protocol, in contrast, achieves simpler and industry-viable fabrication of GNRs, allowing for the scale up and efficient integration of the as-grown GNRs into devices. The recent updates in device studies are also addressed using GNRs synthesized by both the UHV method and CVD, mainly for transistor applications. Furthermore, views on the next steps and challenges in the field of on-surface synthesized GNRs are provided.     

Temperature‐Triggered Sulfur Vacancy Evolution in Monolayer MoS2/Graphene Heterostructures

The existence of defects in 2D semiconductors has been predicted to generate unique physical properties and markedly influence their electronic and optoelectronic properties. In this work, it is found that the monolayer MoS₂ prepared by chemical vapor deposition is nearly defect‐free after annealing under ultrahigh vacuum conditions at ≈400 K, as evidenced by scanning tunneling microscopy observations. However, after thermal annealing process at ≈900 K, the existence of dominant single sulfur vacancies and relatively rare vacancy chains (2S, 3S, and 4S) is convinced in monolayer MoS₂ as‐grown on Au foils. Of particular significance is the revelation that the versatile vacancies can modulate the band structure of the monolayer MoS₂, leading to a decrease of the bandgap and an obvious n‐doping effect. These results are confirmed by scanning tunneling spectroscopy data as well as first‐principles theoretical simulations of the related morphologies and the electronic properties of the various defect types. Briefly, this work should pave a novel route for defect engineering and hence the electronic property modulation of three‐atom‐thin 2D layered semiconductors.     

Modified Engineering of Graphene Nanoribbons Prepared via On-Surface Synthesis

1D graphene nanoribbons (GNRs) have a bright future in the fabrication of next-generation nanodevices because of their nontrivial electronic properties and tunable bandgaps. To promote the application of GNRs, preparation strategies of miscellaneous GNRs have to be developed. The GNRs prepared by top-down approaches are accompanied by uncontrolled edges and structures. In order to overcome the difficulties, bottom-up methods are widely used in the growth of various GNRs due to controllability of GNRs' features. Among those bottom-up methods, the on-surface synthesis is a promising approach to prepare GNRs with distinct widths, edge/backbone structures, and so forth. Therefore, modified engineering of the GNRs prepared via on-surface synthesis is of great significance in controllable preparation of GNRs and their potential applications. In the past decade, there have been a lot of reports on controllable preparation of GNRs using on-surface synthesis approach. Herein, the advances of GNRs grown via on-surface growth strategy are described. Several growth parameters, the latest advances in the modification of the GNR structure and width, the GNR doping/co-doping with heteroatoms, a variety of GNR heterojunctions, and the device application of GNRs are reviewed. Finally, the opportunities and challenges are discussed.     

Massive Dirac Fermion Behavior in a Low Bandgap Graphene Nanoribbon Near a Topological Phase Boundary

Graphene nanoribbons (GNRs) have attracted much interest due to their largely modifiable electronic properties. Manifestation of these properties requires atomically precise GNRs which can be achieved through a bottom–up synthesis approach. This has recently been applied to the synthesis of width-modulated GNRs hosting topological electronic quantum phases, with valence electronic properties that are well captured by the Su–Schrieffer–Heeger (SSH) model describing a 1D chain of interacting dimers. Here, ultralow bandgap GNRs with charge carriers behaving as massive Dirac fermions can be realized when their valence electrons represent an SSH chain close to the topological phase boundary, i.e., when the intra- and interdimer coupling become approximately equal. Such a system has been achieved via on-surface synthesis based on readily available pyrene-based precursors and the resulting GNRs are characterized by scanning probe methods. The pyrene-based GNRs (pGNRs) can be processed under ambient conditions and incorporated as the active material in a field effect transistor. A quasi-metallic transport behavior is observed at room temperature, whereas at low temperature, the pGNRs behave as quantum dots showing single-electron tunneling and Coulomb blockade. This study may enable the realization of devices based on carbon nanomaterials with exotic quantum properties.     

Multiscale Plasma‐Catalytic On‐Surface Assembly

Controlled modification of surfaces is one of the key pursuits of the nanoscience and nanotechnology fields, allowing for the fabrication of bespoke materials with targeted functionalities. However, many surface modifications currently require painstakingly precise and/or energy intensive processing to implement, and are thus limited in scope and scale. Here, a concept which can enhance the capacity for control of surfaces is introduced: plasma‐assisted nucleation and self‐assembly at atomic to nanoscales, scalable at atmospheric pressures.     

Layer‐by‐Layer Decoupling of Twisted Graphene Sheets Epitaxially Grown on a Metal Substrate

The electronic properties of graphene can be efficiently altered upon interaction with the underlying substrate resulting in a dramatic change of charge carrier behavior. Here, the evolution of the local electronic properties of epitaxial graphene on a metal upon the controlled formation of multilayers, which are produced by intercalation of atomic carbon in graphene/Ir(111), is investigated. Using scanning tunneling microscopy and Landau‐level spectroscopy, it is shown that for a monolayer and bilayers with small‐angle rotations, Landau levels are fully suppressed, indicating that the metal–graphene interaction is largely confined to the first graphene layer. Bilayers with large twist angles as well as twisted trilayers demonstrate a sequence of pronounced Landau levels characteristic for a free‐standing graphene monolayer pointing toward an effective decoupling of the top layer from the metal substrate. These findings give evidence for the controlled preparation of epitaxial graphene multilayers with a different degree of decoupling, which represent an ideal platform for future electronic and spintronic applications.     

Surface Supported Gold–Organic Hybrids: On‐Surface Synthesis and Surface Directed Orientation

The surface‐assisted synthesis of gold–organic hybrids on Au (111) and Au (100) surfaces is repotred by thermally initiated dehalogenation of chloro‐substituted perylene‐3,4,9,10‐tetracarboxylic acid bisimides (PBIs). Structures and surface‐directed alignment of the Au–PBI chains are investigated by scanning tunnelling microscopy in ultra high vacuum conditions. Using dichloro‐PBI as a model system, the mechanism for the formation of Au–PBI dimer is revealed with scanning tunnelling microscopy studies and density functional theory calculations. A PBI radical generated from the homolytic C‐Cl bond dissociation can covalently bind a surface gold atom and partially pull it out of the surface to form stable PBI‐Au hybrid species, which also gives rise to the surface‐directed alignment of the Au–PBI chains on reconstructed Au (100) surfaces.     

Electronic Property Modification of Single‐Walled Carbon Nanotubes by Encapsulation of Sulfur‐Terminated Graphene Nanoribbons

The use of carbon nanotubes (CNTs) as cylindrical reactor vessels has become a viable means for synthesizing graphene nanoribbons (GNRs). While previous studies demonstrated that the size and edge structure of the as‐produced GNRs are strongly dependent on the diameter of the tubes and the nature of the precursor, the atomic interactions between GNRs and surrounding CNTs and their effect on the electronic properties of the overall system are not well understood. Here, it is shown that the functional terminations of the GNR edges can have a strong influence on the electronic structure of the system. Analysis of SWCNTs before and after the insertion of sulfur‐terminated GNRs suggests a metallization of the majority of semiconducting SWCNTs. This is indicated by changes in the radial breathing modes and the D and G band Raman features, as well as UV–vis–NIR absorption spectra. The variation in resonance conditions of the nanotubes following GNR insertion make direct (n,m) assignment by Raman spectroscopy difficult. Thus, density functional theory calculations of representative GNR/SWCNT systems are performed. The results confirm significant changes in the band structure, including the development of a metallic state in the semiconducting SWCNTs due to sulfur/tube interactions. The GNR‐induced metallization of semiconducting SWCNTs may offer a means of controlling the electronic properties of bulk CNT samples and eliminate the need for a physical separation of semiconducting and metallic tubes.     

Dielectric‐Screening Reduction‐Induced Large Transport Gap in Suspended Sub‐10 nm Graphene Nanoribbon Functional Devices

The predicted quasiparticle energy gap of more than 1 eV in sub‐6 nm graphene nanoribbons (GNRs) is elusive, as it is strongly suppressed by the substrate dielectric screening. The number of techniques that can produce suspended high‐quality and electrically contacted GNRs is small. The helium ion beam milling technique is capable of achieving sub‐5 nm patterning; however, the functional device fabrication and the electrical characteristics are not yet reported. Here, the electrical transport measurement of suspended ≈6 nm wide mono‐ and bilayer GNR functional devices is reported, which are obtained through sub‐nanometer resolution helium ion beam milling with controlled total helium ion budget. The transport gap opening of 0.16–0.8 eV is observed at room temperature. The measured transport gap of the different edge orientated GNRs is in good agreement with first‐principles simulation results. The enhanced electron–electron interaction and reduced dielectric screening in the suspended quasi‐1D GNRs and anti‐ferromagnetic coupling between opposite edges in the zigzag GNRs substantiate the observed large transport gap.     

Graphene Acoustic Phonon‐Mediated Pseudo‐Landau Levels Tailoring Probed by Scanning Tunneling Spectroscopy

Graphene has attracted great interests in various areas including optoelectronics, spintronics, and nanomechanics due to its unique electronic structure, a linear dispersion with a zero bandgap around the Dirac point. Shifts of Dirac cones in graphene creates pseudo‐magnetic field, which generates an energy gap and brings a zero‐magnetic‐field analogue of the quantum Hall effect. Recent studies have demonstrated that graphene pseudo‐magnetic effects can be generated by vacancy defects, atom adsorption, zigzag or armchair edges, and external strain. Here, a larger than 100 T pseudo‐magnetic field is reported that generated on the step area of graphene; and with the ultrahigh vacuum scanning tunneling microscopy, the observed Landau levels can be effectively tailored by graphene phonons. The zero pseudo‐Landau level is suppressed due to the phonon‐mediated inelastic tunneling, and this is observed by the scanning tunneling spectroscopy spectrum and confirmed by the Vienna ab initio simulation package calculation, where graphene phonons modulate the flow of tunneling electrons and further mediate pseudo‐Landau levels. These observations demonstrate a viable approach for the control of pseudo‐Landau levels, which tailors the electronic structure of graphene, and further ignites applications in graphene valley electronics.     

Functionalized Graphdiyne Nanowires: On‐Surface Synthesis and Assessment of Band Structure,Flexibility, and Information Storage Potential

Carbon nanomaterials exhibit extraordinary mechanical and electronic properties desirable for future technologies. Beyond the popular sp²‐scaffolds, there is growing interest in their graphdiyne‐related counterparts incorporating both sp² and sp bonding in a regular scheme. Herein, we introduce carbonitrile‐functionalized graphdiyne nanowires, as a novel conjugated, one‐dimensional (1D) carbon nanomaterial systematically combining the virtues of covalent coupling and supramolecular concepts that are fabricated by on‐surface synthesis. Specifically, a terphenylene backbone is extended with reactive terminal alkyne and polar carbonitrile (CN) moieties providing the required functionalities. It is demonstrated that the CN functionalization enables highly selective alkyne homocoupling forming polymer strands and gives rise to mutual lateral attraction entailing room‐temperature stable double‐stranded assemblies. By exploiting the templating effect of the vicinal Ag(455) surface, 40 nm long semiconducting nanowires are obtained and the first experimental assessment of their electronic band structure is achieved by angle‐resolved photoemission spectroscopy indicating an effective mass below 0.1m₀ for the top of the highest occupied band. Via molecular manipulation it is showcased that the novel oligomer exhibits extreme mechanical flexibility and opens unexplored ways of information encoding in clearly distinguishable CN‐phenyl trans–cis species. Thus, conformational data storage with density of 0.36 bit nm^?2 and temperature stability beyond 150 K comes in reach.