Quantum Confinement of Dirac Quasiparticles in Graphene Patterned with Sub-Nanometer Precision

Quantum confinement of graphene Dirac-like electrons in artificially crafted nanometer structures is a long sought goal that would provide a strategy to selectively tune the electronic properties of graphene, including bandgap opening or quantization of energy levels. However, creating confining structures with nanometer precision in shape, size, and location remains an experimental challenge, both for top-down and bottom-up approaches. Moreover, Klein tunneling, offering an escape route to graphene electrons, limits the efficiency of electrostatic confinement. Here, a scanning tunneling microscope (STM) is used to create graphene nanopatterns, with sub-nanometer precision, by the collective manipulation of a large number of H atoms. Individual graphene nanostructures are built at selected locations, with predetermined orientations and shapes, and with dimensions going all the way from 2 nm up to 1 µm. The method permits the patterns to be erased and rebuilt at will, and it can be implemented on different graphene substrates. STM experiments demonstrate that such graphene nanostructures confine very efficiently graphene Dirac quasiparticles, both in 0D and 1D structures. In graphene quantum dots, perfectly defined energy bandgaps up to 0.8 eV are found that scale as the inverse of the dot’s linear dimension, as expected for massless Dirac fermions.     

Dirac Fermion Kinetics in 3D Curved Graphene

3D integration of graphene has attracted attention for realizing carbon-based electronic devices. While the 3D integration can amplify various excellent properties of graphene, the influence of 3D curved surfaces on the fundamental physical properties of graphene has not been clarified. The electronic properties of 3D nanoporous graphene with a curvature radius down to 25–50 nm are systematically investigated and the ambipolar electronic states of Dirac fermions are essentially preserved in the 3D graphene nanoarchitectures, while the 3D curvature can effectively suppress the slope of the linear density of states of Dirac fermion near the Fermi level are demonstrated. Importantly, the 3D curvature can be utilized to tune the back-scattering-suppressed electrical transport of Dirac fermions and enhance both electron localization and electron–electron interaction. As a result, nanoscale curvature provides a new degree of freedom to manipulate 3D graphene electrical properties, which may pave a new way to design new 3D graphene devices with preserved 2D electronic properties and novel functionalities.     

On‐Surface Synthesis of 8‐ and 10‐Armchair Graphene Nanoribbons

Armchair graphene nanoribbons (AGNRs) with 8 and 10 carbon atoms in width (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces via lateral fusion of nanoribbons that belong to different subfamilies. Poly‐para‐phenylene (3‐AGNR) chains are pre‐synthesized as ladder ribbons on Au (111). Subsequently, synthesized 5‐ and 7‐AGNRs can laterally fuse with 3‐AGNRs upon annealing at higher temperature, producing 8‐ and 10‐AGNRs, respectively. The synthetic process, and their geometric and electronic structures are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). STS investigations reveal the band gap of 10‐AGNR (2.0 ± 0.1 eV) and a large apparent band gap of 8‐AGNRs (2.3 ± 0.1 eV) on Au (111) surface.     

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.     

Advance in Close‐Edged Graphene Nanoribbon: Property Investigation and Structure Fabrication

The absence of dangling bonds in close‐edged graphene nanoribbons (CEGNRs) confers upon them a series of fascinating properties, especially when compared with cylindrical carbon nanotubes and open‐edged GNRs. Here, the configuration of CEGNRs is described, followed by the structure‐related properties, including mechanical, thermal, electrical, optical, and magnetic properties. Based on the unique structures and extraordinary properties, their potential applications in a variety of fields, such as field‐effect transistors, energy suppliers, nanoactuators, and fibers, are discussed. Remarkably, the strategies applied for generating CEGNRs, mainly from the collapse of carbon nanotubes and graphene tubes, are depicted in detail. Finally, the prospects in the research area of CEGNRs are proposed.     

Reversible hydrogenation and bandgap opening of graphene and graphite surfaces probed by scanning tunneling spectroscopy

The effects of hydrogenation on the topography and electronic properties of graphene and graphite surfaces are studied by scanning tunneling microscopy and spectroscopy. The surfaces are chemically modified using an Ar/H(2) plasma. By analyzing thousands of scanning tunneling spectroscopy measurements it is determined that the hydrogen chemisorption on the surface of graphite/graphene opens on average an energy bandgap of 0.4 eV around the Fermi level. Although the plasma treatment modifies the surface topography in an irreversible way, the change in the electronic properties can be reversed by moderate thermal annealing and the samples can be hydrogenated again to yield a similar, but slightly reduced, semiconducting behavior after the second hydrogenation.     

Contrast Reversal in Scanning Tunneling Microscopy and Its Implications for the Topological Classification of SmB6

SmB₆ has recently attracted considerable interest as a candidate for the first strongly correlated topological insulator. Such materials promise entirely new properties such as correlation-enhanced bulk bandgaps or a Fermi surface from spin excitations. Whether SmB₆ and its surface states are topological or trivial is still heavily disputed however, and a solution is hindered by major disagreement between angle-resolved photoemission (ARPES) and scanning tunneling microscopy (STM) results. Here, a combined ARPES and STM experiment is conducted. It is discovered that the STM contrast strongly depends on the bias voltage and reverses its sign beyond 1 V. It is shown that the understanding of this contrast reversal is the clue to resolving the discrepancy between ARPES and STM results. In particular, the scanning tunneling spectra reflect a low-energy electronic structure at the surface, which supports a trivial origin of the surface states and the surface metallicity of SmB₆.     

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.     

Topological Defects: Origin of Nanopores and Enhanced Adsorption Performance in Nanoporous Carbon

A scanning transmission electron microscopy investigation of two nanoporous carbon materials, wood‐based ultramicroporous carbon and poly(furfuryl alcohol)‐derived carbon, is reported. Atomic‐resolution images demonstrate they comprise isotropic, three‐dimensional networks of wrinkled one‐atom‐thick graphene sheets. In each graphene plane, nonhexagonal defects are frequently observed as connected five‐ and seven‐atom rings. Atomic‐level modeling shows that these topological defects induce localized rippling of graphene sheets, which interferes with their graphitic stacking and induces nanopores that lead to enhanced adsorption of H₂ molecules. The poly(furfuryl alcohol)‐derived carbon contains larger regions of stacked layers, and shows significantly smaller surface area and pore volume than the ultramicroporous carbon.     

Sulfur-doped graphene nanoribbons with a sequence of distinct band gaps

Unlike graphene sheets,graphene nanoribbons (GNRs) can exhibit semiconducting band gap characteristics that can be tuned by controlling impurity doping and the GNR widths and edge structures.However,achieving such control is a major challenge in the fabrication of GNRs.Chevron-type GNRs were recently synthesized via surface-assisted polymerization of pristine or N-substituted oligophenylene monomers.In principle,GNR heterojunctions can be fabricated by mixing two different monomers.In this paper,we report the fabrication and characterization of chevron-type GNRs using sulfur-substituted oligophenylene monomers to produce GNRs and related heterostructures for the first time.First-principles calculations show that the GNR gaps can be tailored by applying different sulfur configurations from cyclodehydrogenated isomers via debromination and intramolecular cyclodehydrogenation.This feature should enable a new approach for the creation of multiple GNR heterojunctions by engineering their sulfur configurations.These predictions have been confirmed via scanning tunneling microscopy and scanning tunneling spectroscopy.For example,we have found that the S-containing GNRs contain segments with distinct band gaps,i.e.,a sequence of multiple heterojunctions that results in a sequence of quantum dots.This unusual intraribbon heterojunction sequence may be useful in nanoscale optoelectronic applications that use quantum dots.     

Local Electronic Structure of Molecular Heterojunctions in a Single‐Layer 2D Covalent Organic Framework

The synthesis of a single‐layer covalent organic framework (COF) with spatially modulated internal potentials provides new opportunities for manipulating the electronic structure of molecularly defined materials. Here, the fabrication and electronic characterization of COF‐420: a single‐layer porphyrin‐based square‐lattice COF containing a periodic array of oriented, type II electronic heterojunctions is reported. In contrast to previous donor–acceptor COFs, COF‐420 is constructed from building blocks that yield identical cores upon reticulation, but that are bridged by electrically asymmetric linkers supporting oriented electronic dipoles. Scanning tunneling spectroscopy reveals staggered gap (type II) band alignment between adjacent molecular cores in COF‐420, in agreement with first‐principles calculations. Hirshfeld charge analysis indicates that dipole fields from oriented imine linkages within COF‐420 are the main cause of the staggered electronic structure in this square grid of atomically–precise heterojunctions.     

Topological to trivial insulating phase transition in stanene

Electronic properties of stanene, the Sn counterpart of graphene are theoretically studied using first-principles simulations. The topological to trivial insulating phase transition induced by an out-of-plane electric field or by quantum confinement effects is predicted. The results highlight the potential to use stanene nanoribbons in gate-voltage controlled dissipationless spin-based devices and are used to set the minimal nanoribbon width for such devices, which is typically approximately 5 nm.

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