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      Graphene-like nanoribbons periodically embedded with four- and eight-membered rings

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          Abstract

          Embedding non-hexagonal rings into sp 2-hybridized carbon networks is considered a promising strategy to enrich the family of low-dimensional graphenic structures. However, non-hexagonal rings are energetically unstable compared to the hexagonal counterparts, making it challenging to embed non-hexagonal rings into carbon-based nanostructures in a controllable manner. Here, we report an on-surface synthesis of graphene-like nanoribbons with periodically embedded four- and eight-membered rings. The scanning tunnelling microscopy and atomic force microscopy study revealed that four- and eight-membered rings are formed between adjacent perylene backbones with a planar configuration. The non-hexagonal rings as a topological modification markedly change the electronic properties of the nanoribbons. The highest occupied and lowest unoccupied ribbon states are mainly distributed around the eight- and four-membered rings, respectively. The realization of graphene-like nanoribbons comprising non-hexagonal rings demonstrates a controllable route to fabricate non-hexagonal rings in nanoribbons and makes it possible to unveil their unique properties induced by non-hexagonal rings.

          Abstract

          Graphene nanoribbons consist of carbon atoms arranged in a hexagonal lattice. Despite non-hexagonal rings generally being more unstable, the authors demonstrate the successful synthesis of graphene-like nanoribbons with periodically embedded four- and eight-membered carbon rings, with tailored electronic properties.

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          Most cited references38

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          Half-metallic graphene nanoribbons.

          Electrical current can be completely spin polarized in a class of materials known as half-metals, as a result of the coexistence of metallic nature for electrons with one spin orientation and insulating nature for electrons with the other. Such asymmetric electronic states for the different spins have been predicted for some ferromagnetic metals--for example, the Heusler compounds--and were first observed in a manganese perovskite. In view of the potential for use of this property in realizing spin-based electronics, substantial efforts have been made to search for half-metallic materials. However, organic materials have hardly been investigated in this context even though carbon-based nanostructures hold significant promise for future electronic devices. Here we predict half-metallicity in nanometre-scale graphene ribbons by using first-principles calculations. We show that this phenomenon is realizable if in-plane homogeneous electric fields are applied across the zigzag-shaped edges of the graphene nanoribbons, and that their magnetic properties can be controlled by the external electric fields. The results are not only of scientific interest in the interplay between electric fields and electronic spin degree of freedom in solids but may also open a new path to explore spintronics at the nanometre scale, based on graphene.
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            On-surface synthesis of graphene nanoribbons with zigzag edge topology

            Graphene-based nanostructures exhibit electronic properties that are not present in extended graphene. For example, quantum confinement in carbon nanotubes and armchair graphene nanoribbons leads to the opening of substantial electronic bandgaps that are directly linked to their structural boundary conditions. Nanostructures with zigzag edges are expected to host spin-polarized electronic edge states and can thus serve as key elements for graphene-based spintronics. The edge states of zigzag graphene nanoribbons (ZGNRs) are predicted to couple ferromagnetically along the edge and antiferromagnetically between the edges, but direct observation of spin-polarized edge states for zigzag edge topologies--including ZGNRs--has not yet been achieved owing to the limited precision of current top-down approaches. Here we describe the bottom-up synthesis of ZGNRs through surface-assisted polymerization and cyclodehydrogenation of specifically designed precursor monomers to yield atomically precise zigzag edges. Using scanning tunnelling spectroscopy we show the existence of edge-localized states with large energy splittings. We expect that the availability of ZGNRs will enable the characterization of their predicted spin-related properties, such as spin confinement and filtering, and will ultimately add the spin degree of freedom to graphene-based circuitry.
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              An extended defect in graphene as a metallic wire.

              Many proposed applications of graphene require the ability to tune its electronic structure at the nanoscale. Although charge transfer and field-effect doping can be applied to manipulate charge carrier concentrations, using them to achieve nanoscale control remains a challenge. An alternative approach is 'self-doping', in which extended defects are introduced into the graphene lattice. The controlled engineering of these defects represents a viable approach to creation and nanoscale control of one-dimensional charge distributions with widths of several atoms. However, the only experimentally realized extended defects so far have been the edges of graphene nanoribbons, which show dangling bonds that make them chemically unstable. Here, we report the realization of a one-dimensional topological defect in graphene, containing octagonal and pentagonal sp(2)-hybridized carbon rings embedded in a perfect graphene sheet. By doping the surrounding graphene lattice, the defect acts as a quasi-one-dimensional metallic wire. Such wires may form building blocks for atomic-scale, all-carbon electronics.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                31 March 2017
                2017
                : 8
                : 14924
                Affiliations
                [1 ]School of Physics and State Key Laboratory for Optoelectronic Materials and Technologies, Sun Yat-Sen University , 510275 Guangzhou, China
                [2 ]CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology , Beijing 100190, China
                [3 ]School of Chemistry, Sun Yat-Sen University , 510275 Guangzhou, China
                Author notes
                Article
                ncomms14924
                10.1038/ncomms14924
                5381008
                28361958
                fddad964-4624-426d-808e-029b667cfcd6
                Copyright © 2017, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 11 June 2016
                : 14 February 2017
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