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用于调控石墨烯纳米带间相互作用和石墨烯纳米孔的原子精确石墨烯纳米带的苯基功能化

Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores.

作者信息

Shekhirev Mikhail, Zahl Percy, Sinitskii Alexander

机构信息

Department of Chemistry , University of Nebraska-Lincoln , Lincoln , Nebraska 68588 , United States.

Center for Functional Nanomaterials , Brookhaven National Laboratory , Upton , New York 11973 , United States.

出版信息

ACS Nano. 2018 Aug 28;12(8):8662-8669. doi: 10.1021/acsnano.8b04489. Epub 2018 Aug 9.

Abstract

Graphene nanoribbons (GNRs) attract much attention from researchers due to their tunable physical properties and potential for becoming nanoscale building blocks of electronic devices. GNRs can be synthesized with atomic precision by on-surface approaches from specially designed molecular precursors. While a considerable number of ribbons with very diverse structures and properties have been demonstrated in recent years, there have been only limited examples of on-surface synthesized GNRs modified with functional groups. In this study, we designed a nanoribbon, in which the chevron GNR backbone is decorated with phenyl functionalities, and demonstrate the on-surface synthesis of these GNRs on Au(111). We show that the phenyl modification affects the assembly of the GNR polymer precursors through π-π interactions. Scanning tunneling spectroscopy of the modified GNRs on Au(111) revealed that they have a band gap of 2.50 ± 0.02 eV, which is comparable to that of the parent chevron GNR. The phenyl functionalization leads to a shift of the band edges to lower energies, suggesting that it could be a useful tool for the GNR band structure engineering. We also investigated lateral fusion of the phenyl-modified GNRs and demonstrate that it could be used to engineer different kinds of atomically precise graphene nanopores. A similar functionalization approach could be potentially applied to other GNRs to affect their on-surface assembly, modify their electronic properties, and realize graphene nanopores with a variety of structures.

摘要

石墨烯纳米带(GNRs)因其可调节的物理性质以及成为电子器件纳米级构建块的潜力而备受研究人员关注。GNRs可以通过表面合成方法,由特殊设计的分子前驱体以原子精度合成。尽管近年来已经展示了大量具有非常多样结构和性质的纳米带,但用官能团修饰的表面合成GNRs的例子仍然有限。在本研究中,我们设计了一种纳米带,其中人字形GNR主链用苯基官能团修饰,并展示了这些GNRs在Au(111)上的表面合成。我们表明苯基修饰通过π-π相互作用影响GNR聚合物前驱体的组装。对Au(111)上修饰的GNRs进行扫描隧道光谱分析表明,它们的带隙为2.50±0.02 eV,这与母体人字形GNR的带隙相当。苯基官能化导致带边向更低能量移动,这表明它可能是GNR能带结构工程的一个有用工具。我们还研究了苯基修饰的GNRs的横向融合,并证明它可用于设计不同种类的原子精确石墨烯纳米孔。类似的官能化方法可能潜在地应用于其他GNRs,以影响它们的表面组装、改变它们的电子性质,并实现具有各种结构的石墨烯纳米孔。

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