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由氟代前体制备的自上而下的石墨烯纳米带的聚合物自组装。

Interpolymer Self-Assembly of Bottom-up Graphene Nanoribbons Fabricated from Fluorinated Precursors.

机构信息

Fujitsu Laboratory Ltd. and Fujitsu Limited , 10-1 Morinosato-Wakamiya , Atsugi , Kanagawa 243-0197 , Japan.

Graduate School of Materials Science , Nara Institute of Science and Technology , 8916-5 Takayama-cho , Ikoma , Nara 630-0192 , Japan.

出版信息

ACS Appl Mater Interfaces. 2018 Sep 19;10(37):31623-31630. doi: 10.1021/acsami.8b11017. Epub 2018 Sep 10.

DOI:10.1021/acsami.8b11017
PMID:30148601
Abstract

Interpolymer self-assembly of bottom-up graphene nanoribbons (GNRs) has been realized by using fluorinated anthracene trimer precursors (HFH-DBTA) deposited onto heated Au(111) substrate. Whereas polymers derived from conventional precursor [10,10'-dibromo-9,9'-bianthryl (DBBA)] are adsorbed on Au(111) without apparent close packing, poly-HFH polymers derived from HFH-DBTA are densely self-assembled and require a long annealing time for cyclo-dehydrogenation because of the steric hindrance. First-principles calculations based on density functional theory revealed that the partially fluorinated edges of HFH-DBTA make molecular-substrate interaction weaker than that of DBBA, accelerate desorption, and leave islands of accumulated and locally aligned polymers. The partially fluorinated precursors also induce templating effects in interpolymer stacking because of H-F hydrogen bonding and F-F repulsion. The statistical analysis revealed that 84% of GNRs is parallel to the adjacent GNRs in the case of HFH-DBTA precursors. Field-effect transistors (FETs) were fabricated using such locally aligned multiple GNRs as channels. It has been found that on average, the on-current of the FETs is three times larger than that of FETs using less-aligned GNR channels made from the conventional DBBA precursors.

摘要

通过在加热的 Au(111) 基底上沉积氟化蒽三聚物前体 (HFH-DBTA),实现了自下而上的石墨烯纳米带 (GNRs) 的聚合物自组装。而源自常规前体 [10,10'-二溴-9,9'-联二蒽 (DBBA)] 的聚合物在 Au(111) 上没有明显的紧密堆积,而是被吸附,而源自 HFH-DBTA 的聚 HFH 聚合物则由于空间位阻而密集自组装,需要较长的退火时间才能进行环脱氢反应。基于密度泛函理论的第一性原理计算表明,HFH-DBTA 的部分氟化边缘使分子-基底相互作用比 DBBA 弱,加速了脱附,并留下了积累和局部排列聚合物的岛。部分氟化的前体还由于 H-F 氢键和 F-F 排斥作用在聚合物间堆积中诱导模板效应。统计分析表明,在 HFH-DBTA 前体的情况下,84%的 GNRs 与相邻的 GNRs 平行。使用这种局部排列的多个 GNR 作为沟道制造了场效应晶体管 (FET)。结果发现,平均而言,使用源自常规 DBBA 前体的对齐程度较低的 GNR 沟道的 FET 的导通电流比 FET 大三倍。

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