Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials
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- 作者：Timothy H. Vo ; U. Gayani E. Perera ; Mikhail Shekhirev ; Mohammad Mehdi Pour ; Donna A. Kunkel ; Haidong Lu ; Alexei Gruverman ; Eli Sutter ; Mircea Cotlet ; Dmytro Nykypanchuk ; Percy Zahl ; Axel Enders ; Alexander Sinitskii ; Peter Sutter
- 刊名：Nano Letters
- 出版年：2015
- 出版时间：September 9, 2015
- 年：2015
- 卷：15
- 期：9
- 页码：5770-5777
- 全文大小：527K
- ISSN：1530-6992
文摘
Narrow graphene nanoribbons (GNRs) constructed by atomically precise bottom-up synthesis from molecular precursors have attracted significant interest as promising materials for nanoelectronics. But there has been little awareness of the potential of GNRs to serve as nanoscale building blocks of novel materials. Here we show that the substitutional doping with nitrogen atoms can trigger the hierarchical self-assembly of GNRs into ordered metamaterials. We use GNRs doped with eight N atoms per unit cell and their undoped analogues, synthesized using both surface-assisted and solution approaches, to study this self-assembly on a support and in an unrestricted three-dimensional (3D) solution environment. On a surface, N-doping mediates the formation of hydrogen-bonded GNR sheets. In solution, sheets of side-by-side coordinated GNRs can in turn assemble via van der Waals and 蟺-stacking interactions into 3D stacks, a process that ultimately produces macroscopic crystalline structures. The optoelectronic properties of these semiconducting GNR crystals are determined entirely by those of the individual nanoscale constituents, which are tunable by varying their width, edge orientation, termination, and so forth. The atomically precise bottom-up synthesis of bulk quantities of basic nanoribbon units and their subsequent self-assembly into crystalline structures suggests that the rapidly developing toolset of organic and polymer chemistry can be harnessed to realize families of novel carbon-based materials with engineered properties.