Lee Jaekwang, Yang Zhiqing, Zhou Wu, Pennycook Stephen J, Pantelides Sokrates T, Chisholm Matthew F
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831;Department of Physics and Astronomy, Vanderbilt University, Nashville, TN 37235;
Shenyang National Laboratory for Material Science, Institute of Metal Research, Chinese Academy of Science, Shenyang 110016, China; and.
Proc Natl Acad Sci U S A. 2014 May 27;111(21):7522-6. doi: 10.1073/pnas.1400767111. Epub 2014 May 12.
Graphene is an ultrathin, impervious membrane. The controlled introduction of nanoscale pores in graphene would lead to applications that involve water purification, chemical separation, and DNA sequencing. However, graphene nanopores are unstable against filling by carbon adatoms. Here, using aberration-corrected scanning transmission electron microscopy and density-functional calculations, we report that Si atoms stabilize graphene nanopores by bridging the dangling bonds around the perimeter of the hole. Si-passivated pores remain intact even under intense electron beam irradiation, and they were observed several months after the sample fabrication, demonstrating that these structures are intrinsically robust and stable against carbon filling. Theoretical calculations reveal the underlying mechanism for this stabilization effect: Si atoms bond strongly to the graphene edge, and their preference for tetrahedral coordination forces C adatoms to form dendrites sticking out of the graphene plane, instead of filling the nanopore. Our results provide a novel way to develop stable nanopores, which is a major step toward reliable graphene-based molecular translocation devices.
石墨烯是一种超薄且不可渗透的薄膜。在石墨烯中可控地引入纳米级孔隙将带来涉及水净化、化学分离和DNA测序的应用。然而,石墨烯纳米孔对于被碳吸附原子填充是不稳定的。在此,我们使用像差校正扫描透射电子显微镜和密度泛函计算,报告硅原子通过桥接孔周边的悬空键来稳定石墨烯纳米孔。即使在强电子束照射下,硅钝化的孔隙仍保持完整,并且在样品制备几个月后仍能观察到,这表明这些结构本质上是坚固的且对碳填充稳定。理论计算揭示了这种稳定化效应的潜在机制:硅原子与石墨烯边缘强烈结合,并且它们对四面体配位的偏好促使碳吸附原子形成伸出石墨烯平面的枝晶,而不是填充纳米孔。我们的结果提供了一种开发稳定纳米孔的新方法,这是迈向可靠的基于石墨烯的分子转运器件的重要一步。