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Molecular Self-Assembly in a Poorly Screened Environment: F4TCNQ on Graphene/BN

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journal contribution
posted on 17.12.2015, 10:25 authored by Hsin-Zon Tsai, Arash A. Omrani, Sinisa Coh, Hyungju Oh, Sebastian Wickenburg, Young-Woo Son, Dillon Wong, Alexander Riss, Han Sae Jung, Giang D. Nguyen, Griffin F. Rodgers, Andrew S. Aikawa, Takashi Taniguchi, Kenji Watanabe, Alex Zettl, Steven G. Louie, Jiong Lu, Marvin L. Cohen, Michael F. Crommie
We report a scanning tunneling microscopy and noncontact atomic force microscopy study of close-packed 2D islands of tetrafluoro­tetracyanoquinodimethane (F4TCNQ) molecules at the surface of a graphene layer supported by boron nitride. While F4TCNQ molecules are known to form cohesive 3D solids, the intermolecular interactions that are attractive for F4TCNQ in 3D are repulsive in 2D. Our experimental observation of cohesive molecular behavior for F4TCNQ on graphene is thus unexpected. This self-assembly behavior can be explained by a novel solid formation mechanism that occurs when charged molecules are placed in a poorly screened environment. As negatively charged molecules coalesce, the local work function increases, causing electrons to flow into the coalescing molecular island and increase its cohesive binding energy.

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