Electron Injection to Control Self-Assembly and Disassembly of Phenylacetylene on Gold

ORAL

Abstract

The power of two-dimensional organic molecular systems for applications including electronics, functionalization and nanolithography is enabled by our ability to produce structures through self-assembly on a surface. Unfortunately, relying on thermal fluctuations to drive the surface attachment reactions has limited self-assembled molecules (SAMs) to little beyond alkanethiols on gold. We demonstrate a seminal example of non-thermal control over molecular self-assembly, where hot-electron injection rather than thermal fluctuations transform a disordered layer of weakly bonded hydrocarbon molecules into an ordered, dense monolayer. The process is reversible, in that injection of holes reverts to a disordered state. Since electron and hole injection is accomplished with a STM, unprecedented local control over ordered and disordered domains is achieved. STM imaging and correlated density functional calculations reveal that ordered domains consist of molecules vertically aligned and more strongly attached to the gold substrate through the acetylene tail, while disordered domains contain weakly bound molecules lying flat.

*Research was conducted at the CNMS, sponsored by the Division of Scientific User Facilities, U.S. Department of Energy.

Authors

  • Arthur P. Baddorf

    • Oak Ridge National Laboratory, Oak Ridge, TN
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Qing Li

    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Chengbo Han

    • NCSU
    • Department of Physics, North Carolina State University
  • J. Bernholc

    • Department of Physics, North Carolina State University
  • Humberto Terrones

    • The Pennsylvania State University
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Bobby Sumpter

    • CNMS, Oak Ridge National Lab
    • Oak Ridge National Laboratory
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN-37831
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Miguel Fuentes-Cabrera

    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
    • Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA
  • Jieyu Yi

    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Zheng Gai

    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
    • Oak Ridge National Laboratory
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Peter Maksymovych

    • Center for Nanophase Materials Sciences
    • Oak Ridge National Laboratory
    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
  • Minghu Pan

    • Center for Nanophase Materials Sciences, Oak Ridge National Laboratory
    • Oak Ridge National Laboratory