4.7 Article

Kinetic control of self-assembly using a low-energy electron beam

Journal

APPLIED SURFACE SCIENCE
Volume 600, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apsusc.2022.154106

Keywords

Low -Energy Electron Microscopy; Surfaces; Kinetics; On -Surface Reactions; Self-Assembly

Funding

  1. MEYS CR [19-01536S, LM2018110]
  2. GACR [19-01536S]
  3. CzechNanoLab - MEYS CR [LM2018110]
  4. MEYS CR through the e-INFRA CZ [CZ.02.2.69/0.0/0.0/20_079/0017436]
  5. ESF [19-01536S]
  6. [90140]

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Self-assembly and on-surface synthesis are important strategies for fabricating surface-confined nanostructures with atomic precision. The resulting structure is typically governed by temperature, but other external factors are rarely utilized to control the kinetics of chemical reactions and self-assembly. This study demonstrates that a low-energy electron beam can be used to steer the chemical reaction kinetics and induce the growth of molecular phases that cannot be obtained through thermal annealing.
Self-assembly and on-surface synthesis are vital strategies used for fabricating surface-confined 1D or 2D su-pramolecular nanoarchitectures with atomic precision. In many systems, the resulting structure is determined by the kinetics of the processes involved, i.e., reaction rate, on-surface diffusion, nucleation, and growth, all of which are typically governed by temperature. However, other external factors have been only scarcely harnessed to control the on-surface chemical reaction kinetics and self-assembly. Here, we show that a low-energy electron beam can be used to steer chemical reaction kinetics and induce the growth of molecular phases unattainable by thermal annealing. The electron beam provides a well-controlled means of promoting the elementary reaction step, i.e., deprotonation of carboxyl groups. The reaction rate increases with the increasing electron beam energy beyond the threshold energy of 6 eV. Our results offer the novel prospect of controlling self-assembly, enhancing the rate of reaction steps selectively, and thus altering the kinetic rate hierarchy.

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