Modification of self-assembled monolayers of perfluoroterphenyl-substituted alkanethiols by low-energy electrons

Frederick Chesneau, Hicham Hamoudi, Björn Schüpbach, Andreas Terfort, Michael Zharnikov

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Using self-assembled monolayers (SAMs) of perfluoroterphenyl-substituted alkanethiols (FTPn) on Au(111) as test systems, we studied the effect of low-energy (10 eV) electron irradiation on fluorinated aromatic SAMs. FTPn films were found to mimic the typical behavior of aromatic hydrocarbon SAMs under ionizing radiation. The dominant process is the cleavage of C-F bonds in the FTP moieties followed by desorption of the released fluorine atoms, rapid conformational and orientational disordering, and cross-linking between the residual skeletons of the FTP backbones. The stability of these skeletons and the development of a cross-linked network hinder other typical irradiation-induced processes such as desorption of molecular fragments and damage of the headgroup-substrate interface. Along with these findings, FTPn SAMs gave a unique possibility to monitor the destiny of the fluorine atoms, which are analogues of the hydrogen atoms in the respective hydrocarbon systems. The extent of fluorine release upon irradiation was estimated and the cleavage of C-F bonds was found to be the main channel of this release, which is in striking contrast to fluorocarbon aliphatic monolayers for which such a release is dominated by the desorption of fluorocarbon fragments. Finally, irradiation-induced reorientation of FTPn films at very small irradiation doses was observed suggesting that their structure is kinetically trapped and can be relaxed toward the thermodynamic minimum by physical means.

Original languageEnglish
Pages (from-to)4773-4782
Number of pages10
JournalJournal of Physical Chemistry C
Volume115
Issue number11
DOIs
Publication statusPublished - 24 Mar 2011
Externally publishedYes

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Self assembled monolayers
Fluorine
Irradiation
electron energy
fluorine
Fluorocarbons
Desorption
irradiation
Electrons
desorption
fluorocarbons
musculoskeletal system
Atoms
cleavage
hydrocarbons
fragments
Aromatic Hydrocarbons
Electron irradiation
Aromatic hydrocarbons
Ionizing radiation

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

Modification of self-assembled monolayers of perfluoroterphenyl-substituted alkanethiols by low-energy electrons. / Chesneau, Frederick; Hamoudi, Hicham; Schüpbach, Björn; Terfort, Andreas; Zharnikov, Michael.

In: Journal of Physical Chemistry C, Vol. 115, No. 11, 24.03.2011, p. 4773-4782.

Research output: Contribution to journalArticle

Chesneau, Frederick ; Hamoudi, Hicham ; Schüpbach, Björn ; Terfort, Andreas ; Zharnikov, Michael. / Modification of self-assembled monolayers of perfluoroterphenyl-substituted alkanethiols by low-energy electrons. In: Journal of Physical Chemistry C. 2011 ; Vol. 115, No. 11. pp. 4773-4782.
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