Controlling gold atom penetration through alkanethiolate self-assembled monolayers on Au{111} by adjusting terminal group intermolecular interactions

Zihua Zhu, Thomas A. Daniel, Masato Maitani, Orlando M. Cabarcos, David L. Allara, Nicholas Winograd

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

The penetration behavior of thermally evaporated Au on S(CH 2)15CH3, S(CH2)15CO 2CH3, S(CH2)15-CO2H, K-modified S(CH2)15CO2CH3, and K-modified S(CH2)15CO2H self-assembled monolayers (SAM) on Au substrates is investigated. Gold is a particularly interesting metal since vapor-deposited Au atoms are known to pass through alkanethiolate SAMs on Au{111} substrates at room temperature. Here we show that it is possible to control Au penetration by adjusting the interactions between terminal groups. It is found that Au atoms evenly penetrate into the CH 3 and CO2CH3 films, forming smooth buried layers below the organic thin films. For the CO2H film, although Au atoms can still penetrate through it, filaments and mushroomlike clusters form due to H-bonding between film molecules. In the case of the K-modified CO 2-CH3 or CO2H films, however, most Au atoms form islands at the vacuum interface. These results suggest that van der Waals forces and H-bonds are not strong enough to block Au from going through but that ionic interactions are able to block Au penetration. The measurements were performed primarily using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and atomic force microscopy (AFM). The combination of these highly complementary probes provides a very useful strategy for the study of metal atom behavior on SAMs.

Original languageEnglish (US)
Pages (from-to)13710-13719
Number of pages10
JournalJournal of the American Chemical Society
Volume128
Issue number42
DOIs
StatePublished - Oct 25 2006

Fingerprint

Self assembled monolayers
Gold
Metals
Secondary Ion Mass Spectrometry
Atoms
Atomic Force Microscopy
Carbon Monoxide
Vacuum
Islands
Temperature
Van der Waals forces
Substrates
Secondary ion mass spectrometry
Atomic force microscopy
Vapors
Thin films
Molecules

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Zhu, Zihua ; Daniel, Thomas A. ; Maitani, Masato ; Cabarcos, Orlando M. ; Allara, David L. ; Winograd, Nicholas. / Controlling gold atom penetration through alkanethiolate self-assembled monolayers on Au{111} by adjusting terminal group intermolecular interactions. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 42. pp. 13710-13719.
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Controlling gold atom penetration through alkanethiolate self-assembled monolayers on Au{111} by adjusting terminal group intermolecular interactions. / Zhu, Zihua; Daniel, Thomas A.; Maitani, Masato; Cabarcos, Orlando M.; Allara, David L.; Winograd, Nicholas.

In: Journal of the American Chemical Society, Vol. 128, No. 42, 25.10.2006, p. 13710-13719.

Research output: Contribution to journalArticle

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AB - The penetration behavior of thermally evaporated Au on S(CH 2)15CH3, S(CH2)15CO 2CH3, S(CH2)15-CO2H, K-modified S(CH2)15CO2CH3, and K-modified S(CH2)15CO2H self-assembled monolayers (SAM) on Au substrates is investigated. Gold is a particularly interesting metal since vapor-deposited Au atoms are known to pass through alkanethiolate SAMs on Au{111} substrates at room temperature. Here we show that it is possible to control Au penetration by adjusting the interactions between terminal groups. It is found that Au atoms evenly penetrate into the CH 3 and CO2CH3 films, forming smooth buried layers below the organic thin films. For the CO2H film, although Au atoms can still penetrate through it, filaments and mushroomlike clusters form due to H-bonding between film molecules. In the case of the K-modified CO 2-CH3 or CO2H films, however, most Au atoms form islands at the vacuum interface. These results suggest that van der Waals forces and H-bonds are not strong enough to block Au from going through but that ionic interactions are able to block Au penetration. The measurements were performed primarily using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and atomic force microscopy (AFM). The combination of these highly complementary probes provides a very useful strategy for the study of metal atom behavior on SAMs.

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