Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films

A. Hooper, G. L. Fisher, K. Konstadinidis, D. Jung, H. Nguyen, R. Opila, R. W. Collins, Nicholas Winograd, D. L. Allara

Research output: Contribution to journalArticle

128 Citations (Scopus)

Abstract

The interaction of vapor-deposited A1 atoms with self-assembled monolayers (SAMs) of HS(CH2)15CH3 and HS(CH2)15CO2CH3 chemisorbed at Au{111} surfaces was studied using X-ray photoelectron spectroscopy, infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and spectroscopic ellipsometry. For the CH3-terminated SAM, no reaction with C-H or C-C bonds was observed. For total A1 doses up to κ 12 atoms/nm2, penetration the the Au-S interface occurs with no disruption of the average chain conformation and tilt, indicating formation of a highly uniform κ1:1 A1 adlayer on the Au. Subsequently, penetration ceases and a metallic overlayer begins to form at the SAMvacuum interface. These results are explained in terms of an initial dynamic hopping of the S headgroups on the Au lattice, which opens transient diffusion channels to the Au-S interface, and the closing of these channels upon completion of the adlayer. In contrast, A1 atom interactions with the CO2CH3-terminated SAM are restricted to the vacuum interface, where in the initial stages discrete organometallic products form via reaction with the CO2CH3 group. First, a 1:1 complex forms with a reduced C==O bond and an intact CH3 moiety. Further exposure leads to the additional reaction of about four A1 atoms per ester, after which a metallic overlayer nucleates in the form of clusters. After the growth progresses to κ30 Å, the clusters coalesce into a uniform metallic film. These results illustrate the extraordinary degree of control that organic substrates can exert during the course of metal film formation.

Original languageEnglish (US)
Pages (from-to)8052-8064
Number of pages13
JournalJournal of the American Chemical Society
Volume121
Issue number35
DOIs
StatePublished - Sep 8 1999

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Secondary Ion Mass Spectrometry
Photoelectron Spectroscopy
Vacuum
Aluminum
Spectrum Analysis
Esters
Self assembled monolayers
Nucleation
Metals
Vapors
Atoms
Growth
Metallic films
Spectroscopic ellipsometry
Organometallics
Secondary ion mass spectrometry
Conformations
Infrared spectroscopy
X ray photoelectron spectroscopy
Substrates

All Science Journal Classification (ASJC) codes

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

Cite this

Hooper, A., Fisher, G. L., Konstadinidis, K., Jung, D., Nguyen, H., Opila, R., ... Allara, D. L. (1999). Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films. Journal of the American Chemical Society, 121(35), 8052-8064. https://doi.org/10.1021/ja9835234
Hooper, A. ; Fisher, G. L. ; Konstadinidis, K. ; Jung, D. ; Nguyen, H. ; Opila, R. ; Collins, R. W. ; Winograd, Nicholas ; Allara, D. L. / Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films. In: Journal of the American Chemical Society. 1999 ; Vol. 121, No. 35. pp. 8052-8064.
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abstract = "The interaction of vapor-deposited A1 atoms with self-assembled monolayers (SAMs) of HS(CH2)15CH3 and HS(CH2)15CO2CH3 chemisorbed at Au{111} surfaces was studied using X-ray photoelectron spectroscopy, infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and spectroscopic ellipsometry. For the CH3-terminated SAM, no reaction with C-H or C-C bonds was observed. For total A1 doses up to κ 12 atoms/nm2, penetration the the Au-S interface occurs with no disruption of the average chain conformation and tilt, indicating formation of a highly uniform κ1:1 A1 adlayer on the Au. Subsequently, penetration ceases and a metallic overlayer begins to form at the SAMvacuum interface. These results are explained in terms of an initial dynamic hopping of the S headgroups on the Au lattice, which opens transient diffusion channels to the Au-S interface, and the closing of these channels upon completion of the adlayer. In contrast, A1 atom interactions with the CO2CH3-terminated SAM are restricted to the vacuum interface, where in the initial stages discrete organometallic products form via reaction with the CO2CH3 group. First, a 1:1 complex forms with a reduced C==O bond and an intact CH3 moiety. Further exposure leads to the additional reaction of about four A1 atoms per ester, after which a metallic overlayer nucleates in the form of clusters. After the growth progresses to κ30 {\AA}, the clusters coalesce into a uniform metallic film. These results illustrate the extraordinary degree of control that organic substrates can exert during the course of metal film formation.",
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Hooper, A, Fisher, GL, Konstadinidis, K, Jung, D, Nguyen, H, Opila, R, Collins, RW, Winograd, N & Allara, DL 1999, 'Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films', Journal of the American Chemical Society, vol. 121, no. 35, pp. 8052-8064. https://doi.org/10.1021/ja9835234

Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films. / Hooper, A.; Fisher, G. L.; Konstadinidis, K.; Jung, D.; Nguyen, H.; Opila, R.; Collins, R. W.; Winograd, Nicholas; Allara, D. L.

In: Journal of the American Chemical Society, Vol. 121, No. 35, 08.09.1999, p. 8052-8064.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Chemical effects of methyl and methyl ester groups on the nucleation and growth of vapor-deposited aluminum films

AU - Hooper, A.

AU - Fisher, G. L.

AU - Konstadinidis, K.

AU - Jung, D.

AU - Nguyen, H.

AU - Opila, R.

AU - Collins, R. W.

AU - Winograd, Nicholas

AU - Allara, D. L.

PY - 1999/9/8

Y1 - 1999/9/8

N2 - The interaction of vapor-deposited A1 atoms with self-assembled monolayers (SAMs) of HS(CH2)15CH3 and HS(CH2)15CO2CH3 chemisorbed at Au{111} surfaces was studied using X-ray photoelectron spectroscopy, infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and spectroscopic ellipsometry. For the CH3-terminated SAM, no reaction with C-H or C-C bonds was observed. For total A1 doses up to κ 12 atoms/nm2, penetration the the Au-S interface occurs with no disruption of the average chain conformation and tilt, indicating formation of a highly uniform κ1:1 A1 adlayer on the Au. Subsequently, penetration ceases and a metallic overlayer begins to form at the SAMvacuum interface. These results are explained in terms of an initial dynamic hopping of the S headgroups on the Au lattice, which opens transient diffusion channels to the Au-S interface, and the closing of these channels upon completion of the adlayer. In contrast, A1 atom interactions with the CO2CH3-terminated SAM are restricted to the vacuum interface, where in the initial stages discrete organometallic products form via reaction with the CO2CH3 group. First, a 1:1 complex forms with a reduced C==O bond and an intact CH3 moiety. Further exposure leads to the additional reaction of about four A1 atoms per ester, after which a metallic overlayer nucleates in the form of clusters. After the growth progresses to κ30 Å, the clusters coalesce into a uniform metallic film. These results illustrate the extraordinary degree of control that organic substrates can exert during the course of metal film formation.

AB - The interaction of vapor-deposited A1 atoms with self-assembled monolayers (SAMs) of HS(CH2)15CH3 and HS(CH2)15CO2CH3 chemisorbed at Au{111} surfaces was studied using X-ray photoelectron spectroscopy, infrared spectroscopy, time-of-flight secondary ion mass spectrometry, and spectroscopic ellipsometry. For the CH3-terminated SAM, no reaction with C-H or C-C bonds was observed. For total A1 doses up to κ 12 atoms/nm2, penetration the the Au-S interface occurs with no disruption of the average chain conformation and tilt, indicating formation of a highly uniform κ1:1 A1 adlayer on the Au. Subsequently, penetration ceases and a metallic overlayer begins to form at the SAMvacuum interface. These results are explained in terms of an initial dynamic hopping of the S headgroups on the Au lattice, which opens transient diffusion channels to the Au-S interface, and the closing of these channels upon completion of the adlayer. In contrast, A1 atom interactions with the CO2CH3-terminated SAM are restricted to the vacuum interface, where in the initial stages discrete organometallic products form via reaction with the CO2CH3 group. First, a 1:1 complex forms with a reduced C==O bond and an intact CH3 moiety. Further exposure leads to the additional reaction of about four A1 atoms per ester, after which a metallic overlayer nucleates in the form of clusters. After the growth progresses to κ30 Å, the clusters coalesce into a uniform metallic film. These results illustrate the extraordinary degree of control that organic substrates can exert during the course of metal film formation.

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