Ordered ultrathin films of perylenetetracarboxylic dianhydride (PTCDA) and dimethylperylenebis(dicarboximide) (Me-PTCDI) on Cu(100)

Characterization of structure and surface stoichiometry by LEED, TDMS, and XPS

A. Schmidt, T. J. Schuerlein, G. E. Collins, Neal R Armstrong

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Abstract

Ordered monolayer and multilayer thin films of perylene-3,4:9,10-tetracarboxylic dianhydride (PTCDA) have been grown on Cu(100) and MoS2(0001) single crystals. Low-energy electron diffraction (LEED) investigations have shown that PTCDA grows on Cu(100) in a commensurate rectangular lattice (4√2×5√2)R = 45°, whose dimensions (b1 = 14.5 Å, b2 = 18.1 Å) are significant different from those seen on the (0001) cleavage faces of single-crystal MoS2, where a coincident rectangular lattice with b1 = 13.1 Å and b2 = 21.2 Å is formed. This latter structure is much closer to the packing in the (102) plane of the bulk crystal of PTCDA. X-ray photoelectron spectra (XPS) and thermal desorption mass spectroscopy (TDMS) show that the first monolayer of PTCDA is strongly chemisorbed on the Cu surface. During the reaction with the copper surface each PTCDA molecule apparently loses the two bridging oxygen atoms in the anhydride groups, leading to a molecular system with close to the same dimensions and symmetry as the parent molecule. XPS data show that the adsorption on the surface of the weakly interacting metal dichalcogenide MoS2 is not accompanied by such a surface reaction. Support for this hypothesis was obtained by deposition of N,N′-dimethylperylene-3,4:9,10-bis(dicarboximide) (Me-PTCDI) on the Cu(100) surface. Me-PTCDI forms a rectangular (6 × 8) structure on Cu(100), with b1 = 15.3 Å and b2 = 20.4 Å. XPS data obtained for the deposition of this molecule on clean copper show that Me-PTCDI apparently loses both nitrogen imide groups, for the first monolayer adsorbed. TDMS data confirm this reactivity of Me-PTCDI. Me-PTCDI thin films appear to grow as islands, starting with the second monolayer, in contrast to PTCDA, which appears to adopt a layer-by-layer growth mode for the first six monolayers. Differences in the bulk crystal structures of these two molecules are believed to lead to these differences in growth mode; the layered bulk structure of PTCDA lends itself to a layered growth mode in multilayer ultrathin films.

Original languageEnglish (US)
Pages (from-to)11770-11779
Number of pages10
JournalJournal of Physical Chemistry
Volume99
Issue number30
StatePublished - 1995

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Thermal desorption
Low energy electron diffraction
Ultrathin films
Photoelectrons
Stoichiometry
stoichiometry
Monolayers
photoelectrons
mass spectroscopy
electron diffraction
desorption
Spectroscopy
X rays
Molecules
Multilayer films
molecules
x rays
Copper
copper
Perylene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{3a430952dbc44e25b3365dcb5b434e2e,
title = "Ordered ultrathin films of perylenetetracarboxylic dianhydride (PTCDA) and dimethylperylenebis(dicarboximide) (Me-PTCDI) on Cu(100): Characterization of structure and surface stoichiometry by LEED, TDMS, and XPS",
abstract = "Ordered monolayer and multilayer thin films of perylene-3,4:9,10-tetracarboxylic dianhydride (PTCDA) have been grown on Cu(100) and MoS2(0001) single crystals. Low-energy electron diffraction (LEED) investigations have shown that PTCDA grows on Cu(100) in a commensurate rectangular lattice (4√2×5√2)R = 45°, whose dimensions (b1 = 14.5 {\AA}, b2 = 18.1 {\AA}) are significant different from those seen on the (0001) cleavage faces of single-crystal MoS2, where a coincident rectangular lattice with b1 = 13.1 {\AA} and b2 = 21.2 {\AA} is formed. This latter structure is much closer to the packing in the (102) plane of the bulk crystal of PTCDA. X-ray photoelectron spectra (XPS) and thermal desorption mass spectroscopy (TDMS) show that the first monolayer of PTCDA is strongly chemisorbed on the Cu surface. During the reaction with the copper surface each PTCDA molecule apparently loses the two bridging oxygen atoms in the anhydride groups, leading to a molecular system with close to the same dimensions and symmetry as the parent molecule. XPS data show that the adsorption on the surface of the weakly interacting metal dichalcogenide MoS2 is not accompanied by such a surface reaction. Support for this hypothesis was obtained by deposition of N,N′-dimethylperylene-3,4:9,10-bis(dicarboximide) (Me-PTCDI) on the Cu(100) surface. Me-PTCDI forms a rectangular (6 × 8) structure on Cu(100), with b1 = 15.3 {\AA} and b2 = 20.4 {\AA}. XPS data obtained for the deposition of this molecule on clean copper show that Me-PTCDI apparently loses both nitrogen imide groups, for the first monolayer adsorbed. TDMS data confirm this reactivity of Me-PTCDI. Me-PTCDI thin films appear to grow as islands, starting with the second monolayer, in contrast to PTCDA, which appears to adopt a layer-by-layer growth mode for the first six monolayers. Differences in the bulk crystal structures of these two molecules are believed to lead to these differences in growth mode; the layered bulk structure of PTCDA lends itself to a layered growth mode in multilayer ultrathin films.",
author = "A. Schmidt and Schuerlein, {T. J.} and Collins, {G. E.} and Armstrong, {Neal R}",
year = "1995",
language = "English (US)",
volume = "99",
pages = "11770--11779",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "30",

}

TY - JOUR

T1 - Ordered ultrathin films of perylenetetracarboxylic dianhydride (PTCDA) and dimethylperylenebis(dicarboximide) (Me-PTCDI) on Cu(100)

T2 - Characterization of structure and surface stoichiometry by LEED, TDMS, and XPS

AU - Schmidt, A.

AU - Schuerlein, T. J.

AU - Collins, G. E.

AU - Armstrong, Neal R

PY - 1995

Y1 - 1995

N2 - Ordered monolayer and multilayer thin films of perylene-3,4:9,10-tetracarboxylic dianhydride (PTCDA) have been grown on Cu(100) and MoS2(0001) single crystals. Low-energy electron diffraction (LEED) investigations have shown that PTCDA grows on Cu(100) in a commensurate rectangular lattice (4√2×5√2)R = 45°, whose dimensions (b1 = 14.5 Å, b2 = 18.1 Å) are significant different from those seen on the (0001) cleavage faces of single-crystal MoS2, where a coincident rectangular lattice with b1 = 13.1 Å and b2 = 21.2 Å is formed. This latter structure is much closer to the packing in the (102) plane of the bulk crystal of PTCDA. X-ray photoelectron spectra (XPS) and thermal desorption mass spectroscopy (TDMS) show that the first monolayer of PTCDA is strongly chemisorbed on the Cu surface. During the reaction with the copper surface each PTCDA molecule apparently loses the two bridging oxygen atoms in the anhydride groups, leading to a molecular system with close to the same dimensions and symmetry as the parent molecule. XPS data show that the adsorption on the surface of the weakly interacting metal dichalcogenide MoS2 is not accompanied by such a surface reaction. Support for this hypothesis was obtained by deposition of N,N′-dimethylperylene-3,4:9,10-bis(dicarboximide) (Me-PTCDI) on the Cu(100) surface. Me-PTCDI forms a rectangular (6 × 8) structure on Cu(100), with b1 = 15.3 Å and b2 = 20.4 Å. XPS data obtained for the deposition of this molecule on clean copper show that Me-PTCDI apparently loses both nitrogen imide groups, for the first monolayer adsorbed. TDMS data confirm this reactivity of Me-PTCDI. Me-PTCDI thin films appear to grow as islands, starting with the second monolayer, in contrast to PTCDA, which appears to adopt a layer-by-layer growth mode for the first six monolayers. Differences in the bulk crystal structures of these two molecules are believed to lead to these differences in growth mode; the layered bulk structure of PTCDA lends itself to a layered growth mode in multilayer ultrathin films.

AB - Ordered monolayer and multilayer thin films of perylene-3,4:9,10-tetracarboxylic dianhydride (PTCDA) have been grown on Cu(100) and MoS2(0001) single crystals. Low-energy electron diffraction (LEED) investigations have shown that PTCDA grows on Cu(100) in a commensurate rectangular lattice (4√2×5√2)R = 45°, whose dimensions (b1 = 14.5 Å, b2 = 18.1 Å) are significant different from those seen on the (0001) cleavage faces of single-crystal MoS2, where a coincident rectangular lattice with b1 = 13.1 Å and b2 = 21.2 Å is formed. This latter structure is much closer to the packing in the (102) plane of the bulk crystal of PTCDA. X-ray photoelectron spectra (XPS) and thermal desorption mass spectroscopy (TDMS) show that the first monolayer of PTCDA is strongly chemisorbed on the Cu surface. During the reaction with the copper surface each PTCDA molecule apparently loses the two bridging oxygen atoms in the anhydride groups, leading to a molecular system with close to the same dimensions and symmetry as the parent molecule. XPS data show that the adsorption on the surface of the weakly interacting metal dichalcogenide MoS2 is not accompanied by such a surface reaction. Support for this hypothesis was obtained by deposition of N,N′-dimethylperylene-3,4:9,10-bis(dicarboximide) (Me-PTCDI) on the Cu(100) surface. Me-PTCDI forms a rectangular (6 × 8) structure on Cu(100), with b1 = 15.3 Å and b2 = 20.4 Å. XPS data obtained for the deposition of this molecule on clean copper show that Me-PTCDI apparently loses both nitrogen imide groups, for the first monolayer adsorbed. TDMS data confirm this reactivity of Me-PTCDI. Me-PTCDI thin films appear to grow as islands, starting with the second monolayer, in contrast to PTCDA, which appears to adopt a layer-by-layer growth mode for the first six monolayers. Differences in the bulk crystal structures of these two molecules are believed to lead to these differences in growth mode; the layered bulk structure of PTCDA lends itself to a layered growth mode in multilayer ultrathin films.

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EP - 11779

JO - Journal of Physical Chemistry

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