An intrinsic relationship between molecular structure in self-assembled n-alkylsiloxane monolayers and deposition temperature

Atul N. Parikh, David L. Allara, Issam Ben Azouz, Francis Rondelez

Research output: Contribution to journalArticle

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Abstract

We have studied the effect of preparation temperature, in the range 5-65°C, on the structures of n-octadecylsiloxane monolayers prepared by self-assembly from dilute solution of n-octadecyltrichlorosilane onto the surface of freshly hydrated, oxidized silicon substrates. Structural features of the films were characterized using a combination of liquid drop contact angle measurements, null ellipsometry, and infrared transmission spectroscopy. The contact angle data confirm a previously reported observation of a critical temperature, Tc ∼ 28 ± 5°C, below which the surface energy is constant at a near-limiting value of a pure CH3 surface and above which the surface energy monotonically increases with increasing temperature. Coverages and chain organization, as measured by ellipsometry and vibrational spectroscopic features (peak positions and integrated intensities of methylene C-H stretching modes), respectively, show changes in the same temperature region as the wetting behavior. We conclude that when prepared below Tc, the films exhibit a heterogeneous structure with closely spaced islands of densely packed, nearly all-trans alkyl chains arranged nearly vertical to the surface. In contrast, when prepared above Tc, the films exhibit monotonically diminishing coverage with increasing preparation temperature and the alkyl chains increasingly assume higher contents of conformational disorder. Further, the infrared data indicate that these higher temperature films are heterogeneous with coexisting domains of high and low chain conformational ordering. All the data, taken together, are in good conformity with a film formation mechanism which involves, prior to siloxy group cross-linking, the intervention of intermediate structural phases of mobile alkylsiloxy species adsorbed on a water layer adjacent to the solid substrate surface. In support of this mechanism, a strong parallel is apparent between Tc and the triple point temperature at which gas (G), liquid-expanded (LE), and liquid-condensed (LC) phases coexist for C18 chain Langmuir monolayers at the air/bulk water interface. Below Tc the self-assembled film structure is similar to that of the nearly pure LC Langmuir phase while above Tc the film structure is similar to that of coexisting LE and LC phases. Deviations of the self-assembled film structures for the analogous equilibrium Langmuir phase structures occur at higher preparation temperatures and are rationalized in terms of both the known occurrence of nonequilibrium phases in Langmuir films above the triple point temperature and the relative acceleration of the Si-O-Si cross-linking reaction in the self-assembled film to form structures with frozen-in defects.

Original languageEnglish (US)
Pages (from-to)7577-7590
Number of pages14
JournalJournal of Physical Chemistry
Volume98
Issue number31
StatePublished - 1994
Externally publishedYes

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Molecular structure
Monolayers
molecular structure
Liquids
Temperature
temperature
liquids
Ellipsometry
Interfacial energy
Contact angle
preparation
surface energy
ellipsometry
Infrared transmission
Water
Langmuir Blodgett films
Silicon
Substrates
monomolecular films
Phase structure

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

An intrinsic relationship between molecular structure in self-assembled n-alkylsiloxane monolayers and deposition temperature. / Parikh, Atul N.; Allara, David L.; Azouz, Issam Ben; Rondelez, Francis.

In: Journal of Physical Chemistry, Vol. 98, No. 31, 1994, p. 7577-7590.

Research output: Contribution to journalArticle

Parikh, Atul N. ; Allara, David L. ; Azouz, Issam Ben ; Rondelez, Francis. / An intrinsic relationship between molecular structure in self-assembled n-alkylsiloxane monolayers and deposition temperature. In: Journal of Physical Chemistry. 1994 ; Vol. 98, No. 31. pp. 7577-7590.
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T1 - An intrinsic relationship between molecular structure in self-assembled n-alkylsiloxane monolayers and deposition temperature

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AU - Allara, David L.

AU - Azouz, Issam Ben

AU - Rondelez, Francis

PY - 1994

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N2 - We have studied the effect of preparation temperature, in the range 5-65°C, on the structures of n-octadecylsiloxane monolayers prepared by self-assembly from dilute solution of n-octadecyltrichlorosilane onto the surface of freshly hydrated, oxidized silicon substrates. Structural features of the films were characterized using a combination of liquid drop contact angle measurements, null ellipsometry, and infrared transmission spectroscopy. The contact angle data confirm a previously reported observation of a critical temperature, Tc ∼ 28 ± 5°C, below which the surface energy is constant at a near-limiting value of a pure CH3 surface and above which the surface energy monotonically increases with increasing temperature. Coverages and chain organization, as measured by ellipsometry and vibrational spectroscopic features (peak positions and integrated intensities of methylene C-H stretching modes), respectively, show changes in the same temperature region as the wetting behavior. We conclude that when prepared below Tc, the films exhibit a heterogeneous structure with closely spaced islands of densely packed, nearly all-trans alkyl chains arranged nearly vertical to the surface. In contrast, when prepared above Tc, the films exhibit monotonically diminishing coverage with increasing preparation temperature and the alkyl chains increasingly assume higher contents of conformational disorder. Further, the infrared data indicate that these higher temperature films are heterogeneous with coexisting domains of high and low chain conformational ordering. All the data, taken together, are in good conformity with a film formation mechanism which involves, prior to siloxy group cross-linking, the intervention of intermediate structural phases of mobile alkylsiloxy species adsorbed on a water layer adjacent to the solid substrate surface. In support of this mechanism, a strong parallel is apparent between Tc and the triple point temperature at which gas (G), liquid-expanded (LE), and liquid-condensed (LC) phases coexist for C18 chain Langmuir monolayers at the air/bulk water interface. Below Tc the self-assembled film structure is similar to that of the nearly pure LC Langmuir phase while above Tc the film structure is similar to that of coexisting LE and LC phases. Deviations of the self-assembled film structures for the analogous equilibrium Langmuir phase structures occur at higher preparation temperatures and are rationalized in terms of both the known occurrence of nonequilibrium phases in Langmuir films above the triple point temperature and the relative acceleration of the Si-O-Si cross-linking reaction in the self-assembled film to form structures with frozen-in defects.

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