Applications of atomic force microscopy to structural characterization of organic thin films

J. A. Zasadzinski, R. Viswanathan, D. K. Schwartz, J. Garnaes, L. Madsen, S. Chiruvolu, J. T. Woodward, M. L. Longo

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

The atomic force microscope (AFM) has created exciting new possibilities for imaging thin organic films under ambient conditions at length scales ranging from tens of microns to the sub-molecular scale. We present images of thin organic films prepared by the Langmuir-Blodgett (LB) and self-assembly (SA) techniques that demonstrate the possibilities and limitations of the AFM. Atomic force microscope images of LB films show that manganese arachidate (MnA2) monolayers are short-range ordered and lead stearate (PbSt2) monolayers are long-range ordered on crystalline mica substrates, but disordered on amorphous oxidized silicon substrates. The lattice structures of PbSt2 and MnA2 monolayers on mica were previously unknown and have larger lattice parameters and molecular areas than do multilayer films of the same materials, indicating the strong interactions with the larger mica lattice. Multilayer films of PbSt2, cadmium arachidate (CdA2), and MnA2, have centered rectangular "herringbone" lattices on both silicon and mica substrates. After sufficient layers, the effect of the mica substrate is eliminated and the lattice parameters and area per molecule of films deposited on mica relax to those of multilayer films on amorphous oxidized silicon. This limiting area per molecule correlates well with the degree of ionic versus covalent bonding as estimated by the Pauling electronegativity, with barium arachidate (BaA2) > MnA2 > CdA2 > PbSt2. For BaA2 and MnA2 the increased molecular area is sufficient to induce a tilt in the molecular packing. The lattice parameters, symmetry, and area per molecule are independent of the length of the alkane chain of the fatty acid for all cations and substrates examined. AFM images also show that self-assembled monolayers of octadecyltrichlorosilane (OTS) form on mica by nucleating isolated, self-similar domains. With increasing coverage, the fractal dimension of the growing domains evolves from 1.6 to 1.8. At higher coverage, continued growth is limited by adsorption from solution.

Original languageEnglish (US)
Pages (from-to)305-333
Number of pages29
JournalColloids and Surfaces A: Physicochemical and Engineering Aspects
Volume93
Issue numberC
DOIs
StatePublished - Dec 5 1994

Bibliographical note

Funding Information:
C. Praterf or pastc ollaborationsh, elpfulc omments and ongoing discussionsI. also especiallyt hank Paul Hansmaa nd Calvin Quatef or their generous mentoringd uring the developmento f my STM and AFM laboratory.F inancial support was provided by the Office of Naval Research,G rant #NOOO14-90-J-1551a, Whitaker Foundation BiomedicalE ngineeringG rant, a National Science Foundation Presidential Young Investigator Award #CBT 86-57444N, SF grantsC TS90-IS537 and CTS-9212790, the National Institutes of Health underg rantG M 47334a, nd the Donorso f the Petroleum Research Foundation. D.K.S. acknowledgessu pport under grant CHE89-02354 from NSF (throughC . Knobler).

Keywords

  • Atomic force microscopy
  • Herringbone lattices
  • Langmuir-Blodgett films
  • Organic thin films
  • Triclinic

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