Molecular Single Crystal Interfaces: Topographical Structure and Crystal Growth

Phillip W. Carter, Andrew C. Hillier, Michael D. Ward

Research output: Contribution to journalArticle

Abstract

Atomic force microscopy (AFM) reveals that the nanoscopic surface topography, and growth and dissolution mechanisms of molecular crystals are correlated with intermolecular bonding in the solid state. The orientation and growth of topographical features such as steps, ledges and kinks are primarily a manifestation of the enthalpically favored bonding directions within a given crystallographic plane. Hydrogen bonded crystals and charge transfer salts, which exhibit anisotropic solid state bonding, were found to have analogous topographical motifs in terms of surface features oriented along primary bonding directions. The role of these surface features, particularly ledges, in directing the nucleation and growth of secondary crystalline materials is described. Facile nucleation and oriented crystal growth is observed on substrate ledge sites, behavior that is attributed to lowering of the prenucleation aggregate free energy via “ledge directed epitaxy.” This involves a lattice match between the substrate and growing phase along the ledge direction, and equivalent dihedral angles of the substrate ledge sites and a pair of aggregate planes whose identity is assigned on the basis of the structure of the mature crystal.

Original languageEnglish (US)
Pages (from-to)53-60
Number of pages8
JournalMolecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals
Volume242
Issue number1
DOIs
StatePublished - 1994

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Molecular crystals
ledges
Crystallization
Crystal growth
crystal growth
Single crystals
single crystals
Nucleation
Substrates
Crystals
Surface topography
Dihedral angle
Epitaxial growth
Crystal lattices
nucleation
Free energy
crystals
solid state
Charge transfer
Hydrogen

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

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abstract = "Atomic force microscopy (AFM) reveals that the nanoscopic surface topography, and growth and dissolution mechanisms of molecular crystals are correlated with intermolecular bonding in the solid state. The orientation and growth of topographical features such as steps, ledges and kinks are primarily a manifestation of the enthalpically favored bonding directions within a given crystallographic plane. Hydrogen bonded crystals and charge transfer salts, which exhibit anisotropic solid state bonding, were found to have analogous topographical motifs in terms of surface features oriented along primary bonding directions. The role of these surface features, particularly ledges, in directing the nucleation and growth of secondary crystalline materials is described. Facile nucleation and oriented crystal growth is observed on substrate ledge sites, behavior that is attributed to lowering of the prenucleation aggregate free energy via “ledge directed epitaxy.” This involves a lattice match between the substrate and growing phase along the ledge direction, and equivalent dihedral angles of the substrate ledge sites and a pair of aggregate planes whose identity is assigned on the basis of the structure of the mature crystal.",
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N2 - Atomic force microscopy (AFM) reveals that the nanoscopic surface topography, and growth and dissolution mechanisms of molecular crystals are correlated with intermolecular bonding in the solid state. The orientation and growth of topographical features such as steps, ledges and kinks are primarily a manifestation of the enthalpically favored bonding directions within a given crystallographic plane. Hydrogen bonded crystals and charge transfer salts, which exhibit anisotropic solid state bonding, were found to have analogous topographical motifs in terms of surface features oriented along primary bonding directions. The role of these surface features, particularly ledges, in directing the nucleation and growth of secondary crystalline materials is described. Facile nucleation and oriented crystal growth is observed on substrate ledge sites, behavior that is attributed to lowering of the prenucleation aggregate free energy via “ledge directed epitaxy.” This involves a lattice match between the substrate and growing phase along the ledge direction, and equivalent dihedral angles of the substrate ledge sites and a pair of aggregate planes whose identity is assigned on the basis of the structure of the mature crystal.

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