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Modeling the polymorphism of pentacene.

Christine C Mattheus1, Gilles A de Wijs, Robert A de Groot

  • 1Solid State Chemistry Laboratory, Materials Science Centre, Nijenborgh 4, NL-9747 AG Groningen, The Netherlands.

Journal of the American Chemical Society
|June 6, 2003
PubMed
Summary

Pentacene thin films exhibit diverse polymorphs with varying interlayer spacing. A new model links this spacing to molecular shifts within layers, explaining structural variations in pentacene crystals.

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Area of Science:

  • Materials Science
  • Solid-State Physics
  • Organic Electronics

Background:

  • Pentacene thin films are crucial organic semiconductors.
  • These films can crystallize into multiple polymorphs, each with distinct structural properties.
  • The interlayer spacing (d(001)) is a key characteristic influencing electronic properties.

Purpose of the Study:

  • To develop a theoretical model explaining the diverse interlayer spacings observed in pentacene polymorphs.
  • To correlate intralayer molecular shifts with observed interlayer spacing.
  • To investigate the role of intermolecular interactions in determining pentacene crystal structures.

Main Methods:

  • Development of a theoretical model based on intralayer molecular shifts.
  • Application of two theoretical models to analyze interatomic interactions (van der Waals, electrostatic, covalent).
  • Analysis of four known pentacene polymorphs, including substrate-induced ones.

Main Results:

  • A model was developed that rationalizes interlayer spacing (d(001)) based on intralayer shifts of pentacene molecules.
  • The model successfully explains the wide variety of interlayer spacings without distorting the characteristic herringbone molecular packing.
  • Consistent correlations between intralayer shifts and intermolecular interactions were found for two polymorphs.

Conclusions:

  • Intralayer molecular shifts are a primary factor determining interlayer spacing in pentacene thin films.
  • The proposed model provides a unified explanation for the structural diversity of pentacene polymorphs.
  • Further investigation into interlayer interactions is necessary for a complete understanding of substrate-induced polymorphs.