• charge transport;
  • crystallization;
  • structure-property relations;
  • thin films;
  • X-ray


Using X-ray diffraction-based pole figures, we present quantitative analysis of the microstructure of poly(3-hexylthiophene) thin films of varying thicknesses, which allows us to determine the crystallinity and microstructure at the semiconductor-dielectric interface. We find that the interface is approximately one fourth as crystalline as the bulk of the material. Furthermore, the use of a self-assembled monolayer (SAM) enhances the density of interface-nucleated crystallites by a factor of ∼20. Charge transport measurements as a function of film thickness correlate with interface crystallinity. Hence, we establish the crucial role of SAMs as nucleating agents for increasing carrier mobility in field-effect devices. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013