Polymer semiconductors frequently form crystals or mesophases with lamellae, that comprise alternating layers of stacked backbones and side chains. Controlling lamellar orientation in films is essential for obtaining efficient charge carrier transport. Herein, lamellar orientation is investigated in an application-relevant setup: lamellae assembled on a substrate that strongly favors face-on orientation, but exposed to a film surface that promotes orientation along an "easy" direction, other than face on. It is assumed that the face-on order propagates from the substrate, but the lamellae bend to reduce their surface energy. A qualitative free-energy model is developed. The deformation is investigated as a function of film thickness, effective Young modulus, anchoring coefficient, and easy direction at the free surface. The calculations highlight the importance of elastic constants - lamellae can substantially deform already when Young moduli are only an order of magnitude smaller than the values that are reported for crystals. Softer Young moduli are expected when lamellar assembly occurs in a non-solidified mesophase that can be an equilibrium or (more speculatively) a transient state prior to crystallization. The alternative scenario of a two-layered film is also evaluated, where edge-on and face-on grains form, respectively, at the free surface and substrate.
Keywords: films; lamellae; microstructures; semiconducting polymers; theory.
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