Stearic acid mediated growth of edge-on oriented bilayer poly(3-hexylthiophene) Langmuir films

Abstract

The growth and structural evolution of stearic acid (SA) blended poly(3-hexylthiophene) [P3HT] Langmuir and Langmuir-Blodgett (LB) films were studied using complimentary surface and interface sensitive techniques to understand the possibility of ordering and layering of promising charge carrier mobility polymers, at the air-water interface and on the transferred solid substrate. SA-induced and subsequent compression-induced transitions in P3HT structure, from aggregated-3D to soft-2D and from in-plane mixed to unmixed layer, are evident at low and high pressures, respectively. The blending of SA molecules enhances the amphiphilic character of P3HT, which reduces the extent of the out-of-plane aggregation to form edge-on oriented (EO) bottom side-chain folded-bilayer (f-BL) islands (of size ~60 nm) within SA monolayer (ML), of commensurate thickness (~2.6 nm). Further compression, gradually rejects the less hydrophilic f-BL islands from the mixed layer to form EO P3HT BL islands (of coverage in-tune with starting composition) on top of SA ML. The formation of nearly covered P3HT(BL)/SA(ML) structured film on solid substrate is evident for the first time, which (even of limited P3HT thickness) has immense importance in the device properties, as the current in the bottom-gated organic thin-film transistors is known to travel only within few ML region near gate-dielectric.

Keywords: 3D to 2D transition; Atomic force microscopy; Conjugated polymers; Edge-on orientation; Fatty acid blending; Langmuir and LB films; Ordering and layering; X-ray reflectivity.