Two-dimensional charge transport in self-organized, high-mobility conjugated polymers

Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix(I). This has important consequences for electrical properties of these materials: charge transport is usually limited by the most difficult hopping processes and is therefore dominated by the disordered matrix, resulting in low charge-carrier mobilities(2) (less than or equal to 10(-5) cm(2)V(-1)s(-1)). Here we use thin-film, field-effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT, Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different orientations-parallel and normal to the substrate-the mobilities of which differ by more than a factor of 100, and can reach values as high as 0.1 cm(2) V-1 s(-1) (refs 3, 4). Optical spectroscopy of the field-induced charge, combined with the mobility anisotropy, reveals the two-dimensional interchain character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications of polymer transistors in logic circuits(5) and active-matrix displays(4,6).