Effect of Molecular Weight and Annealing of Poly(3‐hexylthiophene)s on the Performance of Organic Field‐Effect Transistors

Abstract The optical, structural, and electrical properties of thin layers made from poly(3‐hexylthiophene) (P3HT) samples of different molecular weights are presented. As reported in a previous paper by Kline et al., Adv. Mater. 2003 , 15 , 1519, the mobilities of these layers are a strong function of the molecular weight, with the largest mobility found for the largest molecular weight. Atomic force microscopy studies reveal a complex polycrystalline morphology which changes considerably upon annealing. X‐ray studies show the occurrence of a layered phase for all P3HT fractions, especially after annealing at 150 °C. However, there is no clear correlation between the differences in the transport properties and the data from structural investigations. In order to reveal the processes limiting the mobility in these layers, the transistor properties were investigated as a function of temperature. The mobility decreases continuously with increasing temperatures; with the same trend pronounced thermochromic effects of the P3HT films occur. Apparently, the polymer chains adopt a more twisted, disordered conformation at higher temperatures, leading to interchain transport barriers. We conclude that the backbone conformation of the majority of the bulk material rather than the crystallinity of the layer is the most crucial parameter controlling the charge transport in these P3HT layers. This interpretation is supported by the significant blue‐shift of the solid‐state absorption spectra with decreasing molecular weight, which is indicative of a larger distortion of the P3HT backbone in the low‐molecular weight P3HT layers.