High performance semiconducting polymers containing bis(bithiophenyl dithienothiophene)‐based repeating groups for organic thin film transistors

New dithienothiophene‐containing conjugated polymers, such as poly(2,6‐bis(2‐thiophenyl‐3‐dodecylthiophene‐2‐yl)dithieno3,2‐b;2′,3′‐d]thiophene, 4 and poly(2,6‐bis (2‐thiophenyl‐4‐dodecylthiophene‐2‐yl)dithieno3,2‐b;2′,3′‐d]thiophene, 8 have been successfully synthesized via Stille coupling reactions using dodecyl‐substituted thiophene‐based monomers, bistributyltin dithienothiophene, and bistributyltin bithiophene; these polymers have been fully characterized. The main difference between the two polymers is the substitution position of the dodecyl side chains in the repeating group. Grazing‐incidence X‐ray diffraction (GI‐XRD) gave clear evidence of edge‐on orientation of polycrystallites to the substrate. The semiconducting properties of the two polymers have been evaluated in organic thin film transistors (OTFTs). The two conjugated polymers 4 and 8 exhibit fairly high hole carrier mobilities as high as μ_ave = 0.05 cm²/Vs (I_ON/OFF = 3.42 × 10⁴) and μ_ave = 0.01 cm²/Vs, (I_ON/OFF = 1.3 × 10⁵), respectively, after thermal annealing process. The solvent annealed films underwent reorganization of the molecules to induce higher crystallinity. Well‐defined atomic force microscopy (AFM) topography supported a significant improvement in TFT device performance. The hole carrier mobilities of the solvent annealed films are comparable to those obtained for a thermally annealed sample, and were one‐order higher than those obtained with a pristine sample. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010