A series of novel electroactive and photoactive conjugated copolymers based on N-alkyl dithieno[3,2-b:2',3'-d]pyrroles (DTP) and thiophene (TH) units (DTP-co-THs) were synthesized using a Stille coupling reaction and exhibited molecular weights of 1.6 x 10(4) to 5.0 x 10(4) g/mol. The incorporation of soluble substituted thiophenes and planar DTP units resulted in low band gap, highly conductive polymers. DTP-co-THs exhibited excellent solubility in common organic solvents and formed high-quality films. Optical characterization revealed that the band gaps of DTP-co-THs were between 1.74 and 2.00 eV, lower than regioregular poly(3-alkylthiophenes). Electrochemical characterization showed that the HOMO energy levels of DTP-co-THs are between -4.68 and -4.96 eV. When doped, DTP-co-THs exhibited high conductivities up to 230 S/cm with excellent stability. The different thiophene substituent patterns' effect on the polymers' optical and electronic properties was then examined by density functional theory computations. The microstructure and surface morphologies of poly(2,6-(4-dodecyl-4H-bisthieno[3,2-b:2',3'-d]pyrrole)-random-2,5-(3-dodecylthiophene)) (P4) and poly(2-(4,4'-didodecyl-2,2'-bithiophen-5-yl)-4-octyl-4H-bisthieno[3,2-b:2',3'-d]pyrrole) (P6) thin films were studied by X-ray diffraction and atomic force microscopy. As-cast P4 and P6 thin films exhibited poorly defined, randomly ordered lamellar structure that improved significantly after thermal annealing. Field effect transistor devices fabricated from P4 and P6 showed typical p-channel transistor behavior. Interestingly, the mobilities of as-cast, less ordered samples were much higher than those observed after annealing. The highest values of maximum and average mobilities were observed for the polymer P6 as-cast (0.21 and 0.13 cm(2) V(-1) s(-1), respectively). One of our goals was to test the idea that high mobility and excellent electrical and structural reproducibility could perhaps be achieved by the creation of amorphous pi-conjugated materials that could possess long arrange pi connectivity on the microscopic scale. The results of these studies strongly suggest that the presence of highly ordered microcrystalline structures in thin films of organic semiconductors is not necessary for excellent performance of organic transistors.

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New thiazolothiazole-thiophene copolymers show high mobilities of ∼0.1 cm2/(V s) despite the fact that the polymer chains are disordered. The polymers demonstrated excellent stability, as they maintained the initial OFET performance after 50 days in ambient air (30−50% humidity).