Modification of the Poly(bisdodecylquaterthiophene) Structure for High and Predominantly Nonionic Conductivity with Matched Dopants

Four p-type polymers were synthesized by modifying poly(bisdodecylquaterthiophene) (PQT12) to increase oxidizability by p-dopants. A sulfur atom is inserted between the thiophene rings and dodecyl chains, and/or 3,4-ethylenedioxy groups are appended to thiophene rings of PQT12. Doped with NOBF4, PQTS12 (with sulfur in side chains) shows a conductivity of 350 S cm(-1), the highest reported nonionic conductivity among films made from dopant polymer solutions. Doped with tetrafluorotetracyanoquinodimethane (F4TCNQ), PDTDE12 (with 3,4-ethylenedioxy groups on thiophene rings) shows a conductivity of 140 S cm(-1). The converse combinations of polymer and dopant and formulations using a polymer with both the sulfur and ethylenedioxy modifications showed lower conductivities. The conductivities are stable in air without extrinsic ion contributions associated with PEDOT:PSS that cannot support sustained current or thermoelectric voltage. Efficient charge transfer, tighter pi-pi stacking, and strong intermolecular coupling are responsible for the conductivity. Values of nontransient Seebeck coefficient and conductivity agree with empirical modeling for materials with these levels of pure hole conductivity; the power factor compares favorably with prior p-type polymers made by the alternative process of immersion of polymer films into dopant solutions. Models and conductivities point to significant mobility increases induced by dopants on the order of 1-5 cm(2) V-1 s(-1), supported by field-effect transistor studies of slightly doped samples. The thermal conductivities were in the range of 0.2-0.5 W m(-1) K-1, typical for conductive polymers. The results point to further enhancements that could be obtained by increasing doped polymer mobilities.