Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions

Small angle X-ray scattering (SAXS) studies of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH–PPV) with varying conjugation, and polyethylene dioxythiophene complexed with polystyrene sulfonate (PEDOT–PSS) in different solvents have shown the importance of the role of π-electron conjugation and solvent–chain interactions in controlling the chain conformation and assembly. In MEH–PPV, by increasing the extent of conjugation from 30 to 100%, the persistence length (lp) increases from 20 to 66 A. Moreover, a pronounced second peak in the pair distribution function has been observed in the fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. In the case of PEDOT–PSS, the chains undergo solvent induced expansion and enhanced chain organization. The clusters formed by chains are better correlated in dimethyl sulfoxide (DMSO) solution than water, as observed in the scattered intensity profiles. The values of radius of gyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtained from the unified scattering function (Beaucage) analysis, give evidence for chain expansion from compact (in water) to an extended coil in DMSO solutions, which is consistent with the Kratky plot analysis. The mechanism of this transition and the increase in dc conductivity of PEDOT–PSS in DMSO solution are discussed. The onset frequency for the increase in ac conduction, as well as its temperature dependence, probes the extent of the connectivity in the PEDOT–PSS system. The enhanced charge transport in PEDOT–PSS in DMSO is attributed to the extended chain conformation, as observed in the SAXS results.