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This study investigates the solid-state charge transport properties of the oxidized forms of dioxythiophene-based alternating copolymers consisting of an oligoether-functionalized 3,4-propylenedioxythiophene (ProDOT) copolymerized with different aryl groups, dimethyl ProDOT (DMP), 3,4-ethylenedioxythiophene (EDOT), and 3,4-phenylenedioxythiophene (PheDOT), respectively, to yield copolymers P(OE3)-D, P(OE3)-E, and P(OE3)-Ph. At a dopant concentration of 5 mM FeTos3, the electrical conductivities of these copolymers vary significantly (ranging between 9 and 195 S cm-1) with the EDOT copolymer, P(OE3)-E, achieving the highest electrical conductivity. UV-vis-NIR and X-ray spectroscopies show differences in both susceptibility to oxidative doping and extent of oxidation for the P(OE3) series, with P(OE3)-E being the most doped. Wide-angle X-ray scattering measurements indicate that P(OE3)-E generally demonstrates the lowest paracrystallinity values in the series, as well as relatively small π-π stacking distances. The significant (i.e., order of magnitude) increase in electrical conductivity of doped P(OE3)-E films versus doped P(OE3)-D or P(OE3)-Ph films can therefore be attributed to P(OE3)-E exhibiting both the highest carrier ratios in the P(OE3) series, along with good π-π overlap and local ordering (low paracrystallinity values). Furthermore, these trends in the extent of doping and paracrystallinity are consistent with the reduced Fermi energy level and transport function prefactor parameters calculated using the semilocalized transport (SLoT) model. Observed differences in carrier ratios at the transport edge (ct) and reduced Fermi energies [η(c)] suggest a broader electronic band (better overlap and more delocalization) for the EDOT-incorporating P(OE3)-E polymer relative to P(OE3)-D and P(OE3)-Ph. Ultimately, we rationalize improvements in electrical conductivity due to microstructural and doping enhancements caused by EDOT incorporation, a structure-property relationship worth considering in the future design of highly electrically conductive systems.

Chemically doped poly[2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) shows promise for many organic electronic applications, but rationalizing its charge transport properties is challenging because conjugated polymers are inhomogeneous, with convoluted optical and solid-state transport properties. Herein, we use the semilocalized transport (SLoT) model to quantify how the charge transport properties of PBTTT change as a function of iron(III) chloride (FeCl3) doping level. We use the SLoT model to calculate fundamental transport parameters, including the carrier density needed for metal-like electrical conductivities and the position of the Fermi energy level with respect to the transport edge. We then contextualize these parameters with other polymer-dopant systems and previous PBTTT reports. Additionally, we use grazing incidence wide-angle X-ray scattering and spectroscopic ellipsometry techniques to better characterize inhomogeneity in PBTTT. Our analyses indicate that PBTTT obtains high electrical conductivities due to its quickly rising reduced Fermi energy level, and this rise is afforded by its locally high carrier densities in highly ordered microdomains. Ultimately, this report sets a benchmark for comparing transport properties across polymer-dopant-processing systems.

Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal-like charge transport properties using a fully solution processable precursor polymer is reported. This is achieved via an ester-functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film-forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20-60 S cm-1 and hopping-like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos3 ). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm-1 and demonstrate metal-like (i.e., thermally deactivated and band-like) transport properties and high stability at comparable doping levels.