Solubilizing Benzodifuranone-Based Conjugated Copolymers with Single-Oxygen-Containing Branched Side Chains.

Single-oxygen-containing branched side chains are designed and used to solubilize n-type copolymers consisting of BDF (benzodifuranone), isatin, and thiophene-based units. We present a simple synthetic approach to side chains with varying linker distances between the backbone and the branching point. The synthetic pathway is straightforward and modular and starts with commercially available reagents. The side chains give rise to excellent solubilities of BDF-thiophene copolymers of up to 90 mg/mL, while still being moderate in size (26-34 atoms large). The excellent solubility furthermore allows high molar mass materials. BDF-thiophene copolymers are characterized in terms of optoelectronic and thermoelectric properties. The electrical conductivity of chemically doped polymers is found to scale with molar mass, reaching ∼1 S/cm for the highest molar mass and longest backbone-branching point distance.

Spontaneous Modulation Doping in Semi-Crystalline Conjugated Polymers Leads to High Conductivity at Low Doping Concentration.

The possibility to control the charge carrier density through doping is one of the defining properties of semiconductors. For organic semiconductors, the doping process is known to come with several problems associated with the dopant compromising the charge carrier mobility by deteriorating the host morphology and/or introducing Coulomb traps. While for inorganic semiconductors these factors can be mitigated through (top-down) modulation doping, this concept has not been employed in organics. Here, this work shows that properly chosen host/dopant combinations can give rise to spontaneous, bottom-up modulation doping, in which the dopants preferentially sit in an amorphous phase, while the actual charge transport occurs predominantly in a crystalline phase with an unaltered microstructure, spatially separating dopants and mobile charges. Combining experiments and numerical simulations, this work shows that this leads to exceptionally high conductivities at relatively low dopant concentrations.

Interplay between Side Chain Density and Polymer Alignment: Two Competing Strategies for Enhancing the Thermoelectric Performance of P3HT Analogues.

A series of polythiophenes with varying side chain density was synthesized, and their electrical and thermoelectric properties were investigated. Aligned and non-aligned thin films of the polymers were characterized in the neutral and chemically doped states. Optical and diffraction measurements revealed an overall lower order in the thin films with lower side chain density, also confirmed using polarized optical experiments on aligned thin films. However, upon doping the non-aligned films, a sixfold increase in electrical conductivity was observed for the polythiophene with the lowest side chain density compared to poly(3-hexylthiophene) (P3HT). We found that the improvement in conductivity was not due to a larger charge carrier density but an increase in charge carrier mobility after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). On the other hand, doped aligned films did not show the same trend; lower side chain density instead led to a lower conductivity and Seebeck coefficient compared to those for P3HT. This was attributed to the poorer alignment of the polymer thin films with lower side chain density. The study demonstrates that optimizing side chain density is a synthetically simple and effective way to improve electrical conductivity in polythiophene films relevant to thermoelectric applications.