Conjugated backbones play a fundamental role in determining the electronic properties of organic semiconductors. On the basis of two solution-processable dihydropyrrolo[3,4-c]pyrrole-1,4-diylidenebis(thieno[3,2-b]thiophene) derivatives with aromatic and quinoid structures, we have carried out a systematic study of the relationship between the conjugated-backbone structure and the thermoelectric properties. In particular, a combination of UV-vis-NIR spectra, photoemission spectroscopy, and doping optimization are utilized to probe the interplay between energy levels, chemical doping, and thermoelectric performance. We found that a moderate change in the conjugated backbone leads to varied doping mechanisms and contributes to dramatic changes in the thermoelectric performance. Notably, the chemically doped A-DCV-DPPTT, a small molecule with aromatic structure, exhibits an electrical conductivity of 5.3 S cm and a high power factor (PF) up to 236 μW m K, which is 50 times higher than that of Q-DCM-DPPTT with a quinoid structure. More importantly, the low thermal conductivity enables A-DCV-DPPTT to possess a figure of merit (ZT) of 0.23 ± 0.03, which is the highest value reported to date for thermoelectric materials based on organic small molecules. These results demonstrate that the modulation of the conjugated backbone represents a powerful strategy for tuning the electronic structure and mobility of organic semiconductors toward a maximum thermoelectric performance.

Conjugation-break spacers (CBSs) are intentionally introduced into the diketopyrrolopyrrole (DPP)-based polymer backbones. We reveal that the solution processability progressively increases with the percentage of CBSs, while charge mobility inversely varies to the CBS ratio. For instance, the polymer DPP-30 with solubility of ∼10 mg/mL in dichlorobenzene provides an average mobility over 1.4 cm 2 V −1 s −1 , while DPP-0 exhibits an average mobility of 4.3 cm 2 V −1 s −1 with solubility of ∼3 mg/mL. This correlation provides a general guidance to design polymers with desired electronic performance and solution processability for large-scale roll-to-roll processing. Most encouraging, DPP-70 can be melt processed in air and provide hole mobilities up to 0.30 cm 2 V −1 s −1 , substantially higher value than their solution-processed counterparts about 0.1 cm 2 V −1 s −1 . The mobility boost in melt-processed devices, together with completely eliminating the need to use toxic solvent in the processing, encourages to design meltprocessable polymers for electronic devices.