Solution‐Processed High‐Performance Tetrathienothiophene‐Based Small Molecular Blends for Ambipolar Charge Transport.

Abstract: Four soluble dialkylated tetrathienoacene (TTAR)‐based small molecular semiconductors featuring the combination of a TTAR central core, π‐conjugated spacers comprising bithiophene (bT) or thiophene (T), and with/without cyanoacrylate (CA) end‐capping moieties are synthesized and characterized. The molecule DbT‐TTAR exhibits a promising hole mobility up to 0.36 cm² V⁻¹ s⁻¹ due to the enhanced crystallinity of the microribbon‐like films. Binary blends of the p‐type DbT‐TTAR and the n‐type dicyanomethylene substituted dithienothiophene‐quinoid (DTTQ‐11) are investigated in terms of film morphology, microstructure, and organic field‐effect transistor (OFET) performance. The data indicate that as the DbT‐TTAR content in the blend film increases, the charge transport characteristics vary from unipolar (electron‐only) to ambipolar and then back to unipolar (hole‐only). With a 1:1 weight ratio of DbT‐TTAR DTTQ‐11 in the blend, well‐defined pathways for both charge carriers are achieved and resulted in ambipolar transport with high hole and electron mobilities of 0.83 and 0.37 cm² V⁻¹ s⁻¹, respectively. This study provides a viable way for tuning microstructure and charge carrier transport in small molecules and their blends to achieve high‐performance solution‐processable OFETs. [ABSTRACT FROM AUTHOR]