Development of Benzobisoxazole-Based Novel Conjugated Polymers for Organic Thin-Film Transistors.

Benzo[1,2-d:4,5-d']bis(oxazole) (BBO) is a heterocyclic aromatic ring composed of one benzene ring and two oxazole rings, which has unique advantages on the facile synthesis without any column chromatography purification, high solubility on the common organic solvents and planar fused aromatic ring structure. However, BBO conjugated building block has rarely been used to develop conjugated polymers for organic thin film transistors (OTFTs). Three BBO-based monomers, BBO without π-spacer, BBO with non-alkylated thiophene π-spacer and BBO with alkylated thiophene π-spacer, were newly synthesized and they were copolymerized with a strong electron-donating cyclopentadithiophene conjugated building block to give three p-type BBO-based polymers. The polymer containing non-alkylated thiophene π-spacer showed the highest hole mobility of 2.2 × 10 cm V s, which was 100 times higher than the other polymers. From the 2D grazing incidence X-ray diffraction data and simulated polymeric structures, we found that the intercalation of alkyl side chains on the polymer backbones was crucial to determine the intermolecular ordering in the film states, and the introduction of non-alkylated thiophene π-spacer to polymer backbone was the most effective to promote the intercalation of alkyl side chains in the film states and hole mobility in the devices.