Effects of the Polarity and Bulkiness of End-Functionalized Side Chains on the Charge Transport of Dicyanovinyl-End-Capped Diketopyrrolopyrrole-Based n-Type Small Molecules

Abstract

When designing organic semiconductors, side-chain engineering is as important as modifying the conjugated backbone, which has a significant impact on molecular ordering, morphology, and thus electronic device performance. We have developed three dicyanovinyl-end-capped donor-acceptor diketopyrrolopyrrole-based n-type small molecules (C2C9CN, SiC4CN, and EH4PCN) bearing an identical length of alkyl spacer yet different end-functionalized side chains (i.e., alkyl-, siloxane-, and phosphonate-end pendants). The effects of the end-functionalized side chains on the intrinsic molecular properties, microstructure, and charge transport of the small-molecule series were investigated. In comparison with the alkyl-end side chains, incorporating siloxane-end side chains into the backbone facilitates 2D edge-on oriented high intergrain connectivity/crystallinity and compatibility with the substrate surface, whereas the phosphonate-end analogues have an adverse effect on the film-forming quality due to high polarity. Thereby, an organic field-effect transistor fabricated by SiC4CN shows the best electron mobility up to 1.59 x 10(-1) cm(2) V-1 s(-1) along with a high current on/off ratio >10(5). This study contributes to our understanding of the role of the end-functionalized side chains (e.g., the effects of polarity and bulkiness of the end groups) for the development of high-performance semiconductors.