Influence of Branched Alkyl Ester-Labeled Side Chains on Specific Chain Arrangement and Charge-Transport Properties of Diketopyrrolopyrrole-Based Conjugated Polymers

A series of diketopyrrolopyrrole (DPP)-based copolymers, with DPP and bithiophene (BT) as the electron-acceptor and donor backbone units, respectively, are synthesized with branched alkyl side chains that are either directly coupled to the N-positions of DPP or separated by an alkyl ester group. The ester moieties in the side chains induce specific cohesive molecular interactions between these side chains, as compared to the alkyl-only side chains with weak van der Waals interactions. Structure analysis of the DPPBT-based copolymers demonstrated that the introduction of a proper alkyl ester spacer to the branched alkyl chains can shorten the π-π stacking distance between the DPPBT backbones down to 3.61 Å and promote the development of two-dimensionally extended domains. DPPBT-based copolymers, including different branched alkyl ester-labeled side chains, are spun-cast on polymer-treated SiO₂ dielectrics from dilute chloroform solutions for organic thin-film transistors. A DPPBT-based copolymer with properly engineered side chains (i.e., 2-decyltetradecyl ester-labeled side chains) shows the highest hole mobility of 2.30 cm² V^-1 s^-1 and an on/off current ratio of above 10⁶.