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Open AccessArticle

Solid-State Organization and Ambipolar Field-Effect Transistors of Benzothiadiazole-Cyclopentadithiophene Copolymer with Long Branched Alkyl Side Chains

Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz D-55128, Germany
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Polymers 2013, 5(2), 833-846; https://doi.org/10.3390/polym5020833
Received: 15 April 2013 / Revised: 15 May 2013 / Accepted: 16 May 2013 / Published: 18 June 2013
(This article belongs to the Special Issue Supramolecular Chemistry and Self-Assembly)
The solid-state organization of a benzothiadiazole-cyclopentadithiophene copolymer with long, branched decyl-tetradecyl side chains (CDT-BTZ-C14,10) is investigated. The C14,10 substituents are sterically demanding and increase the π-stacking distance to 0.40 nm from 0.37 nm for the same polymer with linear hexadecyls (C16). Despite the bulkiness, the C14,10 side chains tend to crystallize, leading to a small chain-to-chain distance between lamellae stacks and to a crystal-like microstructure in the thin film. Interestingly, field-effect transistors based on solution processed layers of CDT-BTZ-C14,10 show ambipolar behavior in contrast to CDT-BTZ-C16 with linear side chains, for which hole transport was previously observed. Due to the increased π-stacking distance, the mobilities are only 6 × 104 cm²/Vs for electrons and 6 × 105 cm²/Vs for holes, while CDT-BTZ-C16 leads to values up to 5.5 cm²/Vs. The ambipolarity is attributed to a lateral shift between stacked backbones provoked by the bulky C14,10 side chains. This reorganization is supposed to change the transfer integrals between the C16 and C14,10 substituted polymers. This work shows that the electronic behavior in devices of one single conjugated polymer (in this case CDT-BTZ) can be controlled by the right choice of the substituents to place the backbones in the desired packing. View Full-Text
Keywords: organic electronics; ambipolar field-effect transistor; self-assembly; solution processing; donor-acceptor polymer organic electronics; ambipolar field-effect transistor; self-assembly; solution processing; donor-acceptor polymer
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Pisula, W.; Tsao, H.N.; Dudenko, D.; Cho, D.M.; Puniredd, S.R.; Zhao, Y.; Mavrinskiy, A.; Shu, J.; Hansen, M.R.; Baumgarten, M.; Müllen, K. Solid-State Organization and Ambipolar Field-Effect Transistors of Benzothiadiazole-Cyclopentadithiophene Copolymer with Long Branched Alkyl Side Chains. Polymers 2013, 5, 833-846.

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