Design, Synthesis, and Structure–Property Relationships of Isoindigo-Based Conjugated Polymers

• Published in: Accounts of chemical research Vol. 47; no. 4; pp. 1117 - 1126
• Main Authors: Lei, Ting, Wang, Jie-Yu, Pei, Jian
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.04.2014
• Subjects: Chains (polymeric); Devices; Field effect transistors; Performance enhancement; Polymers; Semiconductor devices; Stability; Strategy
• DOI: 10.1021/ar400254j
• ISSN: 0001-4842; 1520-4898

Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor–acceptor (D–A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure–property relationships. Recently, isoindigo has been used as a new acceptor of D–A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure–property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using farther branched alkyl chains can effectively decrease interchain π–π stacking distance and improve carrier mobility. When we introduce electron-deficient functional groups on the isoindigo core, the LUMO levels of the polymers markedly decrease, which significantly improves the electron mobility and device stability. In addition, we present a new polymer system called BDOPV, which is based on the concept of π-extended isoindigo. By application of some strategies successfully used in isoindigo-based polymers, BDOPV-based polymers exhibit high mobility and good stability both in n-type and in ambipolar FETs. We believe that a synergy of molecular engineering strategies towards the isoindigo core, donor units, and side chains may further improve the performance and broaden the application of isoindigo-based polymers.