期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 6, 页码 2338-2349出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja311469y
关键词
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资金
- National Natural Science Foundation [20952001, 60901050, 61171055, 20902105, 51173200]
- MOST [2011CB932300]
- Chinese Academy of Sciences
- Beijing Municipal Education Commission [YB20098000104]
- Shanghai Rising-Star Program [11QA1408100]
- Engineering and Physical Sciences Research Council [EP/E051804/1]
- Australian Research Council [FT100100275]
- Engineering and Physical Sciences Research Council [EP/G068356/1, EP/E051804/1] Funding Source: researchfish
- EPSRC [EP/G068356/1, EP/E051804/1] Funding Source: UKRI
Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility. It is found that the side-chain length has a moderate influence on thin-film microstructure but leads to only limited changes in OTFT performance. In contrast, the position of branching point results in subtle, yet critical changes in molecular packing and leads to dramatic differences in electron mobility ranging from similar to 0.001 to >3.0 cm(2) V-1 s(-1). Incorporating a NDI-DTYM2 core with three-branched N-alkyl substituents of C-11,C-6 results in a dense in-plane molecular packing, with an unit cell area of 127 angstrom(2), larger domain sizes of up to 1000 X 3000 nm(2), and an electron mobility of up to 3.50 cm(2) V-1 s(-1), which is an unprecedented value for ambient stable n-channel solution-processed OTFTs reported to date. These results demonstrate that variation of the alkyl chain branching point is a powerful strategy for tuning of molecular packing to enable high charge transport mobilities.
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