Combining Electron-Neutral Building Blocks with Intramolecular “Conformational Locks” Affords Stable, High-Mobility P- and N-Channel Polymer Semiconductors

• Published in: Journal of the American Chemical Society 2012-07, Vol.134 (26), p.10966-10973
• Main Authors: Huang, Hui, Chen, Zhihua, Ortiz, Rocio Ponce, Newman, Christopher, Usta, Hakan, Lou, Sylvia, Youn, Jangdae, Noh, Yong-Young, Baeg, Kang-Jun, Chen, Lin X., Facchetti, Antonio, Marks, Tobin
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja303401s

Understanding the relationship between molecular/macromolecular architecture and organic thin film transistor (TFT) performance is essential for realizing next-generation high-performance organic electronics. In this regard, planar π-conjugated, electron-neutral (i.e., neither highly electron-rich nor highly electron-deficient) building blocks represent a major goal for polymeric semiconductors, however their realization presents synthetic challenges. Here we report that an easily accessible (minimal synthetic steps), electron-neutral thienyl-vinylene (TVT)-based building block having weak intramolecular S···O “conformational locks” affords a new class of stable, structurally planar, solution-processable, high-mobility, molecular, and macromolecular semiconductors. The attraction of merging the weak TVT electron richness with supramolecular planarization is evident in the DFT-computed electronic structures, favorable MO energetics, X-ray diffraction-derived molecular structures, experimental lattice coehesion metrics, and excellent TFT performance. TVT-based polymer TFTs exhibit stable carrier mobilities in air as high as 0.5 and 0.05 cm2/V·s (n- and p-type, respectively). All-TVT polymer-based complementary inverter circuitry exhibiting high voltage gains (∼50) and ring oscillator circuitry with high f osc(∼1.25 kHz) is readily fabricated from these materials by simple inkjet printing.