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Novel solution-processable dithieno[3,2-d:2′,3′-d]thiophene (DTT) derivatives with alkylated thiophene or alkyl chain substituents, 2,6-bis(5-octylthiophen-2-yl)dithieno[3,2-b:2′,3′-d]thiophene (compound 1), 2,6-bis(5-(2-ethylhexyl)thiophen-2-yl)dithieno[3,2-b:2′,3′-d]thiophene (compound 2), and 2,6-dioctyldithieno[3,2-b:2′,3′-d]thiophene (compound 3), have been synthesized and employed as small molecular organic semiconductors for organic field-effect transistors (OFETs). All compounds exhibited good thermal stability over 290 °C, while different side groups of DTT compounds afforded different melting temperatures. The molecular orbital energy levels were experimentally and theoretically calculated, and their trend was almost the same. The developed compounds were employed as active layers for top-contact/bottom-gate OFETs with average charge carrier mobility as high as 0.10 cm2/Vs and current on/off ratio &gt; 107 in ambient atmosphere. Notably, DTT derivative with linear alkyl chain (-octyl) substituents showed the best device performance. High device performance could be attributed to the large grains and continuous surface coverages as well as high film texture of the corresponding semiconductor films.

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Development of Dithieno[3,2-b:2′,3′-d]thiophene (DTT) Derivatives as Solution-Processable Small Molecular Semiconductors for Organic Thin Film Transistors