Oligoarenes as an alternative group of promising semiconductors in organic optoelectronics have attracted much attention. However, high‐performance and low‐cost opto‐electrical devices based on linear asymmetric oligoarenes with nano/microstructures are still rarely studied because of difficulties both in synthesis and high‐quality nano/microstructure growth. Here, a novel linear asymmetric oligoarene 6‐methyl‐anthra[2,3‐b]benzo[d]thiophene (Me‐ABT) is synthesized and its high‐quality microribbons are grown by a solution process. The solution of Me‐ABT exhibits a moderate fluorescence quantum yield of 0.34, while the microribbons show a glaucous light emission. Phototransistors based on an individual Me‐ABT microribbon prepared by a solution‐phase self‐assembly process showed a high mobility of 1.66 cm2 V−1 s−1, a large photoresponsivity of 12 000 A W−1, and a photocurrent/dark‐current ratio of 6000 even under low light power conditions (30 µW cm−2). The measured photoresponsivity of the devices is much higher than that of inorganic single‐crystal silicon thin film transistors. These studies should boost the development of the organic semiconductors with high‐quality microstructures for potential application in organic optoelectronics.
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