Solution‐Processed Monolayer Organic Crystals for High‐Performance Field‐Effect Transistors and Ultrasensitive Gas Sensors

This work innovatively develops a dual solution‐shearing method utilizing the semiconductor concentration region close to the solubility limit, which successfully generates large‐area and high‐performance semiconductor monolayer crystals on the millimeter scale. The monolayer crystals with poly(methyl methacrylate) encapsulation show the highest mobility of 10.4 cm² V^?1 s^?1 among the mobility values in the reported solution‐processed semiconductor monolayers. With similar mobility to multilayer crystals, light is shed on the charge accumulation mechanism in organic field‐effect transistors (OFETs), where the first layer on interface bears the most carrier transport task, and the other above layers work as carrier suppliers and encapsulations to the first layer. The monolayer crystals show a very low dependency on channel directions with a small anisotropic ratio of 1.3. The positive mobility–temperature correlation reveals a thermally activated carrier transport mode in the monolayer crystals, which is different from the band‐like transport mode in multilayer crystals. Furthermore, because of the direct exposure of highly conductive channels, the monolayer crystal based OFETs can sense ammonia concentrations as low as 10 ppb. The decent sensitivity indicates the monolayer crystals are potential candidates for sensor applications.