Delocalized singlet biradical hydrocarbons hold promise as new semiconducting materials for high‐performance organic devices. However, to date biradical organic molecules have attracted little attention as a material for organic electronic devices. Here, this work shows that films of a crystallized diphenyl derivative of s‐indacenodiphenalene (Ph2‐IDPL) exhibit high ambipolar mobilities in organic field‐effect transistors (OFETs). Furthermore, OFETs fabricated using Ph2‐IDPL single crystals show high hole mobility (μh = 7.2 × 10−1 cm2 V−1 s−1) comparable to that of amorphous Si. Additionally, high on/off ratios are achieved for Ph2‐IDPL by inserting self‐assembled monolayer of alkanethiol between the semiconducting layer and the Au electrodes. These findings open a door to the application of ambipolar OFETs to organic electronics such as complementary metal oxide semiconductor logic circuits.
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