Growth direction dependent separate-channel charge transport in the organic weak charge-transfer co-crystal of anthracene–DTTCNQ

Co-crystallization is an efficient way of molecular crystal engineering to tune the electronic properties of organic semiconductors. In this work, we synthesized anthracene-4,8-bis(dicyanomethylene)4,8-dihydrobenzo[1,2-b:4,5-b']-dithiophene (DTTCNQ) single crystals as a template to study the crystal growth direction dependent charge transport properties and attempted to elucidate the mechanism by proposing a separate-channel charge transport model. Single-crystal anthracene-DTTCNQ field-effect transistors showed that ambipolar transport properties could be observed in all crystal growth directions. Furthermore, upon changing the measured crystal directions, the electronic properties experienced a weak change from n-type dominated ambipolar, balanced ambipolar, to p-type dominated ambipolar properties. The theoretical calculations at density functional theory (DFT) and higher theory levels suggested that the anthracene-DTTCNQ co-crystal motif was a weak charge-transfer complex, in line with the experiment. Furthermore, the detailed theoretical analysis also indicated that electron or hole transport properties originated from separated channels formed by DTTCNQ or anthracene molecules. We thus proposed a novel separate-channel transport mechanism to support additional theoretical analysis and calculations. The joint experimental and theoretical efforts in this work suggest that the engineering of co-crystallization of weak charge-transfer complexes can be a practical approach for achieving tuneable ambipolar charge transport properties by the rational choice of co-crystal formers.