Molecular aggregation–performance relationship in the design of novel cyclohexylethynyl end-capped quaterthiophenes for solution-processed organic transistors

The synthesis and characterization of cyclohexylethenyl end-capped quaterthiophenes is reported. Additionally, an investigation of the performance of organic field-effect transistors based on these quaterthiophenes in view of the relationship between the solid-state (or aggregate) order and the electronic performance is described. UV–vis absorption measurements revealed that the quaterthiophene with an asymmetrically substituted cyclohexylethynyl end-group induced the formation of H-type aggregates, whereas the quaterthiophene with a symmetrically substituted cyclohexylethynyl end-groups favored the formation of J-type aggregates. Two-dimensional grazing-incidence wide-angle X-ray scattering studies were performed to support the molecular structure-dependent packing of films of the new quaterthiophenes. Solution-processed quaterthiophenes were tested as the active layers of p-type organic field-effect transistors with a bottom gate/top contact geometry. The field-effect mobility of devices that incorporated asymmetric quaterthiophene molecules was quite high, exceeding 0.02 cm2/V s, due to H-aggregation and good in-plane ordering. In contrast, the field-effect mobility of devices that incorporated symmetrical quaterthiophenes, was low, above 5 × 10−4 cm2/(V s), due to the formation of J-aggregates and poor in-plane ordering. A comparison of the symmetrical and asymmetrical quaterthiophene derivatives revealed that the molecular aggregation-dependent packing, determined by the cyclohexylethynyl end groups, was responsible for influencing the organic field-effect transistor performance.

► We report the synthesis and characterization of cyclohexylethynyl end-capped quaterthiophenes.
► We describe an investigation of the performance of OFETs based on these quaterthiophenes in view of the relationship between the solid-state (or aggregate) order and the electronic performance.
► Two-dimensional grazing-incidence wide-angle X-ray scattering studies were performed to support the molecular structure-dependent packing of films of the new quaterthiophenes.
► The mobility of devices based on H-aggregated molecules was higher than that of devices based on J-aggregated molecules.