Intermolecular interactions in organic semiconductors based on annelated β-oligothiophenes and their effect on the performance of organic field-effect transistors

A series of derivatives based on annelated β-oligothiophenes were synthesized and characterized as active layer in organic field-effect transistors (OFETs). Highest field-effect mobility of 0.52 V−1 s−1 for 2,5-dibiphenyl-dithieno[2,3-b:3′,2′-d]thiophene (DBP-DTT), 2.2 cm2 V−1 s−1 for 2,5-distyryl-dithieno[2,3-b:3′,2′-d]thiophene (DEP-DTT), and 0.16 cm2 V−1 s−1 for 1,4-di[2-dithieno[2,3-b:3′,2′-d] thiophen-2-yl-vinyl]benzene (DDTT-EP) were obtained, while 2,5-diphenyl-dithieno [2,3-b:3′,2′-d]thiophene (DP-DTT) presents no field-effect behaviors. Their thermal, optical and electrochemical properties, topographical and X-ray diffraction patterns of films, and the single crystal structures were also investigated. With the end-capping groups changing in these materials, the intermolecular interactions could transform from S–S in DP-DTT to S–C in DBP-DTT, to S–π in DEP-DTT, and to the coexisting of S–S and S–π in DDTT-EP. According to the device performances and the results of transfer integral calculations, it was revealed that S–π intermolecular interaction benefits not only improving the mobility but also reducing the threshold voltage (VT), while S–S intermolecular interaction is not favorable for promoting the mobility.

Graphical abstractIntermolecular interaction in the single crystals of DTT derivatives.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The intermolecular interaction can transfer from S–S to S–C, to S–π, and to the coexisting of S–S and S–π. ► The molecules adopt a condensed arrangement as the S–C intermolecular interaction existing. ► S–π intermolecular interaction benefits not only improving the mobility but also reducing the threshold voltage.