In bottom-contact organic field-effect transistors (OFETs), the functionalization of source/drain electrodes leads to a tailored surface chemistry for film growth and controlled interface energetics for charge injection. This report describes a comprehensive investigation into separating and correlating the energetic and morphological effects of a self-assembled monolayers (SAMs) treatment on Au, Ag, and Cu electrodes. Fluorinated 5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TES-ADT) and pentafluorobenzenethiol (PFBT) are employed as a soluble small-molecule semiconductor and a SAM material, respectively. Upon SAM modification, the Cu electrode devices benefit from a particularly dramatic performance improvement, closely approaching the performance of OFETs with PFBT-Au and PFBT-Ag. Ultraviolet photoemission spectroscopy, polarized optical microscopy, grazing-incidence wide-angle X-ray scattering elucidate the metal work function change and templated crystal growth with high crystallinity resulting from SAMs. The transmission-line method separates the channel and contact properties from the measured OFET current–voltage data, which conclusively describes the impact of the SAMs on charge injection and transport behavior.

Fluorination has been demonstrated to improve stability and processing in thiophene-containing small-molecule semiconductors. Here, the impact of partial fluorination on these parameters in a pentacene derivative is examined. Although the improvement in photostability is not as dramatic, there is a clear improvement in the stability of the chromophore upon fluorination. The improvement in processability is more dramatic; devices formed by spin-coating with the fluorinated derivative perform substantially better than those formed from the nonfluorinated compound.

The crystallinity of an organic semiconductor film determines the efficiency of charge transport in electronic devices. This report presents a micro-to-nanoscale investigation on the crystal growth of fluorinated 5,11-bis(triethylgermylethynyl)anthradithiophene (diF-TEG-ADT) and its implication for the electrical behavior of organic field-effect transistors (OFETs). diF-TEG-ADT exhibits remarkable self-assembly through spin-cast preparation, with highly aligned edge-on stacking creating a fast hole-conducting channel for OFETs.