The charge‐transport processes in organic p‐channel transistors based on the small‐molecule 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene (diF‐TES ADT), the polymer poly(triarylamine)(PTAA) and blends thereof are investigated. In the case of blend films, lateral conductive atomic force microscopy in combination with energy filtered transmission electron microscopy are used to study the evolution of charge transport as a function of blends composition, allowing direct correlation of the film's elemental composition and morphology with hole transport. Low‐temperature transport measurements reveal that optimized blend devices exhibit lower temperature dependence of hole mobility than pristine PTAA devices while also providing a narrower bandgap trap distribution than pristine diF‐TES ADT devices. These combined effects increase the mean hole mobility in optimized blends to 2.4 cm2/Vs – double the value measured for best diF‐TES ADT‐only devices. The bandgap trap distribution in transistors based on different diF‐TES ADT:PTAA blend ratios are compared and the act of blending these semiconductors is seen to reduce the trap distribution width yet increase the average trap energy compared to pristine diF‐TES ADT‐based devices. Our measurements suggest that an average trap energy of <75 meV and a trap distribution of <100 meV is needed to achieve optimum hole mobility in transistors based on diF‐TES ADT:PTAA blends.

The effect of grain boundaries in high hole mobility organic blend films of diF-TES ADT:PTAA is evaluated using conductive-AFM measurements revealing the presence of unusually conductive grain boundaries. The latter characteristic has not been reported previously for any other organic semiconducting film system and is believed to underpin the excellent and morphology-independent hole transport characteristics seen in these composite films.

Five new molecular semiconductors that differ from dioctylbenzothienobenzothiophene, by the introduction of ether or thioether side chains, have been synthesized and obtained in good yields. Their availability in sufficient quantities has allowed investigation of their electrochemical behaviour in solution and their electronic properties in solid state. Both ether and thioether compounds oxidise rather easily in solution, but nevertheless, they exhibit rather high ionisation potentials. This is a consequence of their crystal structure. Dioctylthioetherbenzothienobenzothiophene is rather sensitive to oxidation and degrades easily in close to ambient conditions. Dioctylletherbenzothienobenzothiophene is more stable. Its charge carrier mobility remains however rather moderate, on the order of 0.5 cm2/V.s, whereas that of dioctylbenzothienobenzothiophene reached 4 cm2/V.s, in the same conditions. The difference is explained by intrinsic factors as shown by a theoretical modelling

Spray-coating techniques have recently emerged as especially effective approaches for the deposition of small semiconducting molecules toward the fabrication of organic field-effect transistors (OFETs). Despite the promising mobility values and the industrial implementation capability of such techniques, the resulted devices still face challenges in terms of morphology control and performance variation. In this work, the efficient process control of electrostatic spraying deposition (ESD) and the excellent film properties of polymer:small molecule blends were successfully combined to develop reliable and high performance transistors. Specifically, a highly efficient blended system of 2,8-difluoro-5,11-bis(triethylsilylethynyl)-anthradithiophene (diF-TES-ADT) and poly(triarylamine) (PTAA) was employed in order to realize top-gate OFETs under ambient conditions, both on rigid and on flexible substrates. The films revealed an extensive crystallization and microstructural organization implying a distinct phase separation in the electrosprayed blend. Furthermore, we investigated the effects of the processing temperature on the film-forming properties by means of film continuity and grains boundaries.Remarkably, the electrosprayed OFETs exhibited field-effect mobilities as high as 1.71 cm 2 /Vs, and enhanced performance consistency when compared to conventional gas-sprayed transistors. Additionally, the transistors showed excellent electrical and environmental stability, indicative of the good interface quality and the selfencapsulation capability of top-gate structure. These results highlight the great potential of electrohydrodynamic atomization techniques for implementation to large-area processing for OFETs fabrication.