In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal–semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the I_on/I_off ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.

Field-effect transistors based on poly(3-hexylthiophene) (P3HT) ultrathin films exhibit maximum charge carrier mobilities of up to 0.1 cm² V⁻¹ s⁻¹.

Thin film field-effect transistors based on binary blends of poly(3-hexylthiophene) (P3HT) and two perylene diimide (PDI) derivatives with different alkyl substituents have been investigated in terms of device performance, microstructure and molecular organization on the surface. For the same blend ratios the PDIs phase separate differently due to solubility variation. Blends with a horizontal phase separation between the donor and acceptor show ambipolar behavior due to well defined homogenous pathways for both charge carriers. In this layer arrangement the polymer is located near the dielectric interface, while the PDI molecules crystallize on top of the film. Interestingly, the electron mobility is improved by a few orders of magnitude in comparison to the pure acceptor. This increase is attributed to the altered microstructure of PDI in the blends. Layers in which the PDI crystals are embedded within the polymer matrix and are not interconnected with each other lead only to hole transport in the transistor. For one blend ratio, the hole mobility improves by one order of magnitude compared to pure P3HT as a result of the reorganization of the polymer in the blend layer. This study provides new insights into the role of microstructure and molecular organization in the charge carrier transport in heterojunction field-effect transistors for the development of high-performance future devices.