In this contribution we review the motivations for, and recent advances in, new gate dielectric materials for incorporation into organic thin‐film transistors (OTFTs) for organic electronics. After a general introduction to OTFT materials, operating principles, and processing requirements for optimizing low‐cost organic electronics, this review focuses on three classes of OTFT‐compatible dielectrics: i) inorganic (high‐k) materials; ii) polymeric materials; and iii) self‐assembled mono‐ and/multilayer materials. The principal goals in this active research area are tunable and reduced OTFT operating voltages, leading to decreased device power consumption while providing excellent dielectric/insulator properties and efficient low‐cost solution‐phase processing characteristics.

Taking up the semiconducting baton: Organic field‐effect transistors fabricated with a new class of extremely electron‐deficient cyanated perylene diimides are air‐stable and exhibit n‐type mobilities as high as 0.64 cm2 V−1 s−1 (see scheme). Devices can be fabricated from vapor‐deposited and solution‐cast films as well as top‐ and bottom‐contact electrode configurations.

The synthesis, comparative physicochemical properties, and solid-state structures of five oligothiophene (nT) series differing in substituent nature and attachment, regiochemistry, and oligothiophene core length (n) are described. These five series include the following 25 compounds: (i) alpha,omega-diperfluorohexyl-nTs 1 (DFH-nTs, n = 2-6), (ii) beta,beta'-diperfluorohexyl-nTs 2 (isoDFH-nTs, n = 2-6), (iii) alpha,omega-dihexyl-nTs 3 (DH-nTs, n = 2-6), (iv) beta,beta'-dihexyl-nTs 4 (isoDH-nTs, n = 2-6), and (v) unsubstituted oligothiophenes 5 (alphanTs, n = 2-6). All new compounds were characterized by elemental analysis, mass spectrometry, and multinuclear NMR spectroscopy. To probe and address quantitatively how the chemistry and regiochemistry of conjugated core substitution affects molecular and solid-state properties, the entire 1-5 series was investigated by differential scanning calorimetry, thermogravimetric analysis, and optical absorption and emission spectroscopies. Single-crystal X-ray diffraction data for several fluorocarbon-substituted oligomers are also presented and compared. The combined analysis of these data indicates that fluorocarbon-substituted nT molecules strongly interact in the condensed state, with unit cell level phase separation between the aromatic core and fluorocarbon chains. Surprisingly, despite these strong intermolecular interactions, high solid-state fluorescence efficiencies are exhibited by the fluorinated derivatives. Insight into the solution molecular geometries and conformational behavior are obtained from analysis of optical and variable-temperature NMR spectra. Finally, cyclic voltammetry data offer a reliable picture of frontier MO energies, which, in combination with DFT computations, provide key information on relationships between oligothiophene substituent effects and electronic response properties.

High-performance thin-film transistors (TFTs) that can be fabricated at low temperature and are mechanically flexible, optically transparent and compatible with diverse substrate materials are of great current interest. To function at low biases to minimize power consumption, such devices must also contain a high-mobility semiconductor and/or a high-capacitance gate dielectric. Here we report transparent inorganic-organic hybrid n-type TFTs fabricated at room temperature by combining In2O3 thin films grown by ion-assisted deposition, with nanoscale organic dielectrics self-assembled in a solution-phase process. Such TFTs combine the advantages of a high-mobility transparent inorganic semiconductor with an ultrathin high-capacitance/low-leakage organic gate dielectric. The resulting, completely transparent TFTs exhibit excellent operating characteristics near 1.0 V with large field-effect mobilities of >120 cm2 V(-1) s(-1), drain-source current on/off modulation ratio (I(on)/I(off)) approximately 10(5), near-zero threshold voltages and sub-threshold gate voltage swings of 90 mV per decade. The results suggest new strategies for achieving 'invisible' optoelectronics.

A new family of perfluoroarene‐modified thiophene semiconductors 1–3 has been synthesized to assess the influence of perfluoroarene introduction and regiochemistry on molecular and thin‐film transistor properties. Compound 1 is an n‐type semiconductor with a mobility approaching 0.1 cm2 V−1 s−1 whereas 2 and 3 exhibit p‐type behavior. These results show that the origin of n‐type carrier mobility is not solely a consequence of solution/film LUMO and HOMO energies.