Development of high-performance printed semiconductor devices is highly desired with the expectation for the nextgeneration technologies of "printable electronics" providing simply fabricated, fl exible, large-area, low-cost, and environmentally friendly electronic products such as paper-like fl exible displays. Patterned arrays of printed organic fi eld-effect transistors (OFETs) based on chemically stable solutionprocessed organic semiconductors are regarded as key devices that operate as fundamental switching components in, for example, pixel-controlling active-matrix elements. However, performance of conventional solution-coated noncrystal organic thin-fi lm transistors has yet to be improved for practical use in general electronic circuitry. Here, newly developed arrays of patterned crystalline OFETs of air-stable compound 2,9-didecyl-dinaphtho[2,3-b:2',3'-f ]thieno[3,2-b]thiophene (C 10 -DNTT) formed from hot solution are presented. A method of oriented growth is introduced to provide the singlecrystalline fi lms of C 10 -DNTT that regulates the crystallizing direction and positions in a single process. The benchmark value, 10 cm 2 V − 1 s − 1 , of the charge mobility is achieved for the present OFETs, far exceeding the performance of former devices and opening a practical way to realize printed and fl exible electronics with suffi cient switching speed. The result is attributed to almost perfect molecular periodicity in the crystal fi lms, which allows effective intermolecular charge transport of the electrons.In the process of forming organic semiconductor fi lms from solution by naturally evaporating the solvent near room temperature, constituent molecules that are independently dispersed in the solvent, are expected to self-organize into a highly ordered assembly with the amazing speed of more than 10 10 molecules per second. [ 1 ] Since the speed of the fi lm growth is directly translated to high-throughput production, solution techniques such as spin-coating and drop-casting are very attractive for the industry. [ 2 ] Regarding the performance of the solution-processed organic fi eld-effect transistors (OFETs), their switching speed is directly determined by charge carrier mobility in the organic semiconductors, which relies on microscopic electronic properties of molecule-to-molecule charge-transfer probability and the extent of molecular ordering. Therefore, it has been intensively challenging to create high-mobility active semiconductor layers using simple solution techniques. In addition, simple methods of forming their patterned arrays during the fi lm growth have been regarded as essential technology for accelerated production of matrix devices. Here, the extent of the molecular order signifi cantly infl uences device performance through the charge carrier mobility in the semiconductor fi lms. In order to realize much higher performance than achieved in present devices, synthesis of functional π -conjugated molecules with superior selfassembling properties, in addition to their high-charge-trans...

Molecular doping: The standard model for molecular p-doping of organic semiconductors (OSCs) assumes integer charge transfer between OSC and dopant. This is in contrast to an alternative model based on intermolecular complex formation instead. By systematically varying the acceptor strength it was possible to discriminate the two models. The latter is clearly favored, suggesting strategies for the chemical design of more efficient molecular dopants.

N-shaped organic semiconductors are synthesized via four steps from a readily available starting material. Such semiconductors exhibit preferable ionization potential for p-type operation, thermally stable crystalline phase over 200 °C, and high carrier mobility up to 16 cm(2) V(-1) s(-1) (12.1 cm(2) V(-1) s(-1) on average) with small threshold voltages in solution-crystallized field-effect transistors.

High‐mobility solution‐processed organic transistors are developed based on a hybrid of solution‐crystallized air‐stable organic semiconductor 2,7‐dioctyl[1]ben­zo­thieno[3,2‐b][1] benzothiophene (C8‐­ BTBT) and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetra­cy­anoquinodimethane (F4‐TCNQ) top layers. Charge mobility as high as 6 cm2/Vs is achieved, owing to the almost perfectly periodic crystal packing and efficient charge supply from the acceptor.