Butyl, hexyl, and decyl derivatives of the liquid-crystalline organic semiconductor 5,5' '-bis(5-alkyl-2-thienylethynyl)-2,2':5',2' '-terthiophene were synthesized and studied with respect to their structural, optical, and electrical properties. By means of an optimized thermal annealing scheme the hexyl and decyl compounds could be processed into self-assembled monodomain films of up to 150 mm in diameter. These were investigated with X-ray diffractometry, which revealed a clearly single-crystalline monoclinic morphology with lamellae parallel to the substrate. Within the lamellae the molecules were found to arrange with a tilt of about 50 degrees with the rubbing direction of the polyimide alignment layer. The resulting, close side-to-side packing was confirmed by measurements of the UV/vis absorption, which showed a dichroic ratio of 19 and indicated H-aggregation. AFM analyses revealed self-affinity in the surface roughness of the monodomain. The compounds showed bipolar charge transport in TOF measurements, with hole mobilities reaching up to 0.02 cm(2)/Vs and maximum electron mobilities around 0.002 cm(2)/Vs. The hexyl derivative was processed into large-area monodomain top-gate field-effect transistors, which were stable for months and showed anisotropic hole mobilities of up to 0.02 cm(2)/Vs. Compared to multidomain bottom-gate transistors the monodomain formation allowed for a mobility increase by 1 order of magnitude.

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An X‐ray method is presented to characterize thin films with unknown crystal structure with specific crystal orientations. The method maps large volumes of the reciprocal space by a series of pole‐figure measurements using a standard texture goniometer. The data can be used for lattice indexing and texture evaluation and in subsequent steps for a complete structural thin‐film characterization. The application of the method is demonstrated on an organic monodomain thin film consisting of uniaxially aligned crystallites.

Highly ordered thin films of organic materials are receiving a great deal of attention as active layers in a new generation of plastic electronic devices, particularly in organic field-effect transistors (OFETs).[1] Numerous organic-film preparation technologies have been tested over the past few decades. For commercial organic electronics, solution-processed, low-cost technologies such as spin-coating, inkjet printing, and screenprinting are preferred.[2] Mostly, these methods produce thin films with moderate structural order from soluble polymers and oligomers. The relevant physical parameters (e.g., chargecarrier mobilities) of thin organic films are strongly affected by the orientation, distribution, and size of the domains and domain boundaries, [3] and, more generally, by the degree of structural order. The endeavor to improve molecular alignment in active organic layers has led to the implementation of high-quality organic single crystals in OFETs with optimized performance.[4] However, recent methods for the fabrication of single-crystal devices are rather complex and inappropriate for practical applications.[5] Therefore, suitable organic compounds and preparation methods that yield highly ordered thin films are quite essential for progress in this field.In this paper, we present highly ordered thin films of 5,5″-bis(5-hexyl-2-thienylethynyl)-2,2′:5′,2″-terthiophene (TR5-C6) prepared from solution by spin-coating and subsequent thermal treatment, and studied using X-ray diffraction (XRD) techniques. The calamitic TR5-C6 molecule consists of a central terthiophene unit with acetylene linkages connecting two terminal thiophene rings with hexyl end groups (Fig. 1a).The thermotropic liquid crystalline behavior of TR5-C6 has been studied by differential scanning calorimetry (DSC), and the mesophases have been assigned by polarized optical microscopy. During cooling, exothermic phase transitions from the nematic to the smectic C phase at 115°C, from the smectic C to the smectic B phase at 109°C, and from the smectic B COMMUNICATIONS 896