The temperature-dependent alignment of semiconducting liquid crystalline fluorene-thiophene copolymer (F8T2) thin film surfaces was investigated using the near-edge X-ray absorption fine structure (NEXAFS) technique. Partial electron yield spectra were recorded over a range of temperatures in order to observe directly the surface orientation as the polymer is heated and cooled through glass, crystal, and liquid crystal phases. In addition, samples annealed under varying processing conditions and quenched to room temperature were analyzed. The NEXAFS data show that (a) in thin F8T2 films at all temperatures the polymer backbone lies in the plane of the substrate, (b) the fluorene and thiophene rings are rotated randomly about the molecular axis, (c) orientation of the polymer backbone can be controlled using a rubbed polyimide alignment layer as a template for liquid crystal orientation, and (d) under proper annealing conditions there is strong temperature-dependent alignment of the copolymer main-chain axis to the rubbing direction which extends from the polyimide/F8T2 interface all the way to the F8T2 surface. The surface alignment does not disappear after annealing at temperatures ∼30 K above the bulk nematic to isotropic transition.
We describe nickel tetrabenzoporphyrin ͑NiTBP͒ as a solution-processible organic semiconductor. Whereas porphyrins in an unmodified state are typically planar and insoluble, a precursor synthetic route ͑NiCP͒ was used to deposit thin films via solution. Amorphous, insulating thin films of NiCP were deposited, and thermally converted to polycrystalline, semiconducting NiTBP. Films were studied using optical absorption and microscopy, atomic force microscopy, and x-ray diffraction. Highly concentrated NiCP was shown to form large, needle-shaped crystals drop-cast from solution. NiTBP thin-film field-effect transistors fabricated from spun-cast films demonstrated charge-carrier field-effect mobilities on the order of 0.1 and 0.2 cm 2 / V s and accumulation threshold voltages of −19 and −13, in the linear and saturation regimes, respectively.
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