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We have studied the structure and growth regularities of highly ordered para-sexiphenyl (C36H26) thin films deposited by Hot Wall Epitaxy on mica. In particular, atomic force microscopy (AFM) was used to investigate the early growth stage of these films, in order to find the process controlling parameters. It was shown that the substrate temperature and the growth time are important parameters for control of the film morphology, in terms of the degree of anisotropy and long range order. X-ray diffraction pole figure technique and transmission electron microscopy were also used to characterize the crystallographic structure of the thicker films. We have shown that the highly ordered crystallites of para-sexiphenyl (showing needle-like morphology by AFM) are oriented with their (11 1 ) or (11 2 ) crystallographic planes parallel to the substrate surface. For each of these two orientations there are two opposite directions for growth of crystallites reflecting the two-fold symmetry of the mica surface.
Poly(dithieno[3,4-b:3',4'-d]thiophene) (pDTT1), poly(dithieno[3,4-b:3',2'-d]thiophene (pDTT2) and poly(dithieno[3,4-b:2',3'-d]thiophene) (pDTT3) are low band-gap polymers that undergo both p- (oxidation) and n- (reduction) type electrochemical reversible doping in organic electrolytes. In this work we report on the in-situ IR spectroscopic characterization of both doping types using attenuated total reflection (ATR) FTIR spectroelectrochemistry. Thin polymer films were prepared on Ge reflection elements by electrosynthesis. During electrochemical potential cycling experiments in a spectroelectrochemical cell, the evolution of infrared active vibrational (IRAV) modes, correlated with the generation of charge within the polymer chain, was studied. In addition to electrochemical doping, the polymers exhibit also charged excitations by photodoping. FTIR spectra recorded by illumination/dark cycles show photoinduced IRAV bands which are similar to those found for the electrochemically p-doped materials. The infrared spectroscopic results are compared with Raman spectra of the neutral polymers. The relationship between vibrational properties and structure of the polymers is discussed in terms of different contribution of the φ-electrons within the repeating units to the electronic structure of the conjugated backbone.
This work focuses on single - and bilayers of para - hexaphenyl (PHP) and C60 grown by Hot Wall Epitaxy. A detailed study of the growth process was performed on glass, ITO and (001)- oriented cleaved mica substrates. The ordering of the layers was investigated by X-ray diffraction, showing clear diffraction peaks for layers grown on mica. The PHP layers grown on mica show high optical anisotropy (dichroic ratios up to 14 in emission) according to the polarization dependent photoluminescence experiments. The highly ordered structure is also reflected in the surface morphology of the layer as observed by atomic force microscopy. The epitaxial growth on mica is mirrored by the main alignment of the surface structure to the orientation of the mica substrate.
Fourier transform infrared (FTIR) spectroscopy is a powerful method to determine the doping induced structural changes and electronic band structure modifications of conjugated polymer films. Here, we report in situ attenuated total reflection (ATR) FTIR spectroelectrochemical results of reduction reactions (n-doping) of the conjugated ladder polymer polybenzimidazophenanthroline, BBL. The ATR-FTIR spectra are recorded in situ during continuous potential cycling of a BBL coated germanium reflection element in a three electrode spectroelectrochemical cell. The spectra and the structural changes during the reduction (n-doping) of the polymer film at different electrode potentials are presented. In contrast to most of the other conjugated polymers, this polymer shows four reversible redox reactions during n-doping, corresponding to various forms of BBL with different conductivities.
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