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Abstract: We report absorption and first reliable photoluminescence (PL) studies at various temperatures on relatively thick films of the basic polyazomethine — PPI, i.e., poly(1,4-phenylene-methylidynenitrilo-1,4-phenylenenitrilomethylidine), prepared by chemical vapor deposition (CVD). Both absorption and PL spectra exhibit the vibronic progression due to the C–C stretching mode, characteristic for conjugated polymers. The absorption spectra appear to be practically temperature independent, in contrast to PL spectra, the intensity of which strongly decreases with increasing temperature. The origin of generally weak photoluminescence of PPI is suggested to be the result of a non-radiative electronic state occupied by the lone electron pair on the nitrogen orbital. [Copyright &y& Elsevier]

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Abstract: Aromatic polyazomethine (PPI) thin film have been obtained by chemical vapor deposition (CVD) method, via polycondensation process and characterized by X-ray diffraction, AFM, FTIR and detailed UV–Vis–NIR studies. Optical transmission and fundamental reflectivity spectra of the film have been examined within the spectral range 200–2500nm. The refractive index (n), film thickness (d) and parameters of the absorption edge i.e. the optical gap (E G) and the Urbach energy (E U) have been found for the PPI film before and after iodine (I2) doping. Then the annealing effect (from 25°C every 25°C up to 225°C) on the absorption edge have been investigated during “in situ” spectral measurements. Amorphous character of the films allowed us to obtain the E G and E U values, in the way typical for amorphous semiconductors. As a result of iodine doping, the energy gap of the PPI film (2.19eV) distinctly reduces to 1.73eV, due to the polaron states and, simultaneously, the Urbach energy decreases. Thermal stability of the pure PPI film, being the typical feature of polyazomethines, was confirmed, while after iodine doping the film turned out to be thermo-stable only below 100°C; then the distinct changes of the optical gap and the Urbach energy, connected with the iodine releasing process, have been presented and discussed. [Copyright &y& Elsevier]

Abstract: Thin films of poly(1,4-phenylenemethilidynenitrilo-1,4-phenylenenitrilomethilidyne) (PPI) have been prepared by chemical vapor deposition in the horizontal geometry using gaseous argon as a transport agent. PPI thin films have been grown by polycondensation of para-phenylene diamine (PPDA) and terephtal aldehyde (TPA). Fourier Transform Infrared spectra confirm formation of PPI layers without end groups. The strongest absorption band with discernible vibronic progression has been found to be due to superposition of 2.64, 2.82 and 3.03 eV bands corresponding to interband transitions connecting electronic ground state and vibrational levels of electronic excited state. A feature seen at about 2.6 eV in the spectra of PPI films prepared at higher temperatures of PPDA and TPA sources are attributed to excitons connected with the π–π⁎ gap. Shoulder at 3.31 eV is attributed to interband transitions between delocalized states, while a peak at 4.2 eV is attributed to excitons formed by localized holes and delocalized electrons and vice versa and interband transitions connecting delocalized and localized bands, with the binding energy of about 0.8 eV. Thin films prepared at low temperatures of monomers consist of randomly distributed PPI chains weakly bound together. [Copyright &y& Elsevier]

Abstract: Optical transmission and fundamental reflectivity spectra of aromatic polyazomethine thin films, obtained by vacuum evaporation via the polycondensation process have been investigated in the wide spectral range 0.49–6.2eV. As initial monomers, terephaldehyde (TPA) and one of four different amines, i.e. paraphenylene-diamine (PPDA), 7,2-diamino-fluorene, 1,1′-biphenyl-3,3′,4,4′-tetramine and 3-amino-4-(1-naphthyldiazenyl)phenylamine (fat brown RR) have been used, respectively. Amorphous character of these films was confirmed by the results of X-ray diffraction and AFM investigations. Absorption coefficient of the films has been obtained and the edge of absorption seems to be similar to the absorption edge typical for amorphous semiconductors, what allowed to obtain the Urbach energy and E T parameter. The energy gaps of the films, following the Tauc relation, are found to change from 2.05 to 2.4eV, depending on the length of conjugated part of the polymer chain. Absorption bands above the absorption edge, observed for different polyazomethine films are connected with their chemical structure and possible electronic transitions. [Copyright &y& Elsevier]