Influence of technological conditions on electronic transitions in chemical vapor deposited poly(azomethine) thin films

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.