We report optical and morphological properties of poly(2-methoxy-5-hexyloxy-p-phenylenevinylene) (OC1OC6-PPV) films processed by casting, spin-coating (SC) and Langmuir-Blodgett (LB) techniques. The absorption spectra are practically the same, with an absorption maximum at approximately at 500 nm. For the photoluminescence (PL) spectra at low temperature (T=10K), a small but significant difference was noted in the cast film, in comparison with the LB and SC films. The zero-phonon transition shifted from 609 nm for the LB film to 615 and 621 nm for the SC and cast films, respectively. At room temperature, the PL spectra are similar for all films, and blue shifted by ca. 25 nm in comparison with the spectra at low temperature due to thermal disorder. Using atomic force microscopy (AFM) we inferred that the distinctive behavior of the cast film, probably associated with structural defects, is related to the large thickness of this film. The surface roughness, which was surprisingly higher for the LB film, apparently played no role in the emission properties of OC1OC6-PPV films.

Site-selective luminescence spectroscopy (SSL) was employed to resolve the vibracional modes in self-assembled poly(p-phenylene vinylene), PPV. Using Franck-Condon analysis, the PPV spectra can be well described by three effective vibrational modes at 330, 1160 and 1550 cm-1. As the temperature increases from 4 to 180 K the electron-phonon coupling (S factor) remains constant for the 1550 cm-1 mode while for other lower energy modes the coupling increases monotonically. This trend is consistent with the decrease of the conjugation length due to the increase of thermal disorder. We find that the temperature dependence of vibrational progression in PPV films is determined mainly by low frequency torsional modes.

We report on time resolved photoluminescence (PLRT) measurements in poly(p-phenylene vinylene) (PPV) films irradiated by laser in the presence of air. We observe a PL intensity enhancement and a biexponential decay dynamics of PL signal for all irradiated films. These results can be understood in terms of a chain shortening process due to carbonyl incorporation and formation of an energy profile that extends and migrates into the film and enables efficient spectral diffusion of excited carriers to a non-degraded PPV segments by Förster energy transfer.

The influence of electron-phonon coupling in the emission spectra of self-assembly (SA) films of poly(p-phenylene vinylene) (PPV) is discussed. PPV is an important polymeric system because it exhibits strong luminescence effect. A semi-empirical model was used to analyze the photoluminescence spectra of PPV. This model assumes that defects along the molecule give rise to a distribution of conjugated segments of different lengths. In addition, it was considered that electronic transition was essentially coupled with three effective phonon modes with correspondent energies at 62, -139 and 192 meV, which were observed experimentally.