Photoluminescence properties of poly (p-phenylene vinylene) films deposited by chemical vapor deposition

Photoluminescence spectra of PPV at varying thicknesses and temperatures have been studied. A study of the quenching of the polymer film using a modified version of fluorescence spectroscopy reveals interface effects dominating at thicknesses below about 600 Å, while bulk effects dominate at higher thicknesses. The application of the Stern-Volmer equation to solid film is discussed. Stern-Volmer plots were nonlinear with downward deviations at higher thickness of the film which was explained due to self-quenching in films and larger conformational change and increased restriction from change in electron density due to electron transition during excitation in bulk polymer films over 60 nm thick. PPV deposited into porous (~4 nm in diameter) nanostructured substrate shows a larger 0-0 than 0-1 transition peak intensity and decreased disorder in the films due to structure imposed by substrate matrix. Temperature dependent effects are measured for a film at 500 Å, right on the border between the two areas. PPV films deposited on porous methyl silsesquioxane (MSQ) were also examined in order to compare the flat film to a substrate that allows for the domination of interface effects. The enthalpies of the first two peaks are very similar, but the third peak demonstrates a lower enthalpy and a larger wavelength shift with temperature. Films deposited inside pores show a smaller amount of disorder than flat films. Calculation of the Huang-Rhys factor at varying temperatures for the flat film and film in porous MSQ shows large temperature dependence for the flat film but a smaller amount of disorder in the nanostructured film.