Time-Resolved Excitonic Luminescence Processes in Poly(phenylenevinylene)

Integrated luminescence spectra, time-resolved luminescence spectra, and luminescence decay times of stretch-oriented poly(phenylenevinylene) (PPV) are studied in the temperature range 300∼12 K. The reflectance spectrum at room temperature is also studied. The luminescence spectrum is composed of vibronic bands and a broad band, which are interpreted as caused by radiative annihilation of free and selftrapped excitons, respectively. Temperature dependence of the intensity of free-exciton luminescence and temperature dependence of the decay time are interpreted in terms of relaxation of excitons. The height of a potential barrier, which separates the free exciton state and the self-trapped state, is found to be 350 cm -1 . At 20 K, exciton relaxation toward the self-trapped state occurs by a quantum-mechanical tunneling process. The tunneling rate obtained is (90 ps) -1 .