Photophysics of an electrophosphorescent platinum (II) porphyrin in solid films.

We examine electronic processes in platinum (II) octaethyl porphyrin (PtOEP) embedded in an organic solid state matrix and in the form of vacuum-evaporated neat films in conjunction with potential applications of this compound to organic photovoltaic and electrophosphorescent devices. Absorption, photoexcitation, and luminescence spectra indicate the excitonic dimers to be dominant excited states, and their dissociation underlies the charge photogeneration process. Different charge separation distance (1.5 nm and 2.6 nm) in opposite charge carrier pairs preceding dissociation can be distinguished based on the fit of the three-dimensional Onsager theory of geminate recombination to electromodulated luminescence and photoconduction measurements. The near-positive electrode concentrated triplet dimer excitons, produced by strongly 370 nm absorbed light in neat PtOEP films, are efficiently quenched by electron transfer to the metal (Al), generating the positive charge with an efficiency eta+ exceeding 0.15 at high electric fields and dominating the measured photocurrent. Their dissociation efficiency in the bulk, eta- (negatively biased illuminated electrode), is more than one order of magnitude lower than eta+. The dissociation of singlet dimer states dominates the bulk photogeneration process induced by the weakly-absorbed light at 450 nm, with comparable eta+ and eta-. The "hot excited state" underlying the temperature-increasing emission at 540 nm has been attributed to the upper excitonic component Q+ of the first absorption band Q consistent with the exciton concept applied successfully to the interpretation of all dimer-underlain spectroscopic features of PtOEP samples studied.