Abstract
The spectroscopy of solid anthracene is examined both experimentally and theoretically. To avoid experimental complications such as self-absorption and polariton effects, ultrathin polycrystalline films deposited on transparent substrates are studied. To separate the contributions from different emitting species, the emission is resolved in both time and wavelength. The spectroscopic data are interpreted in terms of a three-state kinetic model, where two excited states, a high energy state 1 and a low energy state 2, both contribute to the luminescence and are kinetically coupled. Using this model, we analyze the spectral lineshape, relative quantum yield, and relaxation rates as a function of temperature. For state 1, we find that the ratio of the 0-0 vibronic peak to the 0-1 peak is enhanced by roughly a factor of 3.5 at low temperature, while the quantum yield and decay rates also increase by a similar factor. These observations are explained using a theoretical model previously developed for herringbone polyacene crystals. The early-time emission lineshape is consistent with that expected for a linear aggregate corresponding to an edge-dislocation defect. The results of experiment and theory are quantitatively compared at different temperatures in order to estimate that the singlet exciton in our polycrystalline films is delocalized over about ten molecules. Within these domains, the exciton's coherence length steadily increases as the temperature drops, until it reaches the limits of the domain, whereupon it saturates and remains constant as the temperature is lowered further. While the theoretical modeling correctly reproduces the temperature dependence of the fluorescence spectral lineshape, the decay of the singlet exciton appears to be determined by a trapping process that becomes more rapid as the temperature is lowered. This more rapid decay is consistent with accelerated trapping due to increased delocalization of the exciton at lower temperatures. These observations suggest that exciton coherence can play an important role in both radiative and nonradiative decay channels in these materials. Our results show that the spectroscopy of polyacene solids can be analyzed in a self-consistent fashion to obtain information about electronic delocalization and domain sizes. (c) 2008 American Institute of Physics.