Effects of characteristic length scales on the exciton dynamics in rubrene single crystals

We present temperature dependent time-resolved photoluminescence (PL) investigations on well-defined morphologies of the prototypical organic semiconductor rubrene. By their respective degree of spatial constraint these morphologies directly influence the temperature dependent excitonic processes and their dynamics. While in bulk single crystals singlet exciton decay is governed by thermally activated fission at a time constant of 20 ps, this mechanism appears to be absent in rubrene microcrystals. Here the dynamics are characterized by a pronounced increase of the average exciton lifetime as confirmed by the dominating PL decay channel with an effective time constant of 100 ps. The enhanced surface-to-volume ratio indicates that the participating states might originate from microcrystal boundaries which could be reached by the substantial amount of migrating excitons prior to the onset of other decay processes. The suppression of singlet fission in these crystalline microstructures is promoted by the significantly lower activation energy of 25 meV for the 100 ps channel compared to the singlet fission barrier of 44 meV and imposes severe consequences for its utilization in, e.g., thin film photovoltaics. For the crystalline samples, an additional relaxation channel with a time constant of around 500 ps becomes relevant at very low temperatures. As this process is the only one observed for amorphous rubrene thin films it points at the local nature of the underlying decay mechanism.