Spatially, Temporally and Polarization-Resolved Photoluminescence Exploration of Excitons in Crystalline Phthalocyanine Thin Films

The lack of long range order in organic semiconductor thin films prevents the unveiling of the complete nature of excitons in optical experiments, because the diffraction limited beam diameters in the bandgap region far exceed typical crystalline grain sizes. Here we present spatially-, temporally- and polarization-resolved dual photoluminescence/linear dichroism microscopy experiments that investigate exciton states within a single crystalline grain in solution-processed phthalocyanine thin films. These experiments reveal the existence of a delocalized singlet exciton, polarized along the high mobility axis in this quasi-1D electronic system. The strong delocalized {pi} orbitals overlap controlled by the molecular stacking along the high mobility axis is responsible for breaking the radiative recombination selection rules. Using our linear dichroism scanning microscopy setup we further established a rotation of molecules (i.e. a structural phase transition) that occurs above 100 K prevents the observation of this exciton at room temperature.