Relative molecular orientations in organic optoelectronic films probed via polarization-selected UV/IR mixed frequency ultrafast spectroscopy^†

Molecular packing patterns are crucial factors determining electron/energy transfer processes that are critical for the optoelectronic properties of organic thin film devices. Herein, the polarization-selective ultraviolet/infrared (UV/IR) mixed frequency ultrafast spectroscopy is applied to investigate the relative molecular orientations in two organic thin films of 7-(diethylamino)coumarin-3-carboxylic acid (DEAC) and perylene. The signal anisotropy changes caused by intermolecular energy/electron transfers are utilized to calculate the cross angles between the electronic transition dipole moment of the donor and the vibrational transition dipole moments of the acceptor, yielding the relative orientation between two adjacent molecules. Using this method, the relative orientation angle in DEAC film is determined to be 53.4°, close to 60° of its single crystalline structure, and that of the perylene film is determined to be 6.2°, also close to −0.2° of its single crystalline structure. Besides experimental uncertainties, the small difference between the angles determined by this method and those of single crystals also results from the fact that the thin film samples are polycrystalline where some of the molecules are amorphous.