Spray coated perylenebisimide/polymer film with controllable molecular aggregation state and emission properties

Dye doped organic thin films with controllable molecular aggregation and emission properties are of broad interest to the scientific community owing to their large number of potential applications in physics, chemistry, and materials science. Here, a spray coating method was used to prepare perylenebisimides (PBI) doped polymer films. In this study, the effects of the dye concentration, polymer matrix, solvent, and casting process on the optical properties of the resulting films were studied. The aggregation of the PBI into monomer, dimer, and oligomer forms, was rapidly and simply controlled based on the concentration dependence of PBI. The molecular aggregation mechanism in the film forming process for PBI doped polystyrene (PS) was further analyzed by computer simulations. The blends rapidly reached their lowest Gibbs free energy owing to the “frozen” polymer chains and confinement of PBI, molecules with different aggregation states. Therefore, the PBIs/PS films prepared under different conditions had different fluorescent lifetimes and absolute quantum yields. Narrow emission, amplified spontaneous emission (ASE) and random lasing (RL) were observed in PBI doped PS films when photo-pumped at 532 nm in transmittance and waveguide modes, respectively. A lower ASE and RL threshold were obtained for PS films doped with monomeric PBI than those in other aggregation states. Moreover, the solvent use in film deposition greatly influenced the emission properties of the PS films by altering their microstructures. These results indicate potential applications for spray coated dye/polymer films in organic solid-state lasers.