Intrachain Aggregates as the Origin of Green Emission in Polyfluorene Studied on Ensemble and Single-Chain Level

Polyfluorenes are conjugated polymers that show strong blue emission and as such have been explored for potential applications in light-emitting devices. However, heat treatment, prolonged exposure to air, or extended operation in electro-luminescent devices can lead to an appearance of parasitic green emission that degrades the material performance. This phenomenon has been extensively studied over the past two decades, and two main and conflicting explanations, i.e., oxidation and formation of fluorenone species on the one hand and inter- or intrachain aggregation on the other, have been put forward. There is abundant experimental evidence to support either of these theories, and the question is far from settled. Here, we aim at getting deeper insight into the problem of the green emission origin using single-molecule spectroscopy performed on individual chains of poly(9,9-di-n-octylfluorene) (PFO) to resolve the green emission band and reveal its spectral and temporal heterogeneity. We disperse single PFO chains in solid thin-film matrices of polystyrene (PS) and poly(methyl methacrylate), as well as in solutions of cyclohexane, toluene, or PS/toluene, to simulate good and poor-solvent environments and environments with different permeabilities and diffusions of oxygen, to systematically study the effects of intrachain aggregation as well as oxidation on the appearance and characteristics of the green band. The studies are complemented by direct measurement of individual chain conformation by atomic force microscopy and by bulk measurements of photoluminescence (PL) lifetimes and quantum yield. The single-molecule results reveal two PL spectral forms in the region of the green emission, a vibrationally resolved type located around 500 nm and broad structureless type located toward lower energies, none of them sensitive to the presence of oxygen. These two types are characterized by different lifetimes of 1.4 and 5.1 ns, respectively, and their oscillator strengths are 2 orders of magnitude smaller compared to those of the blue emission band. These results point to two different optical transitions comprising the green band, and these have been assigned to the emission of H-aggregates and charge transfer or indirectly excited excimer states, respectively.