On the Origin of Green Emission in Polyfluorene Polymers: The Roles of Thermal Oxidation Degradation and Crosslinking

The green emission of poly(9,9′′‐dioctylfluorenyl‐2,7′′‐diyl), end‐capped by polyhedral oligomeric silsequioxanes, (PFO‐POSS) has been investigated by photoluminescence (PL) and photoexcitation (PE), gel permeation chromatography (GPC), and transmission Fourier transform infrared (FTIR) spectroscopy. The green emission is closely correlated with thermal oxidation degradation and crosslinking of the polymer and is enhanced by annealing at elevated temperatures. The green‐to‐blue emission intensity ratio, used to assess the emission properties of thin (90 nm) films, was 3.70, 4.35, and 1.54 for an air‐annealed film, its insoluble residue (crosslinked), and a film cast from its soluble portion, respectively. For thick (5–6 μm) film, the ratios are 13.33, 13.33, and 0.79, respectively. However, FTIR spectroscopy of thick films leads to the conclusion that the carbonyl‐to‐aromatic ring concentration ratio are 0.018, 0.015, and 0.032, respectively. Focusing on the recast films, the green emission is relatively low while the carbonyl concentration is relatively high. This suggests that the energy traps at crosslinked chains play an important role in green emission. It is likely that the crosslinking enhances the excitation energy migration and energy transfer to the defects by hindering chain segment twisting. Green emission from polyfluorene polymers has been investigated by comparing the chemical and physical properties of the soluble and insoluble portions of films. The soluble portion of air‐annealed films displays a less intense green emission than its insoluble counterpart (see Figure), but the carbonyl concentration is higher in the soluble portion in comparison to its insoluble portion. The results suggest that crosslinking plays a significant role in green emission.