Plasticizer-Induced Enhancement of Mesoscale Dissymmetry in Thin Films of Chiral Polymers with Variable Chain Length

Conjugated polymers with chiral side chains are of interest in areas including chiral photonics, optoelectronics, and chemical and biological sensing. However, the low dissymmetry factors of most neat polymer thin films have limited their practical application. Here, a robust method to increase the absorption dissymmetry factor in a poly-fluorene-thiophene (PF8TS series) system is demonstrated by varying molecular weight and introducing an achiral plasticizer, polyethylene mono alcohol (PEM-OH). Extending chain length within the optimal range and adding this long-chain alcohol significantly enhance the chiroptical properties of spin-coated and annealed thin films. Mueller matrix spectroscopic ellipsometry (MMSE) analysis shows good agreement with the steady-state transmission measurements confirming a strong chiral response (circular dichroism (CD) and circular birefringence (CB)), ruling out linear dichroism, birefringence, and specific reflection effects. Solid-state NMR studies of annealed hybrid chiral polymer systems show enhancement of signals associated with aromatic pi-stacked backbone and the ordered side-chain conformations. Further studies using Raman spectroscopy, X-ray diffraction (XRD), differential scanning calorimetry (DSC), atomic force microscopy (AFM), and polarized optical microscopy (POM) indicate that PEM-OH facilitates mesoscopic crystal domain ordering upon annealing. This provides new insights into routes for tuning optical activity in conjugated polymers. Blending of variable chain length chiral polymers with a plasticizer additive results in dramatic enhancement of the absorbance dissymmetry ratio due to structural order enhancement following annealing of chiral polymer:plasticizer blends. The Mueller matrix ellipsometry confirms strong chiroptical response in agreement with conventional circular dichroism measurements. These findings open a new pathway for tuning optical activity of conjugated chiral polymers.image