Annealing temperature-dependent induced supramolecular chiroptical response of copolymer thin films studied by pump-modulated transient circular dichroism spectroscopy

Copolymer thin films showing induced supramolecular chirality are of considerable interest for optoelectronic applications such as organic light-emitting diodes. Here, we introduce a new helicene-like chiral additive with two octyloxy substituents which displays excellent chiral induction properties in an achiral polyfluorene copolymer, leading to a circular dichroism (CD) response of up to 10,000 mdeg. This chiral inducer also displays very good thermal stability, which enables us to perform an extended study on the induced chiroptical properties of the cholesteric copolymer thin films annealed at different temperatures in the range 140-260 °C. Starting from about 180 °C, a distinct change in the morphology of the CD-active film is observed by CD microscopy, from micrometre-size granular to extended CD-active regions, where the latter ones display skewed distributions of the dissymmetry parameter gabs. Broadband Müller matrix spectroscopy finds a pronounced CD and circular birefringence (CB) response and only weak linear dichroism (LD, LD') and linear birefringence (LB, LB'). Ultrafast transient CD spectroscopy with randomly polarised excitation reveals a clean mirror-image-type transient response, which shows a second-order decay of the S1 population due to singlet-singlet annihilation processes.