| Abstract: | Here, studies on the evolution of photophysics and device performance with annealing of blends of poly(3‐hexylthiophene) with the two polyfluorene copolymers poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐4,7‐bis(3‐hexylthien‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2′′‐diyl) (F8TBT) and poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) are reported. In blends with F8TBT, P3HT is found to reorganize at low annealing temperatures (100 °C or below), evidenced by a redshift of both absorption and photoluminescence (PL), and by a decrease in PL lifetime. Annealing to 140 °C, however, is found to optimize device performance, accompanied by an increase in PL efficiency and lifetime. Grazing‐incidence small‐angle X‐ray scattering is also performed to study the evolution in film nanomorphology with annealing, with the 140 °C‐annealed film showing enhanced phase separation. It is concluded that reorganization of P3HT alone is not sufficient to optimize device performance but must also be accompanied by a coarsening of the morphology to promote charge separation. The shape of the photocurrent action spectra of P3HT:F8TBT devices is also studied, aided by optical modeling of the absorption spectrum of the blend in a device structure. Changes in the shape of the photocurrent action spectra with annealing are observed, and these are attributed to changes in the relative contribution of each polymer to photocurrent as morphology and polymer conformation evolve. In particular, in as‐spun films from xylene, photocurrent is preferentially generated from ordered P3HT segments attributed to the increased charge separation efficiency in ordered P3HT compared to disordered P3HT. For optimized devices, photocurrent is efficiently generated from both P3HT and F8TBT. In contrast to blends with F8TBT, P3HT is only found to reorganize in blends with F8BT at annealing temperatures of over 200 °C. The low efficiency of the P3HT:F8BT system can then be attributed to poor charge generation and separation efficiencies that result from the failure of P3HT to reorganize. |
