A spectroscopic assessment of static and dynamic disorder in a film of a polythiophene with a planarized backbone

The optoelectronic performance of organic semiconductor devices is related to the static and dynamic disorder in the film. The disorder can be assessed by considering the linewidth of its optical spectra. We focus on identifying the effect of conjugation length distribution on the static energetic disorder. Hence, we disentangle the contributions of static and dynamic disorder to the absorption and emission spectra of poly(3-(2,5-dioctylphenyl)-thiophene) (PDOPT) by exploring how the linewidth and energy of the spectra evolve upon cooling the sample from 300 K to 5 K. PDOPT has sterically hindered side chains that arrange such as to cause a planarized polymer backbone. This makes it a suitable model for a quasi-one-dimensional molecular system. By modelling the conjugated segments as coupled oscillators we find that the linewidth contribution resulting from the variation of conjugation length decreases linearly with decreasing exciton energy and extrapolates to zero at the energy corresponding to an infinite chain. These results provide a new avenue to the design of low disorder and hence high mobility polymeric semiconductors.