Exploring the phase behavior of C8-BTBT-C8 at ambient and high temperatures: insights and challenges from molecular dynamics simulations.

C8-BTBT-C8 is one promising candidate for the development of high-performance electronic devices based on thin-film technologies. Its monoclinic polymorph has a well-established role in thin-film growth. Yet, quite little information is available about its dynamics on the molecular scale, and the structures of the mesophases which form at high temperature (about 100 K above ambient temperature). The present study is devoted to the analysis of such phases, with the ultimate goal of developing molecular models. Already at ambient temperature, our molecular dynamics simulations reveal a rich conformational behavior of the alkyl side chains, with conformations as leading structural defects. Heating promotes the formation of a stacking faulted mesophase (380 K), and a smectic phase, at 385 K, upon side chain melting. Although more disordered, this phase bears several analogies with the smectic A phase, experimentally observed at 382.5 K. At higher temperatures, the increase in configurational disorder is brought by molecular diffusion and other phenomena, finally leading to an isotropic molten phase. Our in-depth analysis, complemented by hot-stage polarizing microscopy data, provides interesting insights into this material, highlighting the challenges associated with the modeling of soft semiconducting systems.