Rapid formation and real-time observation of micron-sized conjugated nanofibers with tunable lengths and widths in 20 minutes by living crystallization-driven self-assembly

Preparing well-defined semiconducting nanostructures from conjugated polymers is of paramount interest for organic optoelectronic devices. Several studies have demonstrated excellent structural and size control from block copolymers ( BCPs ) containing non-conjugated blocks via crystallization-driven self-assembly (CDSA); however, the precise control of their size and shape remains a challenge due to their poor solubility, causing rapid and uncontrolled aggregation. This study presents a new type of fully conjugated BCP comprising two polyacetylene derivatives termed poly(cyclopentenylene-vinylene) to prepare semiconducting 1D nanofibers. Interestingly, the widths of nanofibers were tuned from 12 to 32 nm based on the contour lengths of their crystalline core blocks. Their lengths could also be controlled from 48 nm to 4.7 μm using the living CDSA. Monitoring of the growth kinetics of the living CDSA revealed the formation of micron-sized 1D nanofibers in less than 20 min. The rapid CDSA enabled us to watch real-time growth using confocal fluorescence microscopy. New fully conjugated block copolymers formed semiconducting 1D nanofibers with excellent structural and size control. The rapid living CDSA enabled us to watch the real-time video of the whole self-assembly process.