Towards General Guidelines for Aligned, Nanoscale Assemblies of Hairy-Rod Polyfluorene


  • This work is funded by One North East (UK) UIC Nanotechnology Grant. We acknowledge U. Scherf of the University of Wuppertal; J. P. Foreman, T. P. A. Hase, C. Pearson, and M. C. Petty of the University of Durham; K. Kisko and R. Serimaa of the University of Helsinki; O. H. Seeck of HASYLAB am DESY; and M. J. Winokur of the University of Wisconsin-Madison for contributions and discussions. Thanks are also due to W1.1 beamline at DESY and the XMaS beamline at the ESRF.


This account highlights recent progress towards understanding the complex hierarchical levels of solid-state structure in a prototypical helical hairy-rod polyfluorene, poly[9,9-bis(2-ethylhexyl)fluorene-2,7-diyl] (or PF2/6). This branched-side-chain containing polyfluorene undergoes a systematic intermolecular self-assembly and liquid-crystalline phase behavior in combination with uniaxial and biaxial alignment. The latter processes yield full three-dimensional orientation of the crystallites and polymer chains. Also reviewed are the impact of the molecular structure and phase behavior on surface morphology, anisotropic film formation, and, ultimately, the overall impact of these physical attributes on optical constants. This particular polyfluorene also represents a model system for demonstrating the applicability of mean-field theory in detailing the self-organization of aligned hairy-rod block-copolymer systems. These results of PF2/6 are compared to those of other archetypical π-conjugated hairy-rod polymers. General guidelines of how molecular weight influences nanostructure, phase behavior, alignment, and surface morphology are given.