Exploring the “Living” Growth of Block Copolymer Nanofibers from Surface-Confined Seeds by In Situ Solution-Phase Atomic Force Microscopy

Living crystallization-driven self-assembly of polymeric and molecular amphiphiles is of growing interest as a seeded growth route to uniform 1D, 2D, and more complex micellar nanoparticles with controlled dimensions and a range of potential applications. Although most studies have been performed using colloidally stable seeds in bulk solution, growth of block copolymer (BCP) nanofibers from seeds confined to a surface is attracting increased attention. Herein, we have used atomic force microscopy (AFM) to undertake detailed studies of the growth of BCP nanofibers from immobilized seeds located on a Si surface. Through initial ex situ AFM studies and in situ AFM video analysis in solution, we determined that growth occurred in four stages, whereby an initial surface-bound growth regime transitions to surface-limited growth. As the nanofiber length increases, surface influence is diminished as the newly grown micelle segment is no longer bound to the Si substrate. Finally, a surface-independent regime occurs where nanofiber growth continues into bulk solution. In addition to the anticipated nanofiber elongation, our studies revealed occasional examples of AFM tip-induced core fragmentation. In these cases, the termini of the newly formed fragments were also active to further growth. Furthermore, unidirectional growth was detected in cases where the seed was oriented at a significant angle with respect to the surface, thereby restricting unimer access to one terminus.