Elucidation of novel nanostructures by time-lapse monitoring of polystyrene-block-polyvinylpyridine under chemical treatment.

Nanoscale micellar structures of polystyrene-block-polyvinylpyridine (PS-b-PVP) diblock copolymers have proven their effectiveness in lithography and biological detection by serving as a choice material to produce nanoscale guides and delivery systems in a straightforward and rapid manner through self-assembly. Such applications can greatly benefit from having high versatility for the selection of template sizes (pattern repeat spacing) and shapes (pattern geometry), especially when reaching a size regime that conventional top-down fabrication techniques may not readily be able to provide desired feature dimensions. Selective chemical treatments of the diblock copolymers are one of the useful methods yielding a rich set of nanoscale features on PS-b-PVP. Exposure to selective vapor can induce reorganization of the polymeric chains of PS-b-PVP and alter the original micellar nanostructures. In this Article, we identify for the first time a host of new nanostructures formed at different stages of chloroform vapor annealing by performing time-lapse atomic force microscopy measurements. We determine key, time-dependent, topological parameters defining each nanostructure and present the likely scenario of polymeric chain reorganization during the morphological evolution of the diblock polymer nanodomains over time. We also ascertain intermediate morphological states containing the characteristic nanostructures from two consecutive phases as well as transition states appearing for a short time in between two subsequent phases. These research efforts may not only provide insight into the domain evolution steps of the micellar to the cylindrical structures of PS-b-PVP but may also be technologically advantageous for subwavelength mask design in nanolithography and high-density array fabrication in high throughput biodetection.