Confinement-Induced Crystal Growth in One-Dimensional Isotactic Polystyrene Nanorod Arrays

This work demonstrates the anomalous crystal growth of isotactic polystyrene (iPS) in nanorod arrays with different rod sizes. At the bottom of the nanorods, the crystals in bulk film grow into nanorods along either the [110] or [100] direction parallel to the rod axis. On the top side of the nanorods, the polymer exhibits different orientations corresponding to weak or strong confinement. In the weaker confinement (bigger nanorods of 300 nm diameter), the crystals grow with the [100] direction along the nanorod, which is similar to the crystals developed in the radial of spherulite. In the stronger confinement (smaller nanorods of 65 nm diameter), the splaying of crystals in the rod is significantly suppressed, and the preferred growth direction of iPS crystals is kept in either the [110] or [100] direction. The precise control of polymer crystal orientation and crystallinity at a local scale opens important perspectives for the design of one-dimensional nanomaterials whose performance depends on the anisotropic crystal properties.