Direct Imaging of the Crystalline Domains and Their Orientation in the PS‑<i>b</i>‑PEO Block Copolymer with 4D-STEM

The arrangement of crystalline domains in semicrystalline polymers is key to understanding how to optimize the nanostructured morphology for enabling better properties. For example, in polystyrene-b-poly(ethylene oxide) (PS-b-PEO), the degree of crystallinity and arrangement of the crystallites within the PEO phase plays a crucial role in determining the physical properties of the electrolyte. Here, we used four-dimensional scanning transmission electron microscopy to directly visualize the crystal domains within the PEO-rich region of the PS-b-PEO block copolymer and show the relative angle of the domain with respect to the PEO–PS interface. As demonstrated here, our analysis method is applicable to other electron-beam sensitive materials, especially semicrystalline polymers, to unveil their local phase condition and distribution.