Ordered Nanostructures in Thin Films of Precise Ion-Containing Multiblock Copolymers

[Image: see text] We demonstrate that ionic functionality in a multiblock architecture produces highly ordered and sub-3 nm nanostructures in thin films, including bicontinuous double gyroids. At 40 °C, precise ion-containing multiblock copolymers of poly(ethylene-b-lithium sulfosuccinate ester)(n) (PESxLi, x = 12 or 18) exhibit layered ionic assemblies parallel to the substrate. These ionic layers are separated by crystalline polyethylene blocks with the polymer backbones perpendicular to the substrate. Notably, above the melting temperature (T(m)) of the polyethylene blocks, layered PES18Li thin films transform into a highly oriented double-gyroid morphology with the (211) plane (d(211) = 2.5 nm) aligned parallel to the substrate. The cubic lattice parameter (a(gyr)) of the double gyroid is 6.1 nm. Upon heating further above T(m), the double-gyroid morphology in PES18Li transitions into hexagonally packed cylinders with cylinders parallel to the substrate. These layered, double-gyroid, and cylinder nanostructures form epitaxially and spontaneously without secondary treatment, such as interfacial layers and solvent vapor annealing. When the film thickness is less than ∼3a(gyr), double gyroids and cylinders coexist due to the increased confinement. For PES12Li above T(m), the layered ionic assemblies simply transform into disordered morphology. Given the chemical tunability of ion-functionalized multiblock copolymers, this study reveals a versatile pathway to fabricating ordered nanostructures in thin films.