Resolving Triblock Terpolymer Morphologies by Vapor-Phase Infiltration

The spontaneous formation of well-organized three-dimensional (3D) nanostructures from self-assembled block copolymers (BCPs) holds promise for nanofabrication and lithography. The addition of a third block to BCPs provides access to a plethora of 3D geometries, but it remains difficult to resolve the geometry of such "three-color" structures when there is low contrast between the polymeric components at length scales of a few nanometers. Here, we apply vapor-phase infiltration synthesis to a silicon-containing triblock terpolymer, poly(1,1-dimethyl silacyclobutane-b-styrene-b-lactide) (PDMSB-b-PS-b-PLA or DSL) to distinguish the 3D microdomain morphologies of the two organic blocks, PLA and PS. Selective infiltration of ZnO within the PLA microdomains reveals morphologies consisting of three-color lamellae or lamellae combined with vertically aligned core-shell cylinders, depending on the volume fractions of each block. The infiltration produces ZnO nanoparticles throughout the 260 nm thickness of the DSL film, generating 3D nanocomposites containing ZnO and SiOx. These results provide a strategy for synthesizing multicomponent 3D nanostructures as well as visualizing the phase behavior of multiblock copolymers.