RESUMO
In this study, we aim to examine the morphological evolution of block copolymer (BCP) nanostructured thin films through solvent evaporation at different rates for solvent swollen polystyrene-block-poly(l-lactide) (PS-PLLA). Interesting phase transitions from disorder to perpendicular cylinder and then gyroid can be found while using a partially selective solvent for PS to swell PS-PLLA thin film followed by solvent evaporation. During the transitions, gyroid-forming BCP thin film with characteristic crystallographic planes of (111)G, (110)G, and (211)G parallel to air surface can be observed, and will gradually transform into coexisting (110)G and (211)G planes, and finally transforms to (211)G plane due to the preferential segregation of constituted block to the surface (i.e., the thermodynamic origin for self-assembly) that affects the relative amount of each component at the air surface. With the decrease on the evaporation rate, the disorder phase will transform to parallel cylinder and then directly to (211)G without transition to perpendicular cylinder phase. Most importantly, the morphological evolution of PS-PLLA thin films is strongly dependent upon the solvent removal rate only in the initial stage of the evaporation process due to the anisotropy of cylinder structure. Once the morphology is transformed back to the isotropic gyroid structure after long evaporation, the morphological evolution will only relate to the variation of the surface composition. Similar phase transitions at the substrate can also be obtained by controlling the ratio of PLLA-OH to PS-OH homopolymers to functionalize the substrate. As a result, the fabrication of well-defined nanostructured thin films with controlled orientation can be achieved by simple swelling and deswelling with controlled evaporation rate.
RESUMO
This work presents a new method for forming well-defined nanostructured thin films from self-assembled polystyrene-block-poly(l-lactide) (PS-PLLA) on Si wafers with a functionalized SiO2 surface. Large, well-ordered, perpendicular PLLA cylinders in PS-PLLA thin films can be formed using the functionalized substrate. In contrast to random copolymers, a neutral substrate for the PS and PLLA blocks is formed by functionalizing a substrate with hydroxyl-terminated PS (PS-OH) followed by hydroxyl-terminated PLLA (PLLA-OH). The heterogeneous grafting of PS-OH and PLLA-OH can be substantially alleviated using this two-step functionalization. Accordingly, the surface properties can be fine-tuned by controlling the ratio of grafted PS-OH to PLLA-OH to control the orientation of the PLLA cylinders on the functionalized SiO2. Nevertheless, the orientation that is driven by the neutral substrate is surprisingly limited in that the effective length of orienting cylinders is less than twice the interdomain spacing. Thermal annealing at high temperature can yield a neutral air surface, rendering perpendicular PLLA cylinders that stand sub-micrometers from the air surface. Consequently, the neutral substrate can be used to enable truly film-spanning perpendicular cylinders in films to be fabricated using the high-temperature thermal treatment. In addition, the perpendicular cylinders can be laterally ordered by further increasing the annealing temperature. The ability to create these film-spanning perpendicular cylinders in films with a well-ordered texture and sub-micrometer thickness opens up possible applications in nanotechnology.
RESUMO
Nanoporous polymers with gyroid nanochannels can be fabricated from the self-assembly of degradable block copolymer, polystyrene-b-poly(l-lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. A well-defined nanohybrid material with SiO2 gyroid nanostructure in a PS matrix can be obtained using the nanoporous PS as a template for sol-gel reaction. After subsequent UV degradation of the PS matrix, a highly porous inorganic gyroid network remains, yielding a single-component material with an exceptionally low refractive index (as low as 1.1).
