Controlling the orientation of nanostructured thin films of block copolymers (BCPs) is essential for next-generation lithography using BCPs. According to conventional wisdom, the orientation of BCP thin films is mainly determined by molecular interactions (enthalpy-driven orientation). Here, we show that the entropic effect can be used to control the orientation of BCP thin films. Specifically, we used the architecture of star-block copolymers consisting of polystyrene (PS) and poly­(dimethylsiloxane) (PDMS) blocks to regulate the entropic contribution to the self-assembled nanostructures. The study unequivocally demonstrate that for star-block copolymers with the same volume fractions of PS and PDMS, perpendicularly oriented BCP nanostructures could be induced via an entropic effect regulated by the number of arms. Also, the feasibility of using the star-block copolymer thin films for practical applications is demonstrated by using the thin film as a mask for nanolithography or as a template for the fabrication of nanoporous monolith.

A simple method to create a variety of nanostructures via the self-assembly of a single composition silicon-containing block copolymer (BCP) is developed. By using selective solvents for the self-assembly of polystyreneblock-poly(dimethylsiloxane) (PS−PDMS), the phase behavior of intrinsic BCP can be enriched due to the strong segregation of the PS−PDMS enabling the diversity of the phase behavior of PS−PDMS/solvent mixtures and clear-cut phase transitions upon solvent evaporation. The solution-state phase behaviors of the strong segregation BCP system in different solvents are systematically studied using temperature-resolved and time-resolved SAXS experiments. A variety of phases, such as sphere, cylinder, gyroid, lamellar phases and even inverted phases, can be acquired by simply tuning the selectivity of solvent for casting. Meanwhile, owing to the high etching contrast of the silicon-containing block versus the PS block, various nanostructured SiOC can be fabricated by using one-step oxidation. This approach suggests an easy way to create inorganic oxide nanostructures for various applications.

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.

This work presents an approach to achieve controlled ordering of polystyrene-block-poly(l-lactide) (PS–PLLA) gyroid thin films on a neutral substrate using solvent annealing. Interesting morphological evolution from gyroid to cylinder can be found while using a partially selective solvent for the PS block to anneal the PS–PLLA thin film. To acquire a thin-film sample with thermodynamically stable gyroid morphology, a nonpreferential solvent should be used for solvent annealing to enable controlled ordering of gyroid thin film with the (211)G plane parallel to the air surface and also the functionalized substrate. By taking advantage of degradable character of the PLLA block, nanoporous PS with well-defined texture can be fabricated by hydrolysis and used as a template for synthesis of various nanohybrids and nanoporous materials.

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Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for next-generation lithography. However, obtaining BCP with perpendicular orientation remains a challenge because of the surface selectivity to the different blocks. This challenge is especially severe for silicon-containing BCPs which is notorious for its high surface energy difference between constituted blocks. Here, we demonstrate a new approach to achieve perpendicular orientation with high aspect ratio using a combination of architecture effect (entropy effect) and surface air plasma treatment (enthalpy effect). Specifically, perpendicular cylinders of star-block copolymers composed of polystyrene and poly­(dimethylsiloxane) blocks can be formed from the bottom substrate to the top surface of the thin film.

Three-dimensional (3D) morphology of hierarchically self-assembled mixed poly(tert-butyl acrylate) (PtBA)/polystyrene (PS) brush-grafted 67 nm silica nanoparticles cast from chloroform on a carbon-coated transmission electron microscopy (TEM) grid was directly visualized using electron tomography (i.e., 3D TEM). The number-average molecular weights for PtBA and PS were 22.2 and 23.4 kDa, and their grafting densities were 0.51 and 0.34 chains/nm2, respectively. For a dense monolayer of mixed brush-grafted silica particles, a rippled phase structure was observed, and the monolayer consisted of protruded top portions from large nanoparticles and a bottom continuous film. In the top protruded part of large nanoparticles, isolated cylindrical PS microdomains were formed in the PtBA matrix due to the low PS volume fraction (i.e., 37%). The morphology in the lower continuous film was strongly influenced by interparticle interactions via mixed polymer brushes. As a result, bicontinuous nanostructures instead of isolated PS microdomains in the PtBA matrix were formed, even though the PS was a minor phase. In the continuous film, the top and bottom regions gave better microphase separation due to the larger interstitial spaces, and the microphase-separated pattern was dictated by the hexagonal packing of hairy silica particles. For isolated individual particles cast from chloroform, different morphology was observed because of the lack of interparticle interactions. Clear lateral microphase separation was observed only in the bottom part of the particle, likely because the mixed brush layer in the top portion was too thin. In the bottom part, isolated PS microdomains with a truncated wedge shape radiated out from the projected center of the individual particle. This is the first time that detailed 3D morphology was thoroughly characterized for self-assembled mixed brush-grafted nanoparticles cast from a nonselective good solvent.

Well-defined linear (n = 1, 2) and star (n = 3, 4) architecture (PS-b-PDMS)n block copolymers were synthesized by anionic polymerization in combination with chlorosilane chemistry. The self-assembly is significantly influenced by entropy constraints for the star samples due to overcrowding.