Threading Subunits for Polymers to Predict the Equilibrium Ensemble of Solid Polymer Electrolytes

We present a computational method for polymer growth called “threading subunits for polymers (TSP)” that can efficiently sample solid polymer electrolyte structures with extended conformations. The TSP method involves equilibrating subunit (e.g., monomer) conformations that form favorable solvation ion shells, followed by consecutively connecting the subunits and minimizing the structures. The TSP method can sample polymers with good solvent-like conformations and from near-equilibrium structures in which ions are well-dispersed, avoiding unusual ion clustering under ambient conditions. Using the TSP method, the equilibration time can be reduced significantly by effectively sampling the polymer conformations near equilibrium. We anticipate that the TSP method can be applied to simulate various polymer electrolytes

Morphological Evolution of Block Copolymer Particles: Effect of Solvent Evaporation Rate on Particle Shape and Morphology

Shape and morphology of polymeric particles are of great importance in controlling their optical properties or self-assembly into unusual superstructures. Confinement of block copolymers (BCPs) in evaporative emulsions affords particles with diverse structures, including prolate ellipsoids, onion-like spheres, oblate ellipsoids, and others. Herein, we report that the evaporation rate of solvent from emulsions encapsulating symmetric polystyrene-<i>b</i>-polybutadiene (PS-<i>b</i>-PB) determines the shape and internal nanostructure of micron-sized BCP particles. A distinct morphological transition from the ellipsoids with striped lamellae to the onion-like spheres was observed with decreasing evaporation rate. Experiments and dissipative particle dynamics (DPD) simulations showed that the evaporation rate affected the organization of BCPs at the particle surface, which determined the final shape and internal nanostructure of the particles. Differences in the solvent diffusion rates in PS and PB at rapid evaporation rates induced alignment of both domains perpendicular to the particle surface, resulting in ellipsoids with axial lamellar stripes. Slower evaporation rates provided sufficient time for BCP organization into onion-like structures with PB as the outermost layer, owing to the preferential interaction of PB with the surroundings. BCP molecular weight was found to influence the critical evaporation rate corresponding to the morphological transition from ellipsoid to onion-like particles, as well as the ellipsoid aspect ratio. DPD simulations produced morphologies similar to those obtained from experiments and thus elucidated the mechanism and driving forces responsible for the evaporation-induced assembly of BCPs into particles with well-defined shapes and morphologies

Block Copolymer with an Extremely High Block-to-Block Interaction for a Significant Reduction of Line-Edge Fluctuations in Self-Assembled Patterns

Directed self-assembly (DSA) of block copolymers (BCPs) with a high Flory–Huggins interaction parameter (χ) provides advantages of pattern size reduction below 10 nm and improved pattern quality. Despite theoretical predictions, however, the questions of whether BCPs with a much higher χ than conventional high-χ BCPs can further improve the line edge roughness (LER) and how to overcome their extremely slow self-assembly kinetics remain unanswered. Here, we report the synthesis and assembly of poly­(4vinylpyridine-<i>b</i>-dimethylsiloxane) BCP with an extremely high χ-parameter (estimated to be approximately 7 times higher compared to that of poly­(styrene-<i>b</i>-dimethylsiloxane) – a conventional high-χ BCP) and achieve a markedly low 3σ line edge roughness of 0.98 nm, corresponding to 6% of its line width. Moreover, we demonstrate the successful application of an ethanol-based 60 °C warm solvent annealing treatment to address the extremely slow assembly kinetics of the extremely high-χ BCP, considerably reducing the self-assembly time from several hours to a few minutes. This study suggests that the use of BCPs with an even larger χ could be beneficial for further improvement of self-assembled BCP pattern quality

Single Nanoparticle Localization in the Perforated Lamellar Phase of Self-Assembled Block Copolymer Driven by Entropy Minimization

Although precisely controlled microdomains of block copolymers (BCP) provide an excellent guiding matrix for multiple nanoparticles (NPs) to be controllably segregated into a desired polymer block, localization and positioning of individual NPs have not been demonstrated. Here, we report a unique one-to-one positioning phenomenon of guest Au NPs in the host BCP microdomains; each of polystyrene-functionalized Au NPs is embedded within the perforation domain of hexagonally perforated lamellar (HPL) morphology of poly­(dimethyl­siloxane-<i>b</i>-styrene) BCP. The local minimization of free energy achieved by the placement of Au NPs into the center of the perforation domain is theoretically supported by the self-consistent field theory (SCFT) simulation. We propose a novel design principle for more precisely controllable nanocomposites by developing a new route of NP arrangement within a polymer matrix