Advances in synthetic polymer chemistry have unleashed seemingly unlimited strategies for producing block polymers with arbitrary numbers (n) and types (k) of unique sequences of repeating units. Increasing (k,n) leads to a geometric expansion of possible molecular architectures, beyond conventional ABA-type triblock copolymers (k = 2, n = 3), offering alluring opportunities to generate exquisitely tailored materials with unparalleled control over nanoscale-domain geometry, packing symmetry, and chemical composition. Transforming this potential into targeted structures endowed with useful properties hinges on imaginative molecular designs guided by predictive theory and computer simulation. Here, we review recent developments in the field of block polymers.

Block polymers have undergone extraordinary evolution since their inception more than 60 years ago, maturing from simple surfactants to an expansive class of macromolecules encoded with exquisite attributes. Contemporary synthetic accessibility coupled with facile characterization and rigorous theoretical advances have conspired to continuously generate fundamental insights and enabling concepts that target applications spanning chemistry, biology, physics, and engineering. Here, we parse the vast literature to examine the forefront of the field and identify exciting themes and challenging opportunities that portend a bracing future trajectory. This Perspective celebrates the visionary role played by Macromolecules in advancing our understanding of this remarkable class of materials.

This Perspective addresses the current state of block copolymer lithography and identifies key challenges and opportunities within the field. Significant strides in experimental and theoretical thin film research have nucleated the transition of block copolymers “from lab to fab”, but outstanding questions remain about the optimal materials, processes, and analytical techniques for first-generation devices and beyond. Particular attention herein is focused on advances and issues related to thermal annealing. Block copolymers are poised to change the traditional lithographic resolution enhancement paradigm from “top-down” to “bottom-up”.

Block copolymers (BCPs) must necessarily have high interaction parameters (χ), a fundamental measure of block incompatibility, to self-assemble into sub-10-nanometer features. Unfortunately, a high χ often results from blocks that have disparate interfacial energies, which makes the formation of useful thin-film domain orientations challenging. To mitigate interfacial forces, polymers composed of maleic anhydride and two other components have been designed as top coats that can be spin-coated from basic aqueous solution in the ring-opened, acid salt form. When baked, the anhydride reforms and switches polarity to create a neutral layer enabling BCP feature alignment not possible by thermal annealing alone. Top coats were applied to the lamella-forming block copolymers poly(styrene-block-trimethylsilylstyrene-block-styrene) and poly(trimethylsilylstyrene-block-lactide), which were thermally annealed to produce perpendicular features with linewidths of 15 and 9 nanometers, respectively.

The self-assembly of block polymers into well-ordered nanostructures underpins their utility across fundamental and applied polymer science, yet only a handful of equilibrium morphologies are known with the simplest AB-type materials. Here, we report the discovery of the A15 sphere phase in single-component diblock copolymer melts comprising poly(dodecyl acrylate)−block−poly(lactide). A systematic exploration of phase space revealed that A15 forms across a substantial range of minority lactide block volume fractions (fL = 0.25 − 0.33) situated between the σ-sphere phase and hexagonally close-packed cylinders. Self-consistent field theory rationalizes the thermodynamic stability of A15 as a consequence of extreme conformational asymmetry. The experimentally observed A15−disorder phase transition is not captured using mean-field approximations but instead arises due to composition fluctuations as evidenced by fully fluctuating field-theoretic simulations. This combination of experiments and field-theoretic simulations provides rational design rules that can be used to generate unique, polymer-based mesophases through self-assembly.