Hierarchically engineered nanostructures from compositionally anisotropic molecular building blocks.

The inability to synthesize hierarchical structures with independently tailored nanoscale and mesoscale features limits the discovery of next-generation multifunctional materials. Here we present a predictable molecular self-assembly strategy to craft nanostructured materials with a variety of phase-in-phase hierarchical morphologies. The compositionally anisotropic building blocks employed in the assembly process are formed by multicomponent graft block copolymers containing sequence-defined side chains. The judicious design of various structural parameters in the graft block copolymers enables broadly tunable compositions, morphologies and lattice parameters across the nanoscale and mesoscale in the assembled structures. Our strategy introduces advanced design principles for the efficient creation of complex hierarchical structures and provides a facile synthetic platform to access nanomaterials with multiple precisely integrated functionalities.

Single Gyroid Self-Assembled by Linear BABAB Pentablock Copolymer.

Although the double-gyroid (DG) structure has been commonly formed from the self-assembly of block copolymers, the single-gyroid (SG) structure is rarely reported. Moreover, the SG structure even shows better performance than DG in some optical applications. How to prepare the SG structure has become an attractive but challenging topic. We speculate that the SG structure can be stabilized by the synergistic effect of released packing frustration and stretched bridging block in AB-type block copolymers. Accordingly, we propose the minimum conditions for the design of architecture that enables the two mechanisms simultaneously. Following these conditions, a simple linear BABAB pentablock copolymer is successfully devised. SCFT calculations confirm that the SG phase can be stabilized by tailoring the architecture. Our work is hopeful to promote relevant experimental studies for engineering the unusual SG structure.

Regulate the Stability of Gyroids of ABC-Type Multiblock Copolymers by Controlling the Packing Frustration.

We propose to regulate the stability of gyroids of ABC-type multiblock copolymers by controlling the packing frustration of majority-component B-blocks. Accordingly, we investigate the self-assembly behaviors of the BABCB linear terpolymer with a variable length ratio τ of the middle B-block relative to the total B-blocks using self-consistent field theory. It is observed that the gyroid region exhibits a maximal width with respect to τ, which is attributed by the nonmonotonical change of the packing frustration of three B-blocks in the morphology of discrete domains, for example, cylinders. Then we further purposely design another ABC-type copolymer composed of an ABC linear triblock tethered by another B-block at the middle of the B-block. In contrast, the packing frustration of B-blocks of the second terpolymer drops down continuously as the middle B-block shortens, thus, expanding the stable regions of cylinders and spheres while contracting those of lamella and gyroid.

Stabilizing Phases of Block Copolymers with Gigantic Spheres via Designed Chain Architectures.

It is generally believed that the spherical domains self-assembled from AB-type block copolymers are composed of the minority A blocks with a volume fraction of fA < 1/2. Breaking this generic rule so that the spherical domains are formed by the majority A blocks (fA > 1/2) requires mechanisms to drastically expand the stable region of spherical packing phases. Self-consistent field theory predicts that dendron-like AB-type block copolymers, composed of G - 1 generations of A blocks connected with the outermost generation of B blocks, exhibit a stable region of spherical packing phases extending to fA ∼ 0.7. The extremely expanded spherical regions shed light on the mechanisms governing the self-assembly of amphiphilic macromolecules, as well as provide opportunities to engineer complex spherical packing phases.

Synergistic Effect of Stretched Bridging Block and Released Packing Frustration Leads to Exotic Nanostructures.

The self-assembly of amphiphilic macromolecules into various mesocrystals has attracted abiding interest. Although many interesting mesocrystals have been achieved, mesocrystals of a low coordination number (CN) such as simple cubic are rarely reported. Here we purposely design an AB-type multiblock copolymer to target exotic spherical phases of low CNs. Self-consistent field theory reveals that two sophisticated mechanisms are realized in the copolymer, that is, stretched bridging block and released packing frustration, synergistically leading to the formation of three spherical phases with extremely low CNs, including the simple cubic spheres (CN = 6), the cubic diamond spheres (CN = 4), and normally aligned hexagonal-packing spheres (6 < CN < 8) in a considerable parameter region. Moreover, we demonstrate that these exotic phases are hard to be stabilized by either of the two mechanisms individually.

Tetragonal phase of cylinders self-assembled from binary blends of AB diblock and (A'B)n star copolymers.

The phase behavior of binary blends composed of AB diblock and (A'B)n star copolymers is studied using the polymeric self-consistent field theory, focusing on the formation and stability of the stable tetragonal phase of cylinders. In general, cylindrical domains self-assembled from AB-type block copolymers are packed into a hexagonal array, although a tetragonal array of cylinders could be more favourable for lithography applications in microelectronics. The polymer blends are designed such that there is an attractive interaction between the A and A' blocks, which increases the compatibility between the two copolymers and thus suppresses the macroscopic phase separation of the blends. With an appropriate choice of system parameters, a considerable stability window for the targeted tetragonal phase is identified in the blends. Importantly, the transition mechanism between the hexagonal and tetragonal phases is elucidated by examining the distribution of the two types of copolymers in the unit cell of the structure. The results reveal that the short (A'B)n star copolymers are preferentially located in the bonding area connecting two neighboring domains in order to reduce extra stretching, whereas the long AB diblock copolymers are extended to further space of the unit cell.

Chiral selection of single helix formed by diblock copolymers confined in nanopores.

Chiral selection has attracted tremendous attention from the scientific communities, especially from biologists, due to the mysterious origin of homochirality in life. The self-assembly of achiral block copolymers confined in nanopores offers a simple but useful model of forming helical structures, where the helical structures possess random chirality selection, i.e. equal probability of left-handedness and right-handedness. Based on this model, we study the stimulus-response of chiral selection to external conditions by introducing a designed chiral pattern onto the inner surface of a nanopore, aiming to obtain a defect-free helix with controllable homochirality. A cell dynamics simulation based on the time-dependent Ginzburg-Landau theory is carried out to demonstrate the tuning effect of the patterned surface on the chiral selection. Our results illustrate that the chirality of the helix can be successfully controlled to be consistent with that of the tailored surface patterns. This work provides a successful example for the stimulus response of the chiral selection of self-assembled morphologies from achiral macromolecules to external conditions, and hence sheds light on the understanding of the mechanism of the stimulus response.

Stabilizing the Frank-Kasper Phases via Binary Blends of AB Diblock Copolymers.

The emergence of the complex Frank-Kasper phases from binary mixtures of AB diblock copolymers is studied using the self-consistent field theory. The relative stability of different ordered phases, including the Frank-Kasper σ and A15 phases containing nonspherical minority domains with different sizes, is examined by a comparison of their free energy. The resulting phase diagrams reveal that the σ phase occupies a large region in the phase space of the system. The formation mechanism of the σ phase is elucidated by the distribution of the two diblock copolymers with different lengths and compositions. In particular, the segregation of the two types of copolymers, occurring among different domains and within each domain, provides a mechanism to regulate the size and shape of the minority domains, thus enhancing the stability of the Frank-Kasper phases. These findings provide insight into understanding the formation of the Frank-Kasper phases in soft matter systems and a simple route to obtain complex ordered phases using block copolymer blends.