Directed Self-Assembly by Sparsely Prepatterned Substrates with Self-Responsive Polymer Brushes.

The guiding pattern in the chemoepitaxially directed self-assembly (DSA) of block copolymers is often fabricated by periodically functionalizing homogeneously random copolymer brushes tethered on a substrate. The prepatterned copolymer brushes constitute a soft penetrable surface, and their two components can in principle locally segregate in response to the overlying self-assembly process of block copolymers. To reveal how the self-responsive behavior of the copolymer brushes affects the directing effect, we develop a dissipative particle dynamics model to explicitly include the prepatterned polymer brushes and implement it to simulate the DSA of a cylinder-forming diblock copolymer melt on the sparse pattern of polymer brushes. Through large-scale dynamic simulations, we identify the windows of the content of the random copolymer, the film thickness, and the diameter of the patterned spot, for the formation of perfectly ordered hexagonal patterns composed of perpendicular cylinders. Our dynamic simulations reveal that the random copolymer brushes grafted on the unpatterned area exhibit a remarkable self-responsive ability with respect to the self-assembly of the diblock copolymers overlying them, which may widen the effective window of the content of the random copolymer. Within the processing windows of these key parameters, defect-free patterns are successfully achieved both in simulations and in experiments with sizes as large as a few micrometers for 4-fold density multiplications. This work demonstrates that highly efficient computer simulations based on an effective model can provide helpful guidance for experiments to optimize the critical parameters and even may promote the application of DSA.

Tetragonally and Rectangularly Packed Hierarchical Cylinders from A1 BA2 C Tetrablock Terpolymer.

Hierarchical cylindrical nanostructures with different diameters (or shapes) have received much attention because of potential applications to next-generation lithography or advanced optical devices. Herein, via small-angle X-ray scattering and transmission electron microscopy, tetragonally and rectangularly packed hierachical cylindrical nanostructures are observed by tailoring the volume fraction of polystyrene mid-block in polystyrene-b-polyisoprene-b-polystyrene-b-poly(2-vinylpyridine) tetrablock terpolymer (S1 IS2 V). P2VP becomes the main cylinder, while PI forms satellite cylinders surrounding the main P2VP cylinder. When the length of S2 block is relatively short, tetragonal arrangement of cylinders is observed. But, a rectangular arrangement of cylinders is formed for larger S2 block. The experimentally observed hierarchical cylindrical nanostructures are in good agreement with the prediction by the self-consistent field theory.

Theoretical Study of Phase Behaviors of Symmetric Linear B1A1B2A2B3 Pentablock Copolymer.

The nanostructures that are self-assembled from block copolymer systems have attracted interest. Generally, it is believed that the dominating stable spherical phase is body-centered cubic (BCC) in linear AB-type block copolymer systems. The question of how to obtain spherical phases with other arrangements, such as the face-centered cubic (FCC) phase, has become a very interesting scientific problem. In this work, the phase behaviors of a symmetric linear B1A1B2A2B3 (fA1 = fA2, fB1 = fB3) pentablock copolymer are studied using the self-consistent field theory (SCFT), from which the influence of the relative length of the bridging B2-block on the formation of ordered nanostructures is revealed. By calculating the free energy of the candidate ordered phases, we determine that the stability regime of the BCC phase can be replaced by the FCC phase completely by tuning the length ratio of the middle bridging B2-block, demonstrating the key role of B2-block in stabilizing the spherical packing phase. More interestingly, the unusual phase transitions between the BCC and FCC spherical phases, i.e., BCC → FCC → BCC → FCC → BCC, are observed as the length of the bridging B2-block increases. Even though the topology of the phase diagrams is less affected, the phase windows of the several ordered nanostructures are dramatically changed. Specifically, the changing of the bridging B2-block can significantly adjust the asymmetrical phase regime of the Fddd network phase.

Isothermal Chirality Switching in Liquid-Crystalline Azobenzene Compounds with Non-Polarized Light.

Spontaneous mirror-symmetry breaking is a fundamental process for development of chirality in natural and in artificial self-assembled systems. A series of triple chain azobenzene based rod-like compounds is investigated that show mirror-symmetry breaking in an isotropic liquid occurring adjacent to a lamellar LC phase. The transition between the lamellar phase and the symmetry-broken liquid is affected by trans-cis photoisomerization, which allows a fast and reversible photoinduced switching between chiral and achiral states with non-polarized light.

Automated Search Strategy for Novel Ordered Structures of Block Copolymers.

Block copolymers with different architectures can possibly generate innumerable stable or metastable structures and thus provide an irreplaceable platform for theoretically exploring novel structures. Self-consistent field theory (SCFT) is a powerful tool to predict the ordered structures of block copolymers; however, it is sensitively dependent on its initial condition. Here we propose to use multiple symmetry-adapted basis functions to generate the initial conditions of SCFT and then apply Bayesian optimization to search for ordered structures by navigating the coefficient space of these basis functions. Without any prior knowledge, our scheme can automatically recover hundreds of ordered structures for two simple block copolymers, including most of the common structures and complex Frank-Kasper structures, together with many novel structures. By applying the automated scheme to various block copolymers, a huge number of novel structures can be obtained to expand the structural library, which may create new opportunities for the scientific community.

High-Density Packing of Spherical Microdomains from A(AB3)3 Dendron-like Miktoarm Star Copolymer.

An A(AB3)3 dendron-like miktoarm star copolymer consisting of polystyrene (PS, A) and poly(2-vinylpyridine) (P2VP, B) was synthesized using a series of anionic polymerization, atom-transfer radical polymerization (ATRP), and click reaction. The morphology of A(AB3)3 changed greatly depending on the volume fraction of A and the chain asymmetry. Interestingly, a body-centered cubic spherical phase was found even at fA = 0.51 because the chain architecture of A(AB3)3 stabilizes the large interfacial curvature toward A domains. On the other hand, when the length difference between the end and middle A blocks decreased, a hexagonally packed cylindrical phase was formed at fA = 0.50. This is attributed to the fact that the middle A chains are arranged in a more relaxed way, resulting in a milder interfacial curvature toward A domains. The experimental observations are well-consistent with the predictions based on self-consistent-field theory.

Manipulating the processing window of directed self-assembly in contact hole shrinking with binary block copolymer/homopolymer blending.

Directed self-assembly (DSA) lithography has demonstrated significant potential in fabricating integrated circuits. However, DSA encounters limited processing windows due to the requirement for precise matching between the period of block copolymers (BCPs) and graphoepitaxy templates. We propose a binary BCP/homopolymer blending strategy to manipulate the self-assembly behavior and the processing window of graphoepitaxy DSA in contact hole shrinking. By carefully tailoring the blending rates of poly(methyl methacrylate) (PMMA) with different molecular weights in cylindrical polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA), we manipulate the period and morphology of BCP/homopolymer self-assembly. Specifically, we employ BCP/homopolymer blending to fine-tune the critical dimension (CD) of contact holes with PS-affined topographical templates. Subsequent pattern transferring is achieved by selectively etching defect-free shrinkable cylinders as hard masks. Furthermore, self-consistent field theory (SCFT) simulation was employed to explore the self-assembly of BCP/homopolymer blending in confined cylindrical space and the results were in good consistency with the experimental results.

Inverse Design of Complex Block Copolymers for Exotic Self-Assembled Structures Based on Bayesian Optimization.

Variable chain topologies of multiblock copolymers provide great opportunities for the formation of numerous self-assembled nanostructures with promising potential applications. However, the consequent large parameter space poses new challenges for searching the stable parameter region of desired novel structures. In this Letter, by combining Bayesian optimization (BO), fast Fourier transform-assisted 3D convolutional neural network (FFT-3DCNN), and self-consistent field theory (SCFT), we develop a data-driven and fully automated inverse design framework to search for the desired novel structures self-assembled by ABC-type multiblock copolymers. Stable phase regions of three exotic target structures are efficiently identified in high-dimensional parameter space. Our work advances the new research paradigm of inverse design in the field of block copolymers.

Enhanced dielectric permittivity of hierarchically double-gyroid nanocomposites via macromolecular engineering of block copolymers.

It is a challenging task to realize the periodically bicontinuous gyroid nanostructures of flexible nanocomposites with high loading of functionalized nanoparticles, which could exhibit high dielectric permittivity for energy storage and electronic devices. Herein, with the aid of the concept of macromolecular engineering, we propose novel nanocomposites, composed of A'(A''B)n miktoarm star copolymers and nanoparticles, to obtain a double-gyroid structure through self-consistent field theory coupled with density functional theory. By tailoring the architecture of this copolymer, a large window of the double-gyroid phase extending to a high loading concentration of nanoparticles is achieved, leading to a hierarchical structure of a percolation network of nanoparticles within the gyroid channels. Furthermore, the finite difference quasielectrostatic method is integrated to reveal an enhanced dielectric permittivity of the structured nanocomposites by increasing the loading concentration of nanoparticles. The simultaneous achievement of an ordered double-gyroid phase and high loading nanoparticles represents a crucial step toward the realization of fully three-dimensional network-like metamaterials via a rational molecular design of nanocomposites.

Multidomain Helical Nanostructure by A1BA2C Tetrablock Terpolymer Self-Assembly.

Among many possible nanostructures in block copolymer self-assembly, helical nanostructures are particularly important because of potential applications for heterogeneous catalysts and plasmonic materials. In this work, we investigated, via small-angle X-ray scattering and transmission electron microscopy, the morphology of a polystyrene-block-polyisoprene-block-polystyrene-block-poly(2-vinylpyridine) (S1IS2V) tetrablock terpolymer. Very interestingly, when the volume fraction of each block was 0.685, 0.125, 0.060, and 0.130, respectively, a multidomain double-stranded helical nanostructure (MH2) was formed: P2VP chains became a core helix, and PI chains formed double-stranded helices surrounding the core helix. Core and double-stranded helices are connected by short PS2 chains, and PS1 chains become the matrix. The experimentally observed morphology is in good agreement with the prediction by self-consistent field theory. We believe that this multidomain helical structure will be pave the way to the creation of multifunctional helical structures for various applications such as metamaterials.

Mirror symmetry breaking in cubic phases and isotropic liquids driven by hydrogen bonding.

Achiral supramolecular hydrogen bonded complexes between rod-like 4-(4-alkoxyphenylazo)pyridines and a taper shaped 4-substituted benzoic acid form achiral (Ia3[combining macron]d) and chiral "Im3[combining macron]m-type" bicontinuous cubic (I432) phases and a chiral isotropic liquid mesophase (Iso1[*]). The chiral phases, resulting from spontaneous mirror symmetry breaking, represent conglomerates of macroscopic chiral domains eventually leading to uniform chirality.