Single crystals and two‐dimensional crystalline assemblies of block copolymers

Abstract

Block copolymer single crystals (BCPSCs) have attracted widespread attentions due to their unique two-dimensional (2D) structure, good controllability, and great potential applications in recent years. In this paper, the morphology, surface structure of BCPSCs and the related influencing factors are reviewed. We also summarize the studies of 2D crystalline assemblies of block copolymers (BCPs) driven by crystallization and intermolecular π-π interaction. Moreover, the functionalization and properties of BCPSCs and 2D crystalline assemblies of BCPs are introduced. Finally, we put forward some unsolved problems in this field.

Seeded Epitaxial Growth of Crystallizable Polymers Governed by Crystallization Temperatures

“…Crystallization-driven self-assembly (CDSA) of block copolymers (BCPs) with a crystallizable segment is a powerful tool used to create anisotropic polymer nanoparticles with precision control over size, shape, and compositions. − One-dimensional (1D) − and two-dimensional (2D) − precision polymer nanoparticles are extensively fabricated by using this approach. Living CDSA is a seeded growth approach of increasing importance for the creation of 1D/2D core–shell materials with enhanced complex structures from crystallizable BCPs. − In a seeded growth method, the crystallization process of nucleation and crystal growth is divided into two separated steps, i.e., the first step of preparation of crystalline seeds and the second step of crystal growth.…”

Tailoring Self-Assembly of Alternating Copolymers for Ordered and Crystalline 2D Nanostructures via Diverse Strategies

“…In recent years, breakthroughs have been achieved by introducing uniform assembly units, specific crystallizable blocks, or directional noncovalent interactions. − For instance, the self-assembly of quasi-monodisperse polymers or nanoparticles has been utilized to generate 2D nanosheets with ordered structures . Crystallization-driven self-assembly (CDSA) has facilitated arrangements in crystallizable segments, − resulting in uniform 2D structures. − Among directional noncovalent interactions, π–π stacking has proven effective for constructing 2D structures. − In addition to traditional block copolymers, emerging alternating copolymers show promising potential for constructing materials with an ultrasmall or thin dimension, leveraging their consistently small and uniformly distributed repeating subunits. − These advancements have promoted the development of ordered 2D nanomaterials with improved properties and functionalities.…”

Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer

“…Self-assembly of polymers has led to a rich variety of morphologies either in bulk or in solution, attracting considerable attention. − Crystallization-driven self-assembly (CDSA) of amphiphilic block copolymers (BCPs), featuring a crystalline core-forming block, has emerged as a promising and versatile approach for generating one- and two-dimensional structures. Notably, CDSA can often operate as a “living” process similar to living polymerizations of molecular monomers, allowing for the fabrication of micelles with predictable shapes that are both well-defined and complex. , With the increased manipulation of 1D and 2D − core-crystalline micelles, researchers have started to showcase uniform 3D structures. They include dendritic, branched, − multiarmed, scarf-like, , and spherulite-like , structures.…”