Block copolymer solution self‐assembly: Recent advances, emerging trends, and applications

Abstract

The self‐assembly process of block copolymers (BCPs) in solution has been at the focus of extended scientific research over the past several decades owing to the astonishing morphological diversity and attainable complexity of the resulting nanoassemblies, including spheres, cylinders, lamellae, vesicles, and many other complex, bicontinuous or even hierarchical structures. The ever‐increasing sophistication in the development of synthetic chemistry methods and techniques has led to a myriad of available macromolecules with varying chemical compositions, architectures, features, and properties. This assortment of characteristics has led in turn to a plethora of intriguing self‐organized polymeric nanostructures, with countless possible applications in several nanotechnological fields relevant to physics, chemistry, material science, nanomedicine, and biomaterials. The present review aims to illuminate the importance and fascinating potential of BCPs solution self‐assembly by highlighting recent advances and emerging trends in the field, as well as significant application‐oriented progress, through characteristic contemporary examples.

Mesoporous carbons from self‐assembled polymers

“…Self‐assembly of amphiphilic surfactants and block copolymers (BCPs) enables facile preparation of ordered functional nanomaterials with direct access to a wide variety of different structures and domain sizes 51–53 . Leveraging this advantage, Kresge et al reported one of the very first examples of using a surfactant‐mediated self‐assembly approach to fabricate a family of mesoporous silicas, of which the pore sizes can be tailored upon the selection of surfactant type, reaction condition, and auxiliary chemicals 54 .…”

“…Self-assembly of amphiphilic surfactants and block copolymers (BCPs) enables facile preparation of ordered functional nanomaterials with direct access to a wide variety of different structures and domain sizes. [51][52][53] Leveraging this advantage, Kresge et al reported one of the very first examples of using a surfactant-mediated self-assembly approach to fabricate a family of mesoporous silicas, of which the pore sizes can be tailored upon the selection of surfactant type, reaction condition, and auxiliary chemicals. 54 This work pioneered the synthesis of mesoporous solids from calcination of inorganic gels with the presence of surfactants, establishing an important synthetic platform which employs an amphiphilic organic component as the nanostructure templating agent for directing the assembly of inorganic precursors.…”

Solvent-assisted self-assembly of block copolymer thin films

“…Instead, we focus on solvent-driven or solventassisted self-assembly of block copolymers leading to the formation of nanoscale patterns in thin films (10-1000 nm). We have also limited our discussion of BCP self-assembly in solution, thoroughly reviewed elsewhere, 29,30 only to the aspects necessary to understand BCP-solvent interactions in concentrated solutions and solvent-swollen polymer films near and above the onset of the order-disorder phase transition concentration. A complete overview of BCP-solvent interactions over an entire concentration range including a thorough presentation of phase behavior can be found in the review by Alexandridis and Spontak.…”

“…7,8 More narrowly, it has been used in the context of graphoepitaxial and chemoepitaxial ordering. 28–30 ) methods. DSA methods are used to accelerate the self-assembly process and to reduce patterns’ defectivity to an application enabling level and, by using directional biases, to orient (align) anisotropic BCP morphologies.…”

Morphological Diversity from the Solution Self‐Assembly of Block Copolymer Blends Containing High Molecular‐Weight Hydrophobic Blocks

“…The solution self-assembly of block copolymers (BCPs) creates polymer nanostructures with tailored morphology and surface chemistry to meet the requirements for applications, such as drug delivery, nanoreactors, and templates for constructing complex nanostructures. [1][2][3][4][5] The control of the self-assembled structures of BCPs, such as their shapes, sizes, and surface functions has been achieved by the rational design and precision-synthesis of polymer building blocks. [6][7][8] In particular, the molecular weights of the polymer blocks constituting a BCP exert a deciding effect on the self-assembly of macromolecular amphiphiles.…”