Supramolecular Materials via Block Copolymer Self‐Assembly

This review discusses the potential of block copolymer type macromolecular building blocks for the preparation of self‐assembled materials. Three different classes of block copolymer type architectures will be distinguished: (i) coil–coil diblock copolymers, (ii) rod–coil diblock copolymers, and (iii) rod–coil diblock oligomers. The basic principles that underlie the self‐assembly of each of these different building blocks will be discussed. These theoretical considerations are complemented with examples from recent literature that illustrate the potential of the different types of block copolymers to prepare (functional) supramolecular materials. Finally, several strategies will be presented that could allow the preparation of stimuli‐sensitive self‐assembled materials, i.e., materials whose properties can be reversibly manipulated under the action of appropriate external stimuli.     

Templated Self‐Assembly of Block Copolymers: Top‐Down Helps Bottom‐Up

One of the key challenges in nanotechnology is to control a self‐assembling system to create a specific structure. Self‐organizing block copolymers offer a rich variety of periodic nanoscale patterns, and researchers have succeeded in finding conditions that lead to very long range order of the domains. However, the array of microdomains typically still contains some uncontrolled defects and lacks global registration and orientation. Recent efforts in templated self‐assembly of block copolymers have demonstrated a promising route to control bottom‐up self‐organization processes through top‐down lithographic templates. The orientation and placement of block‐copolymer domains can be directed by topographically or chemically patterned templates. This templated self‐assembly method provides a path towards the rational design of hierarchical device structures with periodic features that cover several length scales.