Novel Block Copolymer Architectures for Lithography-Relevant Self-Assembly

This dissertation is focused on the synthesis, characterization, self-assembly, and materials processing of various functionalized block copolymer systems. A variety of monomers were prepared and polymerized through various polymerization techniques including atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, and ring-opening metathesis polymerization. Self-assembly of the functionalized block copolymers led to well-defined nanostructures in bulk and thin films. These materials have the capability to be utilized in various applications including ordered catalysts and templates for nanolithography. In Chapter 1, the overall background of diblock and triblock copolymers and their preparation methods is in this dissertation. Major research objectives of my doctoral work are described. Chapter 2 focuses on the reduction of annealing time and use of industrially compatible solvents in high-humidity solvent annealing with poly(ethylene oxide)-block-poly(styrene). Chapters 3-5 describe the design, synthesis, and characterization of various diblock and triblock polymeric architectures and their self-assembly in both bulk and thin-films. Incorporating desirable functional groups into block copolymer systems can lead to confinement of the functional group to a specific domain upon microphase separation of block copolymers. The resulting materials display desirable characteristics of the functional group in a well-ordered nanostructure. Finally, chapter 6 provides a summary of the work described herein, and provides an outlook into future research with these block copolymer systems