Controlling self-assembly and ordering of block polymer nanostructures in thin films
Date
2016
Authors
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Publisher
University of Delaware
Abstract
Block polymers have garnered significant attention in the past few decades due to their ability to self-assemble into a boundless array of structures such as spheres, cylinders, gyroid, and lamellae. The sizes of the periodical structures typically are ~5 – 100 nm, making them ideal for emerging nanotechnologies, such as nanolithography, nanotemplating, nanoporous membranes, and photonics devices. Many of these applications require thin film geometries, in which the block polymers form well-ordered nanostructures and precisely controlled domain orientations. Understanding the factors that affect thin film phase behavior and being able to control the nanostructures, domain orientation, and domain ordering in thin film is essential to realizing the full potential of these unique materials. In this dissertation, I describe significant efforts to manipulate the block polymer thin film structures, direct the nanostructure ordering, and understand the connection between the macromolecular molecular structures and the block polymer properties. First, substrate surface modification with chlorosilane was employed to manipulate the nanostructure of poly(styrene- b-isoprene-b-styrene) (SIS) thin films. A morphological transformation from parallel cylinders to hexagonally perforated lamellae (HPL) was identified, in a high-throughput fashion, using gradient methods. The gradient methods are highly adaptable for the possible universal manipulation of thin film nanostructures. Second, rastering solvent vapor annealing – soft shear method was developed and demonstrated as a simple, yet highly effective method to achieve macroscopic alignment of SIS cylinders. This method substantially improves on previous approaches by using simple instrumentation to unlock an array of alignment patterns with a variety of self-assembling polymers and provides feasibility and flexibility for practical industrial production. Next, the interfacial mixing characteristics of tapered block polymer were explored quantitatively for the first time, and the tapered interfacial modification has led to unique and diverse self-assembly behavior and properties. Finally, XPS depth profiling with C60+ sputtering was used to determine the lithium ion distribution in a lamellae-forming block polymer electrolyte film. The results provide useful insights for the future design and optimization of block polymer structures for high efficiency energy storage devices. Additionally, the unique capabilities of C60+ depth profiling XPS are demonstrated as a method to determine the nanoscale distributions of molecules in a myriad of polymer thin film systems.