Date of Award


Document Type

Open Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Degree Program

Polymer Science and Engineering

First Advisor

James J. Watkins

Second Advisor

Samuel P. Gido

Third Advisor

Mark T. Tuominen

Subject Categories

Materials Science and Engineering | Polymer and Organic Materials


Diblock copolymers have many interesting properties, which first and foremost include their ability to self-assemble into various ordered, regularly spaced domains with nanometer-scale feature sizes. The work in this dissertation can be logically divided into two parts - the first and the majority of this work describes the phase behavior of certain block copolymer systems, and the second discusses real applications possible with block copolymer templates. Many compressible fluids have solvent-like properties dependent on fluid pressure and can be used as processing aids similar to liquid solvents. Here, compressed CO2 was shown to swell several thin homopolymer films, including polystyrene and polyisoprene, as measured by high pressure ellipsometry at elevated temperatures and pressures. The ellipsometric technique was modified to produce accurate data at these conditions through a custom pressure vessel design. The order-disorder transition (ODT) temperatures of several poly(styrene-b-isoprene) diblock copolymers were also investigated by static birefringence when dilated with compressed CO2. Sorption of CO2 in each copolymer resulted in significant depressions of the ODT temperature as a function of fluid pressure, and the data above was used to estimate the quantitative amount of solvent in each of the diblock copolymers. These depressions were not shown to follow dilution approximation, and showed interesting, exaggerated scaling of the ODT at near-bulk polymer concentrations. The phase behavior of block copolymer surfactants was studied when blended with polymer or small molecule additives capable of selective hydrogen bonds. This work used small angle X-ray scattering (SAXS) to identify several low molecular weight systems with strong phase separation and ordered domains as small as 2-3 nanometers upon blending. One blend of a commercially-available surfactant with a small molecule additive was further developed and showed promise as a thin-film pattern transfer template. In this scenario, block copolymer thin films on domain thick with self-assembled feature sizes of only 6-7 nm were used as plasma etch resists. Here the block copolymer's pattern was successfully transferred into the underlying SiO2 substrate using CF4-based reactive ion etching. The result was a parallel, cylindrical nanostructure etched into SiO2.