Block copolymer photonic crystals

Abstract

This thesis explores the photonic properties of block copolymer systems. One dimensionally periodic dielectric stacks are fabricated with symmetric, lamellar forming, copolymer systems: diblock copolymers, solvent swollen BCP materials, and homopolymer swollen BCP blends. Each system exhibits reflectivity in visible spectrum. These materials are also investigated for their phononic band properties by Brillouin scattering. A copolymer forming the three dimensional double gyroid at optically relevant length scales and its reflective properties are presented as well. Experimental results document the initial observation of photonic optical properties related to the microstructure of a block copolymer. One dimensionally periodic, lamellar polymer block copolymer systems of poly(styrene-b-isoprene) are used to fabricate multilayered optical structures with a range of lamellar dimensions. The lamellar repeat of the copolymer morphology is shown to be adjustable by blending symmetric amounts of like homopolymers of lower molecular weight with the copolymer. The composition of the blends remains symmetric and the morphology is shown to remain lamellar. An isopleth of composition is examined and photonic crystals containing up to 60 wt % homopolymer exhibit wavelength selective reflectivity from the ordered morphology. The wavelength of reflectivity is correlated with the lamellar repeat spacing and morphology. The optical properties of solvent swollen ultrahigh molecular weight block copolymers are examined. The wavelength selective reflectivity is shown to correlate with the expected behavior of the phase segregated morphology. Deformation sensitive ordered gels are fabricated by using a non-volatile, alkyl phthalate plasticizer. The optical properties are shown to respond to the material strain. A simple demonstration of the visualization of the strain field of a deforming system is presented. In addition these gels are shown to exhibit phononic band gap behavior. The system is studied by Brillouin scattering and resonant phonons arising from the morphology are predicted and observed. Three dimensionally periodic photonic crystals formed of a double gyroid styrene- isoprene diblock copolymer are also documented. The copolymer material is considered as formed and also after a series of processing steps.

(cont.) Etching of the isoprene matrix is demonstrated yielding a free standing air-styrene double gyroid. This material is then used to replicate the matrix geometry in titania by infiltration with a sol-gel precursor and subsequent pyrolysis. The structure of the double gyroid material is examined via x-ray scattering and electron microscopy. The photonic band properties of the double gyroid structure for multiple constituent materials with a broad range of refractive indices are examined. Features in optical measurements resulting from the double gyroid structure are observed consistent with the 250nm cubic lattice parameter. A block copolymer photonic crystal platform is outlined and presented. Acousto-optic, phononic crystal properties are noted in these materials and applications are discussed. Strategies for creating a block copolymer based material with an absolute band gap ...