Ceramic nanostructures for block copolymers

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2000.Vita.Includes bibliographical references (leaves 224-234).The field of nanotechnology has received burgeoning interest in recent years as the characteristic dimensions for many applications (such as integrated circuits and magnetic storage media) become smaller and smaller. In this work, block copolymers are harnessed in order to produce both porous and relief nanostructures. The interest in using these materials is due to the unique morphologies that block copolymers form and the fact that these nanostructures do so by self assembly. With careful selection of the relative volume fraction and phases, nanostructures with highly ordered and complex pore structures with a vast range of different symmetries can be produced; structures that are not attainable by more conventional processing techniques such as lithography. In this thesis, we have produced porous and relief ceramic nanostructures from self-assembling (template free) block copolymer precursors using a one-step, room temperature technique. To accomplish this, a silicon containing block copolymer system was used where upon exposure to an oxidation process the material undergoes two steps 1) the selective removal of the hydrocarbon block and 2) the formation of a ceramic from the inorganic containing block, resulting in nanoporous and nanorelief ceramics. These structures have potential to be used at temperatures far above the T 8 of traditional nanoporous or nanorelief polymers. By choosing the appropriate morphologies and parent block copolymers, 30 nanostructured ceramics with interfacial areas of-40 m2/g, masks for one-step lithography with a density of-5 x 1011 dots/cm2 or templates for the next generation of nanomagnets can be produced. In addition to these applications, it is envisioned that these structures can be used as photonic band gap materials, high temperature membranes and low dielectric constant materials. Specifically, the formation of both nanoporous and nanorelief structures from an ABA triblock copolymer system of poly(pentamethyldisilylstyrene) P(PMDSS) with polyisoprene was studied. The focus of this thesis is on the oxidation of the double gyroid and ''inverse" double gyroid morphologies using either ozone/uv and oxygen plasma techniques. By transmission electron microscopy (TEM) and atomic force microscopy (AFM), it is shown that the PI can be preferentially removed by oxidation resulting in a nanoporous material in the case of the double gyroid morphology and a nanorelief material in the case of the inverse double gyroid morphology. Oxidation of the P(PMDSS) homopolymer was also studied chemically using X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Fourier Transform Infra-red Spectroscopy (FTIR), Rutherford Backscattering Spectrometry (RBS) and Forward recoil Spectrometry (FRES) and morphologically by AFM. Through these chemical analysis techniques, it is demonstrated that the ozone + uv and uv only oxidation processes converts thin films of P(PMDSS) to a ceramic, specifically silicon oxycarbide, that is far more stable than the parent homopolymer.by Vanessa Zee-Haye Chan.Ph.D