Graduation Year

2009

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemical Engineering

Major Professor

Vinay Gupta, Ph.D.

Committee Member

Norma Alcantar, Ph.D.

Committee Member

John Wolan, Ph.D.

Committee Member

Maya Trotz, Ph.D.

Committee Member

Hariharan Srikanth, Ph.D.

Keywords

Titania, composites, ceria, PNIPAM, chemical mechanical polishing, remediation, microgels, planarization, slurry, methyl orange, photocatalytic degradation, sedimentation, turbidometry, CMP, Degussa P25, free radical polymerization

Abstract

Composite materials formed from two or more functionally different materials offer a versatile avenue to create a tailored material with well defined traits. Within this dissertation research, multi-functional composites were synthesized based on organic and inorganic materials. The functionally of these composites was experimentally tested and a semi-empirical model describing the sedimentation behavior of these particles was developed.

This first objective involved the fabrication of microcomposites consisting of titanium dioxide (TiO2) nanoparticles confined within porous, microgels of a thermo-responsive polymer for use in the photocatalytic treatment of wastewater. TiO2 has been shown to be an excellent photocatalyst with potential applications in advanced oxidative processes such as wastewater remediation. Upon UV irradiation, short-lived electron-hole pairs are generated, which produce oxidative species that degrade simple organic contaminants. The rapid sedimentation of these microcomposites provided an easy gravimetric separation after remediation. Methyl orange was used as a model organic contaminant to investigate the kinetics of photodegradation under a range of concentrations and pH conditions. Although after prolonged periods of UV irradiation (~8-13 hrs), the titania-microgels also degrade, regeneration of the microcomposites was straightforward via the addition of polymer microgels with no loss in photocatalytic activity of the reformed microcomposites.

The second objective within this dissertation involved the systematic development of abrasive microcomposite particles containing well dispersed nanoparticles of ceria in an organic/inorganic hybrid polymeric particle for use in chemical mechanical polishing/planarization (CMP). A challenge in IC fabrication involves the defect-free planarization of silicon oxide films for successful multi-layer deposition. Planarization studies conducted with the microcomposites prepared in this research, yield very smooth, planar surfaces with removal rates that rival those of inorganic oxides slurries typically used in industry. The density and size of these ceria-microgel particles could be controlled by varying the temperature or composition during synthesis, leading to softer or harder polishing when desired.

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