Hafnium and Zirconium based gate dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in CMOS processing. Furthermore, the addition of nitrogen into this pseudo-binary alloy has been shown to improve their thermal stability, electrical properties, and reduce dopant penetration. Because CMOS processing requires high temperature anneals (up to 1050 °C), it is important to understand the diffusion properties of any metal associated with the gate dielectric in silicon at these temperatures. In addition, dopant penetration from the doped polysilicon gate into the Si channel at these temperatures must also be studied. Impurity outdiffusion (Hf, Zr) from the dielectric, or dopant (B, As, P) penetration through the dielectric into the channel region would likely result in deleterious effects upon the carrier mobility. In this dissertation extensive thermal stability studies of alternate gate dielectric candidates ZrSixOy and HfSixOy are presented. Dopant penetration studies from doped-polysilicon through HfSixOy and HfSixOyNz are also presented. Rutherford backscattering spectroscopy (RBS), heavy ion RBS (HI-RBS), x-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and time of flight and dynamic secondary ion mass spectroscopy (ToF-SIMS, D-SIMS) methods were used to characterize these materials. The dopant diffusivity is calculated by modeling …

Kinetic equation parameters for the curing reaction of a commercial glass fiber reinforced high performance epoxy prepreg composed of the tetrafunctional epoxy tetraglycidyl 4,4-diaminodiphenyl methane (TGDDM), the tetrafunctional amine curing agent 4,4’-diaminodiphenylsulfone (DDS) and an ionic initiator/accelerator, are determined by various thermal analysis techniques and the results compared. The reaction is monitored by heat generated determined by differential scanning calorimetry (DSC). The changes in physical properties indicating increasing conversion are followed by shifts in glass transition temperature determined by DSC and temperature-modulated DSC (TMDSC), thermomechanical (TMA) and dynamic mechanical (DMA) analysis and thermally stimulated depolarization (TSD). Changes in viscosity, also indicative of degree of conversion, are monitored by DMA. Thermal stability as a function of degree of cure is monitored by thermogravimetric analysis (TGA). The parameters of the general kinetic equations, including activation energy and rate constant, are explained and used to compare results of various techniques. The utilities of the kinetic descriptions are demonstrated in the construction of a useful time-temperature-transformation (TTT) diagram for rapid determination of processing parameters in the processing of prepregs. Copyright is held by the author, unless otherwise noted. All rights reserved. Files: Thesis.pdf Special Conditions

Methyl-functionalized porous silica is of considerable interest as a low dielectric constant film for semiconductor devices. The structural development of these materials appears to affect their gelation behaviors and impact their mechanical properties and shrinkage during processing. 29Si solution NMR was used to follow the structural evolution of MTMS (methyltrimethoxysilane) polymerization to gelation or precipitation, and thus to better understand the species that affect these properties and gelation behaviors. The effects of pH, water concentration, type of solvents, and synthesis procedures (single step acid catalysis and two-step acid/base catalysis) on MTMS polymerization were discussed. The reactivity of silicon species with different connectivity and the extent of cyclization were found to depend appreciably on the pH value of the sol. A kinetic model is presented to treat the reactivity of both silicon species involved in condensations separately based on the inductive and steric effects of these silicon species. Extensive cyclization in the presence of acid, which was attributed to the steric effects among numerous reaction pathways for the first time, prevents MTMS gelation, whereas gels were obtained from the two-step method with nearly random condensations. The experimental degree of condensation (DC) at the gel point using the two-step procedure was determined …