Experimental characterization and modeling for the growth rate of oxide coatings from liquid solutions of metalorganic precursors by ultrasonic pulsed injection in a cold-wall low-pressure reactor

Several years ago, a method for depositing ceramic coatings called the Pulsed-MOCVD system was developed by the Raj group at Cornell University in association with Dr. Harvey Berger and Sono-Tek Corporation. The process was used to produce epitaxial thin films of TiO₂ on sapphire substrates under conditions of low pressure, relatively high temperature, and very low growth rate. The system came to CU-Boulder when Professor Raj moved here in 1997. It is quite a simple technique and has several advantages over typical CVD systems. The purpose of this dissertation is two-fold; (1) understand the chemical processes, thermodynamics, and kinetics of the Pulsed-MOCVD technique, and (2) determine the possible applications by studying the film structure and morphology over the entire range of deposition conditions.; Polycrystalline coatings of ceramic materials were deposited on nickel in the low-pressure, cold-wall reactor from metalorganic precursors, titanium isopropoxide, and a mixture of zirconium isopropoxide and yttria isopropoxide. The process utilized pulsed liquid injection of a dilute precursor solution with atomization by ultrasonic nozzle. Thin films (less than 1μm) with fine-grained microstructure and thick coatings (up to 1μm) with columnar-microstructure were deposited on heated metal substrates by thermal decomposition of a single liquid precursor. The influence of each of the primary deposition parameters, substrate temperature, total flow rate, and precursor concentration on growth rate, conversion efficiency and morphology were investigated. The operating conditions were determined for kinetic, mass transfer, and evaporation process control regimes. Kinetic controlled deposition was found to produce equiaxed morphology while mass transfer controlled deposition produced columnar morphology.; A kinetic model of the deposition process was developed and compared to data for deposition of TiO₂ from Ti(OC₃H₇) ₄ precursor. The results demonstrate that growth rate and morphology over the range of process operating conditions would make the Pulsed-MOCVD system suitable for application of thermal barrier coatings, electrical insulating layers, corrosion protection coatings, and the electrolyte layers in solid oxide fuel cells.