Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO2) solvent. The rates of Al(acac)3 (Aluminum acetyl acetonate) and Ga(acac)3 (Gallium acetyl acetonate) thermal decomposition in scCO2 to form conformal Al2O3 and Ga2O3 thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)3 and Ga(acac)3 was found to be initialized at ∼ 150 °C and 160 °C respectively in scCO2 solvent, compared to ∼ 250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)3 in scCO2 is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO2 is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrOx, FeOx, Co2O3, Cr2O3, HfOx from thermal decomposition of metal diketonates or fluorinated diketonates in scCO2 are also presented.