ABSTRACTNew precursors have been found for chemical vapor deposition (CVD) of many metal oxides. Each precursor is a mixture formed by randomly attaching a selected set of organic groups, such as the isomers of the butyl group, to a metal 2,4-pentanedionate (also known as acetylacetonate) in place of the methyl groups of the 2,4-pentanedionate ligand. Most of these new mixed metal beta-diketonates are liquids at room temperature, whereas the corresponding metal 2,4-pentanedionates are solids. In the cases where they were solids or viscous liquids, small amounts of organic solvents were added to reduce the viscosity. We have so far prepared mixed beta-diketonate precursors for barium, strontium, calcium, magnesium, aluminum, indium, tin, lead, bismuth, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, iron, ruthenium, cobalt, nickel, copper, zinc, yttrium, lanthanum and cerium.Liquid sources are much more convenient for CVD than solid sources. These liquid mixtures or solutions were vaporized by ultrasonically nebulizing the liquid into a flow of hot nitrogen carrier gas preheated to 150–250 °C. These vapor mixtures were mixed with air or oxygen and flowed over substrates heated typically to 350–450 °C. Films of the corresponding metal oxide (or carbonate, in the case of barium, strontium and calcium) were deposited on substrates of silicon or glass. Gas pressures from 20–760 Torr were used.Because a common set of ligands is used for each of these metal precursors, they can be mixed as liquids or vapors without any precipitation due to ligand exchange reactions. To demonstrate their use in forming mixed metal oxides, we have prepared films of ferroelectric barium titanate. This method should be applicable to other mixed metal oxides of current interest, such as high dielectric constant strontium titanate, ferroelectric bismuth strontium tantalate, superconducting yttrium barium copper oxide, refractory yttrium zirconium oxide, second-harmonic generating barium borate, metallic lanthanum strontium cobalt oxide and magnetoresistive lanthanum strontium manganate.
Single- and Double-Site Substitutions in Mixed-Metal Oxides: Adjusting the Band Edges Toward the Water Redox Couples
