Spray Pyrolysis of Ternary Oxides: From Precursor Selection to Surface Reactions

Spray pyrolysis is a popular method for the low-cost synthesis of oxides and other compounds in thin-film form. Here, we discuss several nuances of using this method for ternary and quaternary compounds. Specifically, we outline how precursor solubility and thermal decomposition, as well as desorption of intermediate species from the sample surface govern the spray pyrolysis growth process. We demonstrate how the stoichiometry transfer from solution to film can be affected in selected test cases. We present real-time optical growth measurements of the behaviour of individual Cu, Cr, Zn, and Sn precursors, as well as post-growth analysis of film composition by X-ray photoelectron spectroscopy for ternary transparent conducting oxides (TCOs; p-type: Cu_xCrO₂, SnTiO_x; and n-type: a-ZnSnO₃). We illustrate how several steps of spray pyrolysis affect the stoichiometry transfer from the solution to the ternary thin film. Using binary Cu₂O as a test case, we also show how the choice of instrument geometry and nozzle type can affect film homogeneity. All materials discussed have been chosen to highlight potential difficulties of the spray pyrolysis process of ternary, quaternary, or even more complex oxides, and the mechanisms should be considered for other materials as well. We therefore also provide an extensive overview of suitable precursor salts with similar expected properties as used in this experimental work to guide future ternary oxide studies.