AbstractFor the growth of thin zinc group metal oxide films [i.e. cadmium oxide (CdO), cadmium stannate (Cd2SnO4), and zinc oxide (ZnO)] via metal-organic chemical vapor deposition (MOCVD), volatile Cd and Zn precursor families are needed. Starting with Cd, β-ketoiminates of varying substitution were prepared to elucidate structure-property relationships. The nature of the ligand substituents strongly influences the melting point (liquid precursors are desired). Unlike conventional Cd β-diketonates, these complexes are monomeric as determined by x-ray crystallography. Despite these advantageous characteristics, attempts to grow CdO thin films in a cold-wall MOCVD reactor using two such derivatives were not successful. This class of Cd complex appears to decompose thermally with time-- a likely cause of the poor performance. Therefore, a new series of more thermally stable Cd precursors was sought. Using the chelating diamine N,N,N1,N1-tetramethylethylenediamine (TMEDA), monomeric β-diketonates were prepared. The molecular structure of Cd(hfa)2(TMEDA) (hfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate) confirms the monomeric structural assignment. This series of Cd complexes is appreciably more volatile and sublime more cleanly than the aforementioned β-ketoiminates, as determined by vacuum thermogravimetric analysis (TGA). In addition to this advantageous characteristic, these complexes are easily prepared under ambient laboratory conditions from commercially available starting materials in a single step. Following the protocol established for Cd, a volatile series of Zn precursors was also prepared. For the Zn series, the melting point was effectively tuned through variation of both the β-diketonate and diamine ligands. The use of the Cd and Zn β-diketonate precursors in the successful growth of CdO and ZnO thin films, respectively, by MOCVD is also presented.
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