期刊
INORGANIC CHEMISTRY
卷 45, 期 26, 页码 11008-11018出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic061056i
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Novel guanidinato complexes of hafnium [Hf{n(2)-((PrN)-Pr-i)(2)CNR2}(2)(NR2)(2)] (R-2 = Et-2, 1; Et, Me, 2; Me-2, 3), synthesized by insertion reactions of N,N'-diisopropylcarbodiimide into the M-N bonds of homologous hafnium amide complexes 1-3 and {[mu(2)-NC(NMe2)(2)][NC(NMe2)(2)](2)HfCl}(2) (4) using a salt metathesis reaction, are reported. Single-crystal X-ray diffraction analysis revealed that compounds 1-3 were monomers, while compound 4 was found to be a dimer. The observed fluxional behavior of compounds 1-3 was studied in detail using variable-temperature and two-dimensional NMR techniques. The thermal characteristics of compounds 1-3 seem promising for HfO2 thin films by vapor deposition techniques. Metal-organic chemical vapor deposition experiments with compound 2 as the precursor resulted in smooth, uniform, and stoichiometric HfO2 thin films at relatively low deposition temperatures. The basic properties of HfO2 thin films were characterized in some detail.
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