Materials characterization of ZrO2–SiO2 and HfO2–SiO2 binary oxides deposited by chemical solution deposition

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Abstract
The thermal stability, microstructure, and electrical properties of xZrO2⋅(100−x)SiO2 (ZSO) and xHfO2⋅(100−x)SiO2 (HSO) (x=15%, 25%, 50%, and 75%) binary oxides were evaluated to help assess their suitability as a replacement for silicon dioxide gate dielectrics in complementary metal–oxide–semiconductor transistors. The films were prepared by chemical solution deposition using a solution prepared from a mixture of zirconium, hafnium, and silicon butoxyethoxides dissolved in butoxyethanol. The films were spun onto SiOxNy coated Si wafers and furnace annealed at temperatures from 500 to 1200 °C in oxygen for 30–60 min. The microstructure and electrical properties of ZSO and HSO films were examined as a function of the Zr/Si and Hf/Si ratio and annealing temperature. The films were characterized by x-ray diffraction, mid- and far-Fourier transform infrared (FTIR), Rutherford backscattering spectroscopy, and Auger electron spectroscopy. At ZrO2 or HfO2 concentrations ⩾50%, phase separation and crystallization of tetragonal ZrO2 or HfO2 were observed at 800 °C. At ZrO2 or HfO2 concentrations ⩽ 25%, phase separation and crystallization of tetragonal ZrO2 or HfO2 were observed at 1000 °C. As the annealing temperature increased, a progressive change in microstructure was observed in the FTIR spectra. Additionally, the FTIR spectra suggest that HfO2 is far more disruptive of the silica network than ZrO2 even at HfO2 concentrations ⩽25%. The dielectric constants of the 25%, 50%, and 75% ZSO films were measured and were observed to be less than the linear combination of ZrO2 and SiO2 dielectric constants. The dielectric constant was also observed to increase with increasing ZrO2 content. The dielectric constant was also observed to be annealing temperature dependent with larger dielectric constants observed in nonphase separated films. The Clausius–Mossoti equation and a simple capacitor model for a phase separated system were observed to fit the data with the prediction that to achieve a dielectric constant larger than 10 doping concentrations of ZrO2 would have to be greater than 70%.