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

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 crystallizatio...

[1]  G. Lucovsky,et al.  Microscopic model for enhanced dielectric constants in low concentration SiO2-rich noncrystalline Zr and Hf silicate alloys , 2000 .

[2]  S. Honda,et al.  Surface, structural and optical properties of sol-gel derived HfO2 films , 2000 .

[3]  A. Larbot,et al.  Synthesis of Hafnia Powders and Nanofiltration Membranes by Sol-Gel Process , 2000 .

[4]  Robert M. Wallace,et al.  Stable zirconium silicate gate dielectrics deposited directly on silicon , 2000 .

[5]  Robert M. Wallace,et al.  ELECTRICAL PROPERTIES OF HAFNIUM SILICATE GATE DIELECTRICS DEPOSITED DIRECTLY ON SILICON , 1999 .

[6]  C. Serna,et al.  Optical constants of tetragonal and cubic zirconias in the infrared , 1996 .

[7]  V. K. Parashar,et al.  Thermal evolution of sol-gel derived zirconia and binary oxides of zirconia-silica , 1996, Journal of Materials Science Letters.

[8]  P. Escribano,et al.  Effect of hydrolysis time and type of catalyst on the stability of tetragonal zirconia-silica composites synthesized from alkoxides , 1993, Journal of Materials Science.

[9]  P. Pramanik,et al.  Aqueous sol-gel synthesis of powders in the ZrO2SiO2 system using zirconium formate and tetraethoxysilane , 1993 .

[10]  H. Nasu,et al.  Investigation of coordination state of Zr4+ ions in the sol—gel-derived ZrO2SiO2 glasses by EXAFS , 1991 .

[11]  David V. Tsu,et al.  Local bonding environments of Si–OH groups in SiO2 deposited by remote plasma‐enhanced chemical vapor deposition and incorporated by postdeposition exposure to water vapor , 1990 .

[12]  S. W. Lee,et al.  The infrared and Raman spectra of ZrO2-SiO2 glasses prepared by a sol-gel process , 1988 .

[13]  K. S. Mazdiyasni,et al.  Infrared and Raman Spectra of Zirconia Polymorphs , 1971 .

[14]  C. Kittel Introduction to solid state physics , 1954 .

[15]  R. Wallace,et al.  Hafnium and zirconium silicates for advanced gate dielectrics , 2000 .

[16]  Mark E. Smith,et al.  Structure of (ZrO2)x(SiO2)1-x xerogels (x=0.1, 0.2, 0.3 and 0.4) from FTIR, 29Si and 17O MAS NMR and EXAFS , 1999 .

[17]  V. K. Parashar,et al.  The role of N, N, Dimethylformamide and glycol in the preparation and properties of sol-gel derived silica , 1996 .

[18]  M. Nogami Glass preparation of the ZrO2SiO2 system by the sol-gel process from metal alkoxides , 1985 .