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Chemical Vapor Deposition of Titania/Silica and Zirconia Films

Published online by Cambridge University Press:  21 March 2011

Wayne L. Gladfelter ,
Ryan C. Smith ,
David Burleson ,
Charles J. Taylor ,
Jeffrey T. Roberts ,
Stephen A. Campbell ,
Noel Hoilien ,
Mike Tiner ,
Rama Hegde  and
Christopher Hobbs
Wayne L. Gladfelter
Affiliation:
Departments of Chemistry and Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Ryan C. Smith
Affiliation:
Departments of Chemistry and Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Charles J. Taylor
Affiliation:
Departments of Chemistry and Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Jeffrey T. Roberts
Affiliation:
Departments of Chemistry and Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Stephen A. Campbell
Affiliation:
Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Noel Hoilien
Affiliation:
Computer and Electrical Engineering, University of Minnesota, Minneapolis, MN 55455.
Mike Tiner
Affiliation:
Motorola Advanced Products Research and Development Laboratory, Austin, TX 78721.
Rama Hegde
Affiliation:
Motorola Advanced Products Research and Development Laboratory, Austin, TX 78721.
Christopher Hobbs
Affiliation:
Motorola Advanced Products Research and Development Laboratory, Austin, TX 78721.
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Abstract

Amorphous thin films of composition TixSi1−xO2 have been grown by low pressure chemical vapor deposition on silicon (100) substrates using Si(OEt)4 and either Ti(OiPr)4 or anhydrous Ti(NO3)4 as the sources of SiO2 and TiO2, respectively. The substrate temperature was varied between 300 and 535°C, and the precursor flow rates ranged from 5 to 100 sccm. Under these conditions growth rates ranging from 0.6 to 90.0 nm/min were observed. Films were amorphous to X-rays as deposited and SEM micrographs showed smooth, featureless film surfaces. Cross-sectional TEM showed no compositional inhomogeneity. RBS revealed that x (from the formula TixSi1−xO2) was dependent upon the choice of TiO2 precursor. For films grown using TTIP-TEOS x could be varied by systematic variation of the flow of N2 through the precursor vessels or the deposition temperature. For the case of TN-TEOS x remained close to 0.5. The results suggested the existence of a specific chemical reaction between TN and TEOS prior to film deposition.

The CVD of zirconium dioxide (ZrO2) films from zirconium tetra-tert-butoxide {Zr[OC(CH3)3]4} is also described. The films, which were deposited on Si(100), were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ellipsometry, X-ray diffraction (XRD), and Rutherford backscattering spectroscopy (RBS). Deposition was studied between ∼380 and 825 °C, and at precursor pressures between 4 × 10−5 and 1 × 10−4 Torr. The kinetics for steady-state growth were studied as functions of temperature and precursor pressure. Results were fit to a two-step kinetic model involving reversible precursor adsorption followed by irreversible decomposition to ZrO2.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 670: Symposium K – Gate Stack and Sillicide Issues in Silicon , 2001 , K4.1
Copyright
Copyright © Materials Research Society 2001

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References

REFERENCES

1 Melponder, S. M., West, A. W., Barnes, C. L. et al., “Phase transformations in TiO2/SiO2 sol-gel films as a function of composition and heat-treatment,” J. Mater. Sci. 26, 3585–3592 (1991).Google Scholar
2 Syms, R. R. A. and Holmes, A. S., “Deposition of thick silica-titania sol-gel films on Si substrates,” J. Non-Cryst. Sol. 170, 223–233 (1994).Google Scholar
3 Mukhopadhyay, S. M. and Garofalini, S. H., “Surface studies of TiO2-SiO2 glasses by X-ray photoelectron spectroscopy,” J. Non-Cryst. Sol. 126, 202–208 (1990).Google Scholar
4 Schultz, P. C., “Binary Titania-Silica Glasses Containing 10 to 20 Wt% TiO2,” J. Am. Ceram. Soc. 59 (5-6), 214–219 (1976).Google Scholar
5 Kamada, T., Kitagawa, M., Shibuya, M. et al., “Structure and Properties of Silicon Titanium Oxide Films Prepared by Plasma-Enhanced Chemical Vapor Deposition Method,” Jpn. J. Appl. Phys. 30 (12B), 3594–3596 (1991).Google Scholar
6 Martinet, C., Paillard, V., Gagnaire, A. et al., “Deposition of SiO2 and TiO2 Thin Films by Plasma Enhanced Chemical Vapor Deposition for Antireflection Coating,” J. Non-Crystalline Solids 216, 77–82 (1997).Google Scholar
7 Inoue, M., U. S. (1971).Google Scholar
8 Smith, Ryan C., Ma, Tiezhong, Hoilien, Noel et al., “Chemical vapour deposition of the oxides of titanium, zirconium and hafnium for use as high-k materials in microelectronic devices. A carbon-free precursor for the synthesis of hafnium dioxide,” Adv. Mater. Opt. Electron. 10 (3-5), 105–114 (2000).Google Scholar
9 Bradley, D. C., “Metal Alkoxides as Precursors for Electronic and Ceramic Materials,” Chem. Rev. 89, 1317–1322 (1989).Google Scholar
10 Xue, Z., Vaartstra, B. A., Caulton, V. G. et al., “Chemical Vapor Deposition of Cubic-Zirconia Thin Films from Zirconium Alkoxide Complexes,” Eur. J. Solid State Inorg. Chem. 29, 213–225 (1992).Google Scholar
11 Cameron, M. A. and George, S. M., “ZrO2 film growth by chemical vapor deposition using zirconium tetra-tert-butoxide,” Thin Solid Films 348 (1,2), 90–98 (1999).Google Scholar
12 Adams, A. C. and Capio, C. D., “The Deposition of Silicon Dioxide Films at Reduced Pressure,” J. Electrochem. Soc. 126 (6), 1042–1046 (1979).Google Scholar
13 Rojas, S., Modelli, A., Wu, W. S. et al., “Properties of silicon dioxide films prepared by low-pressure chemical vapor deposition from tetraethylorthosilicate,” J. Vac. Sci. Technol. B 8 (6), 1177–1184 (1990).Google Scholar
14 Okuhara, T. and White, J. M., “Preparation of SiO2 Overlayers on Oxide Substrates by Chemical Vapor Deposition of Si(OC2H5)4,” Appl. Surf. Sci. 29, 223–241 (1987).Google Scholar
15 Rausch, N. and Burte, E.P., “Thin High-Dielectric TiO2 Films Prepared by Low Pressure MOCVD,” Microelectronic Engineering 19, 725–728 (1992).Google Scholar
16 Yoon, Y.S., Kang, W. N., Yom, S. S. et al., “Structural Properties of Titanium Dioxide Films Grown On p-Si by Metal-Organic Chemical Vapor Deposition at Low Temperature,” Thin Solid Films 238, 12–14 (1994).Google Scholar
17 Yan, J., Gilmer, D. C., Campbell, S. A. et al., “Structural and electrical characterization of TiO2 grown from titanium tetrakis-isopropoxide (TTIP) and TTIP/H2O ambients,” J. Vac. Sci. Technol., B 14 (3), 1706–1711 (1996).Google Scholar
18 Taylor, Charles J., Gilmer, David C., Colombo, Daniel G. et al., “Does Chemistry Really Matter in the Chemical Vapor Deposition of Titanium Dioxide? Precursor and Kinetic Effects on the Microstructure of Polycrystalline Films,” J. Am. Chem. Soc. 121 (22), 5220–5229 (1999).Google Scholar
19 Hubbard, K. J. and Schlom, D. G., “Thermodynamic Stability of Binary Oxides in Contact with Silicon,” J. Mater. Res. 11, 2757–2776 (1996).Google Scholar
20 Mallard, W. G. and Linstrom, P. J., “NIST Webbook, NIST Standard Reference Database Number 69,”, (National Institute of Standards and Technology (http://webbook.nist.gov), Gaithersburg, 2000).Google Scholar
21 DeVries, R. C. and Roy, R., “A Phase Diagram for the System Ti-TiO2 Constructed from Data in the Literature,” Ceramic Bulletin 33 (12), 370 (1954).Google Scholar
22 Evans, D. L., “Solid Solution of TiO2 in SiO2,” J. Am. Ceram. Soc. 53 (7), 418–419 (1970).Google Scholar
23 Addison, C. C. and Logan, N., “Anhydrous Metal Nitrates,” Adv. Inorg. Chem. and Radiochem. 6, 71–142 (1964).Google Scholar
24 Coles, M. P., Lugmair, C. G., Terry, K. W. et al., “Titania-silica materials from the molecular precursor Ti,” Chem. Mater. 12 (1), 122–131 (2000).Google Scholar
25 Smith, Ryan C., Hoilien, Noel, Taylor, Charles J. et al., “Low temperature chemical vapor deposition of ZrO2 on Si(100) using anhydrous zirconium(IV) nitrate,” J. Electrochem. Soc. 147 (9), 3472–3476 (2000).Google Scholar
26 Wolfe, D., Flock, K., Therrien, R. et al., “Remote plasma enhanced-metal organic chemical vapor deposition of zirconium oxide/silicon oxide alloy, (ZrO2)x-(SiO2)1-x (x.ltoreq. 0.5), thin films for advanced high-K gate dielectrics,” Mater. Res. Soc. Symp. Proc. 567 (Ultrathin SiO2 and High-K Materials for ULSI Gate Dielectrics), 343–348 (1999).Google Scholar