Hostname: page-component-586b7cd67f-2brh9 Total loading time: 0 Render date: 2024-11-23T14:53:34.276Z Has data issue: false hasContentIssue false
  • English
  • Français

Nanocrystalline ZrO2 thin films on silicon fabricated by pulsed-pressure metalorganic chemical vapor deposition (PP-MOCVD)

Published online by Cambridge University Press:  31 January 2011

L. Ramirez ,
M.L. Mecartney  and
S.P. Krumdieck
L. Ramirez*
Affiliation:
Department of Chemical Engineering and Materials Science, University of California–Irvine, Irvine, California 92697-2575
M.L. Mecartney
Affiliation:
Department of Chemical Engineering and Materials Science, University of California–Irvine, Irvine, California 92697-2575
S.P. Krumdieck
Affiliation:
Department of Mechanical Engineering, University of Canterbury, Christchurch, Private Bag 4800, Christchurch, New Zealand
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

ZrO2 films deposited on silicon (100) substrates using pulsed-pressure metalorganic chemical vapor deposition (PP-MOCVD) with zirconium n-propoxide (ZnP) Zr(OC3H7)4 were dense and fully crystalline for substrate temperatures of 500 to 700 °C. Film thicknesses were 40 to 815 nm thick, measured after growth using ellipsometry and scanning electron microscopy (SEM). The growth rate was between 0.1 μm/h at 500 °C and 1 μm/h at 700 °C. Transmission electron microscopy (TEM) and x-ray diffraction (XRD) indicated an average grain size of 10 to 20 nm. There was a random orientation of cubic/tetragonal zirconia at the highest experimental temperature of 700 °C. SEM and atomic force microscopy (AFM) was used to characterize island height of discontinuous films in the initial stages of growth where defects in the substrate caused preferred nucleation of isolated particles. At later stages of growth, the average surface roughness of continuous films was 30 nm, which revealed a more uniform growth had developed. A growth model is proposed, and optimal growth conditions are suggested for targeted microstructures of ZrO2 films.

Keywords

Chemical vapor deposition (CVD) (deposition)Scanning electron microscopy (SEM)Thin film
Type
Articles
Information
Journal of Materials Research , Volume 23 , Issue 8 , August 2008 , pp. 2202 - 2211
Copyright
Copyright © Materials Research Society 2008

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1Chang, J.P., Lin, Y.S.Chu, K.: Rapid thermal chemical vapor deposition of zirconium oxide for metal-oxide-semiconductor field effect transistor application. J. Vac. Sci. Technol., B 19, 1782 2001Google Scholar
2Fakhruddin, M., Singh, R., Poole, K.F., Kondapi, S.V.Narayan, J.: The effect of interfacial layers on high-performance gate dielectrics processed by RTP-ALD. J. Electrochem. Soc. 151, G507 2004Google Scholar
3Ramanathan, S.McIntyre, P.C.: Ultrathin zirconia/SiO2 dielectric stacks grown by ultraviolet-ozone oxidation. Appl. Phys. Lett. 80, 3793 2002CrossRefGoogle Scholar
4Wang, J., Zhao, L., Luu, N.H., Wang, D.Nakashima, H.: Structural and electrical properties of Zr oxide film for high-k gate dielectrics by using electron cyclotron resonance plasma sputtering. Appl. Phys. A, Mater. 80, 1781 2005CrossRefGoogle Scholar
5Jeong, S.H., Bae, I.S., Shin, Y.S., Lee, S.B., Kwak, H.T.Boo, J.H.: Physical and electrical properties of ZrO2 and YSZ high-k gate dielectric thin films grown by RF magnetron sputtering. Thin Solid Films 475, 354 2005CrossRefGoogle Scholar
6Chen, L.B.: Yttria-stabilized zirconia thermal-barrier coatings—A review. Surf. Rev. Lett. 13, 535 2006Google Scholar
7Schulz, U., Saruhan, B., Fritscher, K.Leyens, C.: Review on advanced EB-PVD ceramic topcoats for TBC applications. Int. J. Appl. Ceram. Technol. 1, 302 2004Google Scholar
8Dobbins, T.A., Knight, R.Mayo, M.J.: HVOF thermal spray deposited Y2O3-stabilized ZrO2 coatings for thermal barrier applications. J. Therm. Spray Technol. 12, 214 2003CrossRefGoogle Scholar
9Goswami, B., Sahay, S.K.Ray, A.K.: Application of thermal-barrier coatings on combustion chamber liners—A review. High Temp. Mater. Pr.-Isr. 23, 211 2004Google Scholar
10Tang, F.Schoenung, J.M.: Evolution of Young’s modulus of air plasma sprayed yttria-stabilized zirconia in thermally cycled thermal-barrier coatings. Scr. Mater. 54, 1587 2006CrossRefGoogle Scholar
11Wahl, G., Metz, C.Samoilenkov, S.: Thermal-barrier coatings. J. Phys. [E] IV 11, 835 2001Google Scholar
12Von Dollen, P.Barnett, S.: A study of screen printed yttria-stabilized zirconia layers for solid oxide fuel cells. J. Am. Ceram. Soc. 88, 3361 2005Google Scholar
13Krumdieck, S., Sbaizero, O.Raj, R.: Unique precursor delivery and control afforded by low-pressure pulsed-CVD process with ultrasonic atomization. J. Phys. [E] IV 11, 1161 2001Google Scholar
14Krumdieck, S.Raj, R.: Conversion efficiency or alkoxide precursor to oxide films grown by an ultrasonic-assisted, pulsed liquid injection, metalorganic chemical vapor deposition (pulsed-CVD) process. J. Am. Ceram. Soc. 82, 1605 1999Google Scholar
15Cave, H.M., Krumdieck, S.P.Jermy, M.C.: Development of a model for high precursor conversion efficiency pulsed-pressure chemical vapor deposition (PP-CVD) processing. Chem. Eng. J. 135, 120 2008Google Scholar
16Cameron, M.A.George, S.M.: ZrO2 film growth by chemical vapor deposition using zirconium tetra-tert-butoxide. Thin Solid Films 348, 90 1999CrossRefGoogle Scholar
17Kajikawa, Y.Noda, S.: Growth mode during initial stage of chemical vapor deposition. Appl. Surf. Sci. 245, 281 2005Google Scholar
18Krumdieck, S.Raj, R.: Growth rate and morphology for ceramic films by pulsed-MOCVD. Surf. Coat. Technol. 141, 7 2001Google Scholar
19Krumdieck, S.P., Sbaizero, O., Bullert, A.Raj, R.: Solid yttria-stabilized zirconia films by pulsed chemical vapor deposition from metal–organic precursors. J. Am. Ceram. Soc. 85, 2873 2002Google Scholar
20Williams, P.A., Roberts, J.L., Jones, A.C., Chalker, P.R., Tobin, N.L., Bickley, J.F., Davies, H.O., Smith, L.M.Leedham, T.J.: Novel mononuclear alkoxide precursors for the MOCVD of ZrO2 and HfO2 thin films. Chem. Vap. Deposition 8, 163 20023.0.CO;2-V>CrossRefGoogle Scholar
21Rasband, W.S.: ImageJ in U.S. National Institutes of Health Bethesda, MD 1997–2006Google Scholar
22Weaver, L.: Cross-section TEM sample preparation of multilayer and poorly adhering films. Microsc. Res. Technol. 36, 368 1997Google Scholar
23Burleson, D.J., Roberts, J.T., Gladfelter, W.L., Campbell, S.A.Smith, R.C.: A study of CVD growth kinetics and film microstructure of zirconium dioxide from zirconium tetra-tert-butoxide. Chem. Mater. 14, 1269 2002Google Scholar
24Mathur, S., Altmayer, J.Shen, H.: Nanostructured ZrO2 and Zr–C–N coatings from chemical vapor deposition of metal-organic precursors. Z. Anorg. Allg. Chem. 630, 2042 2004Google Scholar
25Powder Diffraction File, Card No. 30-1468 and Card No. 17-0923, (Joint Committee on Powder Diffraction Standards, Swathmore, PA)Google Scholar
26Tu, R., Kimura, T.Goto, T.: High-speed deposition of yttria stabilized zirconia by MOCVD. Surf. Coat. Technol. 187, 238 2004CrossRefGoogle Scholar
27Warren, B.E.: X-Ray Diffraction Addison-Wesley London 1969Google Scholar
28Meng, G.Y., Song, H.Z., Dong, Q.Peng, D.K.: Application of novel aerosol-assisted chemical vapor deposition techniques for SOFC thin films. Solid State Ionics 175, 29 2004Google Scholar
29Bernard, O., Huntz, A.M., Andrieux, M., Seiler, W., Ji, V.Poissonnet, S.: Synthesis, structure, microstructure and mechanical characteristics of MO CVD deposited zirconia films. Appl. Surf. Sci. 253, 4626 2007Google Scholar
30Belot, J.A., McNeely, R.J., Wang, A., Reedy, C.J., Marks, T.J., Yap, G.P.A.Rheingold, A.L.: Expedient route to volatile zirconium metal-organic chemical vapor deposition precursors using amide synthons and implementation in yttria-stabilized zirconia film growth. J. Mater. Res. 14, 12 1999Google Scholar
31Garcia, G., Caro, J., Santiso, J., Pardo, J.A., Figueras, A.Albrutis, A.: Pulsed injection MOCVD of YSZ thin films onto dense and porous substrates. Chem. Vap. Deposition 9, 279 2003Google Scholar
32Shivashankar, S.A.Dharmaprakash, M.S.: Effect of nature of the precursor on crystallinity and microstructure of MOCVD-grown ZrO2 thin films in Novel Materials and Processes for Advanced CMOS, edited by M.I. Gardner, S. De Gendt, J-P. Maria, and S. Stemmer (Mater. Res. Soc. Symp Proc. 745, Warrendale, PA, 2003), pp. 191–196Google Scholar
33Krumdieck, S.P., Sbaizero, O., Bullert, A.Raj, R.: YSZ layers by pulsed-MOCVD on solid oxide fuel cell electrodes. Surf. Coat. Technol. 167, 226 2003CrossRefGoogle Scholar
34Chour, K.W., Chen, J.Xu, R.: Metal-organic vapor deposition of YSZ electrolyte layers for solid oxide fuel-cell applications. Thin Solid Films 304, 106 1997CrossRefGoogle Scholar
35Jung, I.H., Bae, K.K., Yang, M.S.Ihm, S.K.: A study of the microstructure of yttria-stabilized zirconia deposited by inductively coupled plasma spraying. J. Therm. Spray Technol. 9, 463 2000Google Scholar
36Dahl, P., Kaus, I., Zhao, Z., Johnsson, M., Nygren, M., Wiik, K., Grande, T.Einarsrud, M.A.: Densification and properties of zirconia prepared by three different sintering techniques. Ceram. Int. 33, 1603 2007Google Scholar