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The influence of water of hydrolysis on microstructural development in sol-gel derived LiNbO3 thin films

Published online by Cambridge University Press:  03 March 2011

Vikram Joshi  and
Martha L. Mecartney
Vikram Joshi
Affiliation:
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455
Martha L. Mecartney
Affiliation:
Materials Science and Engineering Program, Department of Mechanical and Aerospace Engineering, University of California, Irvine, California 92717
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Abstract

The effect of water of hydrolysis on nucleation, crystallization, and microstructural development of sol-gel derived single phase LiNbO3 thin films has been studied using transmission electron microscopy (TEM), atomic force microscopy (AFM), x-ray diffraction (XRD), and differential scanning calorimetry (DSC). A precursor solution of double ethoxides of lithium and niobium in ethanol was used for the preparation of sol. DSC results indicated that adding water to the solution for hydrolysis of the double ethoxides lowered the crystallization temperature from 500 °C (no water) to 390 °C (2 moles water per mole ethoxide). The amount of water had no effect on the short-range order in amorphous LiNbO3 gels but rendered significant microstructural variations for the crystallized films. AFM studies indicated that surface roughness of dip-coated films increased with increasing water of hydrolysis. Films on glass, heat-treated for 1 h at 400 °C, were polycrystalline and randomly oriented. Those made with a low water-to-ethoxide ratio had smaller grains and smaller pores than films prepared from sols with higher water-to-ethoxide ratios. Annealing films with a low water concentration for longer times or at higher temperatures resulted in grain growth. Higher temperatures (600 °C) resulted in grain faceting along close-packed planes. Films deposited on c-cut sapphire made with a 1:1 ethoxide-to-water ratio and heat-treated at 400 °C were epitactic with the c-axis perpendicular to the film-substrate interface. Films with higher concentrations of water of hydrolysis on sapphire had a preferred orientation but were polycrystalline. It is postulated that a high amount of water increases the concentration of amorphous LiNbO3 building blocks in the sol through hydrolysis, which subsequently promotes crystallization during heat treatment.

Type
Articles
Information
Journal of Materials Research , Volume 8 , Issue 10 , October 1993 , pp. 2668 - 2678
Copyright
Copyright © Materials Research Society 1993

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References

REFERENCES

1Weis, R. S. and Gaylord, T. K., Appl. Phys. A 37, 191 (1985).CrossRefGoogle Scholar
2Nassau, K., Levinstein, H., and Loiacono, G., J. Phys. Chem. Solids 27, 989 (1966).CrossRefGoogle Scholar
3Nassau, K. and Levinstein, H., Appl. Phys. Lett. 7, 69 (1965).CrossRefGoogle Scholar
4Abouelleil, M. M. and Leonberger, F. J., J. Am. Ceram. Soc. 72, 311 (1989).Google Scholar
5Griffel, G., Ruschin, S., Hardy, A., Itzkovitz, M., and Croitoru, N., Thin Solid Films 126, 185 (1985).CrossRefGoogle Scholar
6Okada, A., Ferroelectrics 14, 739 (1976).CrossRefGoogle Scholar
7Hirano, S. and Kato, K., J. Non-Cryst. Solids 100, 538 (1988).CrossRefGoogle Scholar
8Partlow, D. P. and Greggi, J., J. Mater. Res. 2, 595 (1987).CrossRefGoogle Scholar
9Nashimoto, K. and Cima, M. J., Mater. Lett. 10, 348 (1991).CrossRefGoogle Scholar
10Hsueh, C-C. and Mecartney, M. L., J. Mater. Res. 6, 2208 (1991).CrossRefGoogle Scholar
11Keddie, J. L. and Giannelis, E. P., J. Am. Ceram. Soc. 74, 2669 (1991).CrossRefGoogle Scholar
12Lakeman, C. D. E. and Payne, D. A., J. Am. Ceram. Soc. 75, 3091 (1992).CrossRefGoogle Scholar
13Joshi, V., Goo, G. K., and Mecartney, M. L., in Better Ceramics Through Chemistry V, edited by Hampden-Smith, M. J., Klemperer, W. G., and Brinker, C. J. (Mater. Res. Soc. Symp. Proc. 271, Pittsburgh, PA, 1992), p. 377.Google Scholar
14Hirano, S. and Kato, K., Advanced Ceram. Mater. 3, 503 (1988).CrossRefGoogle Scholar
15Bailey, J. K., Bellare, J. R., and Mecartney, M. L., in Specimen Preparation for Transmission Electron Microscopy of Materials, edited by Bravman, J. C., Anderson, R. M., and McDonald, M. L. (Mater. Res. Soc. Symp. Proc. 115, Pittsburgh, PA, 1988), p. 69.Google Scholar
16Hues, S. M., Colton, R. J., Meyer, E., and Güntherodt, H. J., Mater. Res. Bull. XVIII (1), 41 (1993).CrossRefGoogle Scholar
17Warren, B. E., J. Am. Ceram. Soc. 17, 249 (1934).CrossRefGoogle Scholar
18Eichorst, D. J. and Payne, D. A., in Better Ceramics Through Chemistry IV, edited by Zelinski, B. J. J., Brinker, C. J., Clark, D. E., and Ulrich, D. R. (Mater. Res. Soc. Symp. Proc. 180, Pittsburgh, PA, 1990), p. 669.Google Scholar
19Eichorst, D. J., Howard, K. E., and Payne, D. A. (unpublished research).Google Scholar
20Rauber, A., in Current Topics in Materials Science, edited by Kaldis, E. (North-Holland, Amsterdam, 1978), p. 481.Google Scholar
21Prokhorov, A. M. and Kuz'minov, Y.S., Physics and Chemistry of Crystalline Lithium Niobate (Adam Hilger, Bristol and New York, 1990), p. 18.Google Scholar
22Eichorst, D. J., Payne, D. A., Wilson, S. R., and Howard, K. E., Inorg. Chem. 29, 1459 (1990).CrossRefGoogle Scholar
23Kingery, W. D., Bowen, H. K., and Uhlmann, D. R., Introduction to Ceramics, 2nd ed. (John Wiley & Sons, New York, 1976), pp. 257, 263.Google Scholar
24Brinker, C. J. and Scherer, G. W., Sol-Gel Science (Academic Press, New York, 1990), pp. 799, 814.Google Scholar
25Brinker, C. J., Hurd, A. J., and Ward, K. J., in Ultrastructure Processing of Advanced Ceramics, edited by Mackenzie, J. D. and Ulrich, D. R. (John Wiley & Sons, New York, 1988), p. 223.Google Scholar
26Tiller, W. A., The Science of Crystallization–Microscopic Interfacial Phenomena (Cambridge University Press, New York, 1991), pp. 171, 175.CrossRefGoogle Scholar
27Braunstein, G., Raz-Pujalt, G. R., Mason, M. G., Blanton, T., Barnes, C. L., and Margevich, D., J. Appl. Phys. 73, 961 (1993).CrossRefGoogle Scholar
28Matsunaga, H., Ohno, H., Okamoto, Y., and Nakajima, Y., J. Cryst. Growth 99, 630 (1990).CrossRefGoogle Scholar