Skip to main content Accessibility help

Microstructural development and electrical properties of sol-gel prepared lead zirconate-titanate thin films

  • Cheng-Chen Hsueh (a1) and Martha L. Mecartney (a1)


A systematic investigation of the microstructural evolution of fast fired, sol-gel derived Pb(Zr, Ti)O3 films (Zr/Ti = 54/46) was performed by analytical transmission electron microscopy (TEM). It was found that the nucleation and growth of the sol-gel PZT films were influenced by the precursor chemistry. The precursor solution was composed of Pb 2-ethylhexanoate, Ti isopropoxide, and Zr n-propoxide in n-propanol. Porous and spherulitic perovskite grains nucleated and grew from a pyrochlore matrix for NH4OH-modified films, but no chemical segregation was found. These thin films consisted completely of porous spherulitic PZT grains (∼2 μm) when the firing temperature was increased. Chemical phase separation with regions of Zr-rich pyrochlore particles separated by Zr-deficient perovskite grains was observed in the initial stages of nucleation and growth for CH3COOH-modified PZT films. This phase separation is attributed to the effect of acetate ligands on the modification of molecular structure of the PZT precursor. Firing the acid-modified films at higher temperatures for long times resulted in porous perovskite grain structures. The residual porosity in these films is suggested to be a result of differential evaporation/condensation rates during the deposition process and the gas evolution at high temperatures due to trapped organics in the films. Dielectric and ferroelectric properties were correlated to the microstructure of the films. Lower dielectric constants (∼500) and higher coercive fields (∼65 kV/cm) were found for the acid-modified PZT films with phase separation in comparison to those measured from the sol-gel films with a uniform microstructure (∽ > 600, Ec < 50 kV/cm). All films fired at 650 °C showed relatively good remanent polarization on the order of 20 μC/cm2.



Hide All
1.Bondurant, D. W. and Gnadinger, F. P., IEEE Spectrum 26 (7), 30 (1989).
2.Land, C. E., J. Am. Ceram. Soc. 72 (11), 2059 (1989).
3.Lines, M. E. and Glass, A. M., Principles and Applications of Ferroelectrics and Related Materials (Oxford University Press, London, U. K., 1977), pp. 559607.
4.Bondurant, D. W., Proc. Colorado Microelectronics Conference with The First Symposium on Integrated Ferroelectrics (University of Colorado, Colorado Springs, CO, 1989), p. 212.
5.Blum, J. B. and Gurkovich, S. R., J. Mater. Sci. 20, 4479 (1985).
6.Budd, K. D., Dey, S. K., and Payne, D. A., Proc. Br. Ceram. Soc. 36, 107 (1985).
7.Chen, K. C., Janah, A., and Mackenzie, J. D., in Better Ceramics Through Chemistry II, edited by Brinker, C. J., Clark, D. E., and Ulrich, D. R. (Mater. Res. Soc. Symp. Proc. 73, Pittsburgh, PA, 1986), p. 731.
8.Lipeles, R. A., Coleman, D. J., and Leung, M. S., in Better Ceramics Through Chemistry II, edited by Brinker, C. J., Clark, D. E., and Ulrich, D. R. (Mater. Res. Soc. Symp. Proc. 73, Pittsburgh, PA, 1986), p. 665.
9.Lipeles, R. A. and Coleman, D. J., in Ultrastructure Processing of Advanced Ceramics, edited by Mackenzie, J. D. and Ulrich, D. R. (John Wiley & Sons, New York, NY, 1988), p. 919.
10.Dey, S. K., Budd, K. D., and Payne, D. A., IEEE Trans, on Ultrasonics, Ferroelectrics and Frequency Control 35 (1), 80 (1988).
11.Yi, G., Wu, Z., and Sayer, M., J. Appl. Phys. 64 (5), 2717 (1988).
12.Sanchez, L. E., Wu, S. Y., and Naik, I. K., Appl. Phys. Lett. 56 (24), 2399 (1990).
13.Livage, J., Henry, M., and Sanchez, C., Prog. Solid State Chem. 18, 259 (1988).
14.Schmidt, H., J. Non-Cryst. Solids 100, 51 (1988).
15.Tsui, Y. T., Hinderaker, P. D., and McFadden, F. J., Rev. Sci. Instrum. 39 (10), 1423 (1968).
16.Okada, A., J. Appl. Phys. 48 (7), 2905 (1977).
17.Brinker, C. J. and Scherer, G. W., Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing (Academic Press, San Diego, CA, 1990), p. 818.
18.Keith, H. D. and Padden, F. J., Jr., J. Appl. Phys. 34 (8), 2409 (1963).
19.Keith, H. D. and Padden, F. J., Jr., J. Appl. Phys. 35 (4), 1270 (1964).
20.Keith, H. D. and Padden, F. J., Jr., J. Appl. Phys. 35 (4), 1286 (1964).
21.Sanchez, C., Livage, J., Henry, M., and Babonneau, F., J. Non-Cryst. Solids 100, 65 (1988).
22.Jaffe, B., Cook, W. R., Jr., and Jaffe, H., Piezoelectric Ceramics (Academic Press, London, U. K., 1971), p. 137.
23.Hsueh, C. C. and Mecartney, M. L., in Ferroelectric Thin Films, edited by Myers, E. R. and Kingon, A. I. (Mater. Res. Soc. Symp. Proc. 200, Pittsburgh, PA, 1990), p. 219.
24.Jaffe, B., Roth, R. S., and Marzullo, S., J. Res. National Bureau of Standards 55 (5), 239 (1955).
25.Okazaki, K. and Nagata, K., J. Am. Ceram. Soc. 56 (2), 82 (1973).
26. Note added in proof: See also Carim, A. H., Turtle, B. A., Doughty, D. H., and Martinez, S. L., J. Am. Ceram. Soc. 74 (6), 1455 (1991) for microstructural development in PZT for another solution process.


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed