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

Published online by Cambridge University Press:  31 January 2011

Cheng-Chen Hsueh  and
Martha L. Mecartney
Cheng-Chen Hsueh
Affiliation:
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455
Martha L. Mecartney
Affiliation:
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455
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Abstract

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.

Type
Articles
Information
Journal of Materials Research , Volume 6 , Issue 10 , October 1991 , pp. 2208 - 2217
Copyright
Copyright © Materials Research Society 1991

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