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.
Ferroelectric PZT thin films were prepared by sol-gel methods and RF magnetron sputtering. Sputtered PZT fast fired at 650° for 30 minutes showed microporosity. For the sol-gel route, solution precursors had a significant effect on the microstructure of the crystalline PZT films. PZT thin films derived from metal-organic precursors dissolved in n-propanol were observed to have large and microporous spherulitic grains on the order of 2 μm and phase separation in acetic acid-catalyzed films. In contrast, PZT precursors originated from alcohol exchanges with 2-methoxyethanols resulted in dense films with fine grains of ∼0.2 μm and clear evidence of ferroelectric domains. The dense sol-gel films possessed superior dielectric and ferroelectric properties.
Transmission electron microscopy (TEM) was used to investigate the microstructural evolution of sol-gel derived ferroelectric PZT films. Aggregates of perovskite crystals nucleated and grew out of a pyrochlore matrix at 550°C. A dense, single-phase perovskite PZT film was obtained by fast firing the film at 650°C for 30 minutes. The grain size of this film was approximately 0.2-0.4 μm. Hot-stage TEM observed disappearance of ferroelectric domains as the temperature approaching 325°C.
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