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Structure evolution in the PbO-ZrO2-TiO2 sol-gel system: Part I — Characterization of prehydrolyzed precursors

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Abstract

In this investigation, several spectroscopic and analytical techniques were used to determine the chemical compositions and structures of the lead, zirconium, titanium, and Pb-(Zr, Ti) alkoxides involved in the sol-gel synthesis of PZT thin films. These techniques included 1H, 13C, and 207Pb NMR; FT-IR; gas chromatography; Karl Fischer titration; and number-average molecular weights (M n ) determined by cryoscopy. It was found that the titanium precursor had a M n of 548 and a formula of [Ti(OCH2CH2OCH3)4]1.6; the zirconium precursor had a M n of 1015 and a formula of [Zr(OCH2CH2OCH3)4]2.6; and the lead precursor had a formula Pb6(OOCCH3)5(OCH2CH2OCH3)7. 4 H2O and a molecular weight of 2131 (M n =2113). It was observed that residual water from the incomplete dehydration of lead acetate trihydrate coupled with released water due to the esterification of acetic acid caused M-O-M (M=Pb, Zr, Ti) bonds in the Pb-(Zr, Ti) alkoxide. Two possible isomeric structures of the Pb-(Zr, Ti) alkoxide have been proposed. They are both cyclic and have a formula of Pb2M′M″O2(OR)8(ROH)2, (M′M″=Zr and/or Ti) and a molecular weight of 1336 (M n =1386).

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Authors and Affiliations

  1. Advanced Ceramics Processing Laboratory, Departments of Chemistry and Chemical, Bio, and Materials Engineering, Arizona State University, 85287, Tempe, AZ

    P. R. Coffman & S. K. Dey

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  1. P. R. Coffman
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  2. S. K. Dey
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Coffman, P.R., Dey, S.K. Structure evolution in the PbO-ZrO2-TiO2 sol-gel system: Part I — Characterization of prehydrolyzed precursors. J Sol-Gel Sci Technol 1, 251–265 (1994). https://doi.org/10.1007/BF00486168

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