H and C NMR investigations of Pb(Zr,Ti)O[sub 3] thin-film precursor solutions

Journal Article · Wed Mar 31 23:00:00 EST 1993 · Chemistry of Materials; (United States)

DOI:https://doi.org/10.1021/cm00028a019· OSTI ID:6050679

Assink, R A; Schwartz, R W ^[1]

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1. Sandia National Laboratories, Albuquerque, NM (United States)

Solvent reactions, ligand substitutions, and the oligomer/polymer backbone structure are important factors in the solution preparation of ceramic films. In this study the authors have used H and C NMR spectroscopy to characterize solvent and ligand effects in precursor solutions used for the deposition of ferroelectric PZT (lead zirconate titanate) thin films. Solutions were prepared by a sequential precursor addition method from carboxylate and alkoxide precursors of the three cations, and the solvent, acetic acid, methanol, and water. The results indicate that acetic acid was a key component in the solution preparation process. As observed previously for single metallic component systems, its presence resulted in esterification reactions, leading in the present case to the formation of methyl, isopropyl, and n-butyl acetates. Second, acetic acid functioned as a chemical modifier, or chelating agent, replacing essentially all of the alkoxy ligands of the original precursors. Since alkoxy replacement appeared to be complete, we may describe the PZT species formed in solution as oxo acetate in nature. Finally, the solvent and ligand behavior of a solution prepared by an inverted mixing order was compared to the behavior of the solution prepared by a sequential precursor addition. The spectra for the two solutions were similar, and only differences in the relative intensities of the ester and alcoholic resonances were observed. 29 refs., 5 figs., 3 tabs.

• DOE Contract Number: AC04-76DP00789
• OSTI ID: 6050679
• Journal Information: Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 5:4; ISSN CMATEX; ISSN 0897-4756
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360201* -- Ceramics
Cermets
& Refractories-- Preparation & Fabrication
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
665100 -- Nuclear Techniques in Condensed Matter Physics -- (1992-)
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ACETATES
ACETIC ACID
ALCOHOLS
CARBON 13
CARBON ISOTOPES
CARBOXYLIC ACID SALTS
CARBOXYLIC ACIDS
CATIONS
CHARGED PARTICLES
CHEMICAL ANALYSIS
CHEMICAL REACTIONS
DEPOSITION
ESTERIFICATION
EVEN-ODD NUCLEI
FERROELECTRIC MATERIALS
FILMS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
IONS
ISOTOPES
LEAD COMPOUNDS
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
METHANOL
MONOCARBOXYLIC ACIDS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PRECURSOR
PZT
RESONANCE
SOLVENTS
STABLE ISOTOPES
THIN FILMS
TITANATES
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
WATER
ZIRCONATES
ZIRCONIUM COMPOUNDS