Structure and properties interrelationships of SrBi₂(Ta<sub>1-x</sub>Nb<sub>x</sub>)₂O₉
In recent years, the ferroelectric oxides belonging to the family of layered perovskite, e.g., SrBi₂(Ta₁₋xNbx)₂O₉ (or SBTN), were identified as promising candidates for nonvolatile memory applications. SrBi₂Ta₂O₉ (or SBT) thin films were found to exhibit no fatigue up to 10¹² switching cycles, very good retention properties and low leakage current densities on Pt electrodes. However, high temperature processing, ie. 750 - 800°C, is needed for SBT to exhibit ferroelectric properties. Moreover, the fundamental properties of SBTN have not been fully characterized. In this research, SBTN solid solutions were studied from two aspects: the technical aspect and scientific aspect.
From the technical point of view, low temperature processing of SBTN ferroelectric thin films was developed. In this part of study, SBTN thin films were made by metalorganic decomposition method (MOD) and were deposited on Pt-electrodes. The structure development study by a non-destructive optical method, spectroscopic ellipsometry, was proposed to determine nucleation and grain growth temperatures. The information on structure development can be obtained by observing how the refractive indices and film thicknesses change as functions of annealing temperature. The results of structure development study for SBT thin films suggest that the ferroelectric properties are controlled by grain growth process rather than nucleation process. The critical factor for ferroelectric properties was to have grain size exceeding a critical value, i.e., 0.1 µm. Applying this concept, low temperature processing can be achieved by growing larger grains at lower temperature. The processing temperature of SBTN thin films was reduced by 50 - 100°C by adding excess Bi or increasing Nb/Ta ratio. The optimum excess Bi content in SBT was 30 - 50%; within this range, limited solid solution of Bi₂O₃ and SBT was formed.
From the scientific aspect of view, optical properties and ionic transport phenomena of SBTN bulk ceramics were investigated for the first time. The reason of using bulk ceramics is to exclude the difficulties associated with thin film technology, e.g., grain size effect and electrode-ferroelectric interface effect. These bulk property studies provide fundamental understanding of SBTN materials and provide a guideline for process development in device applications. The optical dispersion functions of bulk SBTN were obtained by using various angle spectroscopic ellipsometry with a surface layer correction. The values of refractive indices were found to vary with composition, which are possibly associated with crystallographic orientation. Using the Lorentz Oscillator model, the approximate energy band gaps of SBTN solid solutions were estimated to be about 5 eV.
The ionic transport phenomena of SBT and SrBi₂Nb₂O₉ (or SBN) were investigated by using impedance spectroscopy. This technique allows to separate the effect of ion transport in grain, grain boundary and electrode-ferroelectric interface. In this study, the fatigue model of bismuth layered oxides was discussed through ionic conductivity and interface absorption effect. One conducting species, oxygen vacancies with positive charges, was assumed in the model. High ionic conductivities of SBT and SBN (~ 10¯⁷ S/cm) comparing to Pb(Zr₁₋xTix)O₃ (~ 10¯¹¹-10¯¹⁰ S/cm) suggests high defect concentration and high charge mobility in bismuth layered oxide materials. As a result, the most possible model to explain high resistance to fatigue of SBT/SBN was the easy recovery of oxygen vacancies from the entrapment at electrode-ferroelectric interfaces.