Metal oxide materials are a broad class of materials found in many current technologies due to their interesting properties such as magnetism and ferroelectricity. Material properties can be tuned and heavily influenced by disorder at the atomic level, as has been shown in the ferrimagnetic and ferroelectric Al2-x-yGaxFeyO3 materials, which adopt the non-centrosymmetric, orthorhombic GaFeO3 crystal structure-type (Pna21). The significant cation disorder and non centrosymmetric nature of the crystal structure underlie the multiferroic properties in these materials and make them one of the few chemical systems to possess multiferroic ordering near room temperature. Unfortunately, while cation site disorder is responsible for the multiferroic properties observed in these compounds, their complex crystal structure has led to inconsistent reports in the ternary Al2-xFexO3 and Ga2-xFexO3 compounds. X-ray absorption near-edge spectroscopy (XANES) is an element specific technique, which can be used to examine cation site disorder as a function of changes in the average coordination environment around the metal, providing a means of studying these complex materials.
In this thesis, XANES was used to investigate factors affecting cation site disorder in a series of Al1-xGaxFeO3 materials (0 ≤ x ≤ 1) adopting the GaFeO3 crystal structure-type. The GaFeO3 crystal structure has four cation sites, of which, the distorted octahedral Fe1 and Fe2 sites are primarily occupied by Fe3+, and the less distorted tetrahedral A1 and octahedral A2 sites are primarily occupied by Al3+ or Ga3+. These materials were initially synthesized using a high temperature ceramic method, and it was found that with increasing Ga3+ content (x) these materials show a decrease in the amount of cation site disorder between the tetrahedral site and the three octahedral sites. This decrease is attributed to the tetrahedral site preference of Ga3+, which inhibits cation site disorder at the A1 site, as opposed to the octahedral site preference observed for Al3+. Additionally, Fe3+ was found to predominantly occupy the three octahedral sites over the tetrahedral site in these materials, likely because of its large ionic size and the strong magnetic coupling between those three sites.
The quaternary Al1-xGaxFeO3 materials (0 ≤ x ≤ 1) were synthesized again via two other techniques: a citrate sol-gel method and a co-precipitation method. The oxide network binding the binary metal oxide precursors limits ion mobility in the high temperature ceramic method. The citrate sol-gel and co-precipitation methods were used to generate mixed-metal precursors with a more homogeneous distribution of the metal cations than the binary metal oxide precursors commonly used by the high temperature ceramic method. Mixed-metal precursors reduce the distance the ions have to diffuse, while the nature of the amorphous matrix was found to affect disorder in the resulting material. From analysis of the XANES spectra, the ceramic method showed the least amount of cation site disorder, followed by the citrate sol-gel method and co-precipitation method, respectively. Greater annealing temperatures resulted in an increase in cation site disorder, with the average coordination number of Al3+ and Ga3+ increasing while the average coordination number of Fe3+ decreased. Al1-xGaxFeO3 materials synthesized via the co-precipitation method showed the greatest amount of cation disorder, followed by the citrate sol-gel and high temperature ceramic techniques, respectively.
The research presented in this thesis is among the first to examine a large number of materials from the relatively unexplored Al1-xGaxFeO3 system, and has contributed to the growing body of knowledge on the factors affecting cation site disorder in these materials and potentially other systems. Further, despite a simple rationale for understanding the features present in Al L2,3- and Ga K-edge spectra, these studies have shown how effectively XANES can be used to understand subtle changes in the atomic structure of solid-state materials.
| Identifer | oai:union.ndltd.org:USASK/oai:ecommons.usask.ca:10388/ETD-2013-11-1293 |
| Date | 2013 November 1900 |
| Contributors | Grosvenor, Andrew P. |
| Source Sets | University of Saskatchewan Library |
| Language | English |
| Detected Language | English |
| Type | text, thesis |
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