Crystal chemistry and properties of bismuth-modified complex oxide perovskites

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(Thesis) Ph.D.
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There is a great interest in developing new high-performance piezo-/ferroelectric materials that are lead-reduced or lead-free. This work focuses on using bismuth as a lead alternative, and studies solid solutions based on the end-member Bi(Zn2/3Nb1/3)O3 (BZN). First, ceramics of the (1-x)PbTiO3-xBi(Zn2/3Nb1/3)O3 [(1-x)PT-xBZN] solid solution were synthesized. The tetragonality (c/a ratio) and A-site displacement increase with increasing BZN content, as revealed by X-ray diffraction analysis. Dielectric measurements show that the Curie temperature TC increases with increasing BZN up to a maximum of 520 °C for the composition of x = 0.20. These results indicate the structural origin of the enhanced tetragonality and properties that arise from the increased anisotropy in the Bi-bonding environment with the increased substitution of Bi3+, with its 6s2 stereochemically active lone electron pair. Synchrotron X-ray pair distribution functions (PDFs) reveal that the tetragonal distortions are preserved down to the local scale, suggesting that studies of the average structure provide reasonable insight into the structure-property relationships in this system. These results provide guidance for designing new materials with high TC. Single crystals of (1-x)PT-xBZN were then successfully grown using the high-temperature solution growth (HTSG) method. The dielectric measurements indicate the ferroelectric-paraelectric phase transition at an average TC of 436 °C. Polarized light microscopy reveals the domain structure of tetragonal symmetry, with domain walls oriented along the cub directions, and birefringence measurements as a function of temperature confirmed the first order phase transition. HTSG allows for a higher BZN content to be incorporated into the crystals in comparison to their ceramic counterpart. Moving toward lead-free materials, ceramics of a novel solid solution, (1−x)BaTiO3 xBi(Zn2/3Nb1/3)O3 (BT-BZN) were synthesized. With increasing BZN content, the materials show a decrease in tetragonality and undergo a transition to pseudocubic symmetry, which is accompanied by a crossover from normal ferroelectric to relaxor behaviour. This crossover is explained by increased cationic disorder that disrupts the ferroelectric order. Synchrotron X-ray PDF analysis reveals that all the compositions show local tetragonal distortions that decrease at larger scales to reach the average structure, demonstrating the striking difference between the local and long-range structures.
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Thesis advisor: Ye, Zuo-Guang
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