The rare earth pyrochlore oxides, with formula R2B2O7, are a chemically versatile family of materials that exhibit a diverse array of magnetic phenomena. In this structure the R and B site cations each form a corner-sharing tetrahedral network, a motif that is prone to intense geometric magnetic frustration. As a consequence of their magnetic frustration, rare earth pyrochlores are observed to host a number of remarkable states such as spin ice and spin liquid states. In this thesis we endeavor to explore the phase diagrams of the rare earth pyrochlores through the lens of chemical pressure. Chemical pressure is applied by varying the ionic radius of the non-magnetic B site cation, which either expands or contracts the lattice, in analogy to externally applied pressure. We apply positive chemical pressure by substituting germanium at the B site and negative chemical pressure by substituting lead at the B site. We also consider the effect of platinum substitution, which has nominally negligible chemical pressure effects. In the ytterbium pyrochlores, we find that positive chemical pressure tunes the magnetic ground state from ferromagnetic to antiferromagnetic. Remarkably, we also find that the ytterbium pyrochlores share a ubiquitous form to their low temperature spin dynamics despite their disparate ordered states. In the terbium pyrochlores, we find that positive chemical pressure promotes ferromagnetic correlations - the opposite effect of externally applied pressure. Our studies of platinum pyrochlores reveal that platinum, while non-magnetic, is able to facilitate superexchange pathways. Thus, the magnetic ground states of the platinum pyrochlores are significantly altered from their titanate analogs. The work in this thesis highlights the delicate balance of interactions inherent to rare earth pyrochlore magnetism and shows that chemical pressure is a powerful tool for navigating their phase spaces. / Thesis / Doctor of Philosophy (PhD) / Rare earth pyrochlores have the chemical formula R2B2O7, where R is a magnetic rare earth element and B is a non-magnetic element. Materials of this type are widely studied because they have a propensity to exhibit exotic magnetic properties. In this thesis, we study the effect of varying the size of the non-magnetic B site atom, which is termed chemical pressure. As B is made larger or smaller, the crystal lattice expands or contracts, mimicking the effect of externally applied pressure. High-pressure synthesis techniques were used to prepare R2B2O7 compounds with B site cations that are typically too small (germanium), too large (lead), or too unstable (platinum) under ambient pressure conditions. Our characterizations of these high-pressure materials have revealed that their magnetism is remarkably sensitive to the application of chemical pressure.
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/22014 |
| Date | 11 1900 |
| Creators | Hallas, Alannah M. |
| Contributors | Luke, Graeme M., Physics and Astronomy |
| Source Sets | McMaster University |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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