Hydrothermal Synthesis of Frustrated Lanthanide Pyrochlores and Transition Metal Double Perovskites and Germanates

Author

Matthew S. Powell, Clemson UniversityFollow

Date of Award

5-2023

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Committee Chair/Advisor

Dr. Joseph W. Kolis

Abstract

Magnetically frustrated materials hold promise of unique behavior allowing for the novel study of quantum phenomena. Such materials are poised to become an integral foundation for technological advancement in the post-Silicon Age. Crystalline materials are given special focus where the rigid lattice allows more detailed study of these quantized effects and frustration behavior. As opposed to polycrystalline powders, large single crystals can be preferentially aligned enabling the study of anisotropic behavior. Two cubic structure types have garnered significant interest due to their 3-D tetrahedral arrangement of symmetry-related metal centers with the potential for magnetic frustration: pyrochlores and perovskites.

The supercritical hydrothermal crystal growth technique has been applied to a host of refractory oxides to enhance phase purity and minimize crystalline defects often introduced by conventional flux or melt-based based techniques. The supercritical growth in aqueous alkali at temperatures much lower than those of floating zone melts, while maintaining a sealed environment, avoids the possibility for reactant sublimation. In comparison to melt-based techniques, the modest thermal conditions also aid in minimizing atomic site displacements by insertion into different sites than those expected (“stuffing”). Through supercritical hydrothermal conditions, it was possible to obtain the entire series of lanthanide stannate pyrochlores. Stannous oxide, originally applied for in situ ceria reduction, was found beneficial for all lanthanide oxide reactants regardless of oxidation state allowing facile growth of faceted, mm-scale stannate octahedra in only days. This has allowed for the first single-crystal neutron scattering study of the quantum spin liquid candidate Ce₂Sn₂O₇ with similar experiments to follow across the lanthanide series.

The sealed, pressurized supercritical hydrothermal technique was also applied in the growth of stoichiometric orthoscandates and site-ordered cubic barium double perovskites. Both systems had structures occur in crystallographic settings previously only possible through thin-film epitaxial growth or application of high pressures and temperatures. Attempts to expand the palette of lanthanide-containing germanium perovskites yielded novel P2₁2₁2₁ LnTM(GeO₄)(OH) (TM = 3d transition metal) adelite-type structures possessing chiral [TMO₄]_∞ a-axis chains. These adelites demonstrated the first known inclusion of lanthanides and germanium in the adelite-descloizite supergroup. The synthetic possibilities of the refractory lanthanide oxides and often-overlooked germanium offer great synthetic possibilities poised to further expand the adelite family while also providing a few magnetically frustrated surprises themselves or through the high-symmetry cubic garnet and spinel products encountered during exploratory adelite synthesis under hydrothermal conditions.

Recommended Citation

Powell, Matthew S., "Hydrothermal Synthesis of Frustrated Lanthanide Pyrochlores and Transition Metal Double Perovskites and Germanates" (2023). All Dissertations. 3281.
https://open.clemson.edu/all_dissertations/3281