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Microscopic dynamics of isolated lithium in crystalline solids revealed by nuclear magnetic relaxation and resonance of ⁸Li

University of British Columbia

This thesis reports measurements on the dynamics of isolated lithium in single crystal materials using ion-implanted ⁸Li β-detected nuclear magnetic resonance. From spin-lattice relaxation and resonance measurements, we identify the kinetic parameters describing the ion’s site-to-site hop rate – the elementary process in long-range solid-state diffusion – and compare the results with theoretical work in the literature, as well as experiments at higher concentration. In addition to these “ionic” details, the nuclear magnetic resonance probe provides information on the electronic properties of the host, whose most intriguing features are also discussed. In the one-dimensional ion conductor rutile TiO₂, we find two sets of thermally activated dynamics: one below 100 K and another at higher temperatures. We suggest the low temperature process is unrelated to lithium motion, but rather a consequence of electron polarons in the vicinity of the implanted ⁸Li⁺. Above 100 K, Li⁺ undergoes diffusion as an isolated uncomplexed cation, characterized by an activation energy and prefactor that are in agreement with macroscopic diffusion measurements, but not with theory. In Bi₂Te₂Se, a topological insulator with layered tetradymite structure, implanted ⁸Li⁺ undergoes ionic diffusion above 150 K, likely in the van der Waals gap between adjacent Te planes. A comparison with structurally related materials reveals the mobility of isolated Li⁺ is exceptional. At lower temperature, we find linear Korringa-like relaxation, but with a field dependent slope and intercept, accompanied by an anomalous field dependence to the resonance shift. We suggest that these may be related to a strong contribution from orbital currents or the magnetic freezeout of charge carriers in this heavily compensated semiconductor. In the doped tetradymite topological insulators Bi₂Se₃:Ca and Bi₂Te₃:Mn, the onset of lithium dynamics is suppressed to above 200 K. At low temperatures, the nuclear magnetic resonance properties are those of a heavily doped semiconductor in the metallic limit, with Korringa relaxation and a small, negative, temperature-dependent Knight shift. From this, we make a detailed comparison with isostructural Bi₂Te₂Se.

Text

2020-04-24

Attribution-NonCommercial-NoDerivatives 4.0 International

http://hdl.handle.net/2429/74167

Chemistry

University of British Columbia

UBCV

http://creativecommons.org/licenses/by-nc-nd/4.0/