Low Dimensional String-like Relaxation Underpins Superionic Conduction in Fluorites and Related Structures

Among the superionic conductors that show a Faraday transition – the continuous increase in the ionic conductivity over a range of temperatures – the fluorite structures have enjoyed incisive examinations over the past four decades; yet the fundamental nature of superionicity has remained largely inconclusive. Departing from the traditional quasi-static defect framework, we provide weighty evidence for string-like dynamical structures that govern the fast ion conduction process in fluorites. We show that lower temperatures encourage the growth of longer but slowly relaxing strings and vice-versa – a direct manifestation of heterogeneous dynamics. Remarkably, the ionic conductivity is inversely correlated to the lifetime of the ions that participate in the strings and not explicitly to the ion population. Our analysis methodology, which resolves a long-standing disagreement on defect structures and the mechanism of ionic transport in fcc fluorite structures, is well-positioned to describe the dynamics of low dimensional conduction in a larger class of superionic conductors.