Neutron scattering studies on ionic diffusion behaviors of superionic $\alpha$-Cu$_{2-\delta}$Se

TL;DR

This study investigates the crystal structure and ionic diffusion mechanisms in superionic Cu$_{2- ext{delta}}$Se using neutron scattering techniques, revealing two diffusion modes and their dependence on Cu content and temperature.

Contribution

It provides a detailed microscopic understanding of Cu ion diffusion modes in superionic Cu$_{2- ext{delta}}$Se, highlighting the role of structure and composition.

Findings

Two diffusion modes identified: localized and long-range.

Long-range diffusion coefficient increases with Cu content.

Temperature has minimal effect on long-range diffusion between 430-650 K.

Abstract

We present studies on crystal structure and ionic diffusion behaviors of superionic Cu$_{2-\delta}$Se ($\delta$=0, 0.04, and 0.2) by utilizing neutron powder diffraction and quasi-elastic neutron scattering. In the superionic phase, the structural model with Cu ions occupying the Wyckoff sites of 8$c$ and 32$f$ provides the best description of the structure. As the content of Cu increasing in Cu$_{2-\delta}$Se, the Cu occupancy increases on the 32$f$ site, but decreases on the 8$c$ site . Fitting to the quasi-elastic neutron scattering spectra reveals two diffusion modes, the localized diffusion between the 8$c$ and 32$f$ sites and the long-range diffusion between the adjacent 8$c$ sites using the 32$f$ site as a bypass, respectively. Between 430 and 650 K, we measured that the compound with more Cu content exhibits a larger long-range diffusion coefficient. Temperature in this range does not affect the long-range diffusion process obviously. Our results suggest the two diffusion modes cooperative and thus provide a microscopic understanding of the ionic diffusion of the Cu ions in superionic Cu$_{2-\delta}$Se.