The solid lithium-ion electrolyte “Li₇La₃Zr₂O₁₂” (LLZO) with a garnet-type structure has been prepared in the cubic and tetragonal modification following conventional ceramic syntheses routes. Without aluminium doping tetragonal LLZO was obtained, which shows a two orders of magnitude lower room temperature conductivity than the cubic modification. Small concentrations of Al in the order of 1 wt% were sufficient to stabilize the cubic phase, which is known as a fast lithium-ion conductor. The structure and ion dynamics of Al-doped cubic LLZO were studied by impedance spectroscopy, dc conductivity measurements, ⁶Li and ⁷Li NMR, XRD, neutron powder diffraction, and TEM precession electron diffraction. From the results we conclude that aluminium is incorporated in the garnet lattice on the tetrahedral 24dLi site, thus stabilizing the cubic LLZO modification. Simulations based on diffraction data show that even at the low temperature of 4 K the Li ions are blurred over various crystallographic sites. This strong Li ion disorder in cubic Al-stabilized LLZO contributes to the high conductivity observed. The Li jump rates and the activation energy probed by NMR are in very good agreement with the transport parameters obtained from electrical conductivity measurements. The activation energy E_a characterizing long-range ion transport in the Al-stabilized cubic LLZO amounts to 0.34 eV. Total electric conductivities determined by ac impedance and a four point dc technique also agree very well and range from 1 × 10⁻⁴ Scm⁻¹ to 4 × 10⁻⁴ Scm⁻¹ depending on the Al content of the samples. The room temperature conductivity of Al-free tetragonal LLZO is about two orders of magnitude lower (2 × 10⁻⁶ Scm⁻¹, E_a = 0.49 eV activation energy). The electronic partial conductivity of cubic LLZO was measured using the Hebb–Wagner polarization technique. The electronic transference number t_{e −} is of the order of 10⁻⁷. Thus, cubic LLZO is an almost exclusive lithium ion conductor at ambient temperature.

The paper reviews materials science aspects of chalcogenide-based phase change thin films relevant for non-volatile memory applications.