Room-temperature superionic-phase nanocrystals synthesized with a twinned lattice.

The engineering of nanoscale features enables the properties of solid-state materials to be tuned. Here, we show the tunable preparation of cuprous sulfide nanocrystals ranging in internal structures from single-domain to multi-domain. The synthetic method utilizes in-situ oxidation to grow nanocrystals with a controlled degree of copper deficiency. Copper-deficient nanocrystals spontaneously undergo twinning to a multi-domain structure. Nanocrystals with twinned domains exhibit markedly altered crystallographic phase and phase transition characteristics as compared to single-domain nanocrystals. In the presence of twin boundaries, the temperature for transition from the ordered phase to the high-copper-mobility superionic phase is depressed. Whereas the superionic phase is stable in the bulk only above ca. 100 °C, cuprous sulfide nanocrystals of ca. 7 nm diameter and a twinned structure are stable in the superionic phase well below ambient temperature. These findings demonstrate twinning to be a structural handle for nanoscale materials design and enable applications for an earth-abundant mineral in solid electrolytes for Li-S batteries.