The metastable semiconductor phase allows for the exploration of unusual properties and functionalities of abnormal structures, although it is often difficult to prevent thermodynamic transformations to lower energy structures from higher, unfavored energy states. Here, we show for the first time the preparation of high-quality ultralong metastable zincblende (ZB)-MnSe nanowires with a four-coordinate structure via solution-solid-solid (SSS) growth in a mild solution-phase synthetic environment (120-220 °C) in the presence of a trace amount of Ag(I). The metastable ZB-MnSe nanowires are stabilized kinetically due to the catalysis of early formed body-centered cubic (bcc) fast-ionic (superionic) Ag2Se nanocrystals from the Ag(I) source, and the ZB-MnSe nanowires grow epitaxially along the ⟨110⟩ axis rather than the ⟨111⟩ axis, as commonly observed for typical four-coordinate Grimm-Sommerfeld bonding solids. Our method provides a new route for the growth of metastable nanostructures.
Keywords: catalytic growth; epitaxial growth; fast-ionic conductor; kinetic growth; metastable phase; solution−solid−solid growth mechanism; superionic conductor; zincblende MnSe nanowire.