Zinc phosphide, Zn3P2, nanowires constitute prospective building blocks for next generation solar cells due to the combination of suitable optoelectronic properties and an abundance of the constituting elements in the Earths crust. The generation of periodic superstructures along the nanowire axis could provide an additional mechanism to tune their functional properties. Here we present the vapour-liquid-solid growth of zinc phosphide superlattices driven by periodic heterotwins. This uncommon planar defect involves the exchange of Zn by In at the twinning boundary. We find that the zigzag superlattice formation is driven by reduction of the total surface energy of the liquid droplet. The chemical variation across the heterotwin does not affect the homogeneity of the optical proerties, as measured by cathodoluminescence. The basic understanding provided here brings new perspectives on the use of II-V semiconductors in nanowire technology.
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