Multipod structures of ZnO hydrothermally grown in the presence of Zn3P2

Zinc phosphide (Zn3P2) is used in the present contribution as an inorganic additive for the surfactant-free hydrothermal synthesis of ZnO structures with controlled morphology. Postulated as a suitable dopant candidate for generating P-related acceptor defects inside the wurtzite structure of ZnO, the obtained results however reveal that a stable P:ZnO solid solution is never formed in the binary ZnO–Zn3P2 system. Instead the amorphized phosphide particles may preferentially locate at the surface of ZnO particles, exerting a strong effect on the morphological development of the material and controlling its crystal growth habit: with the incorporation of Zn3P2 the system evolves from a situation in which just hexagonal bipods are observed to another one in which the ZnO particles merge to form spherical ball-shaped structures and flower-like architectures. The high propensity of ZnO polar structure to twin is behind the observed growth mechanism.