Despite the technological importance of colloidal covalent III-V nanocrystals with unique optoelectronic properties, their synthetic process still has challenges originating from the complex energy landscape of the reaction. Here, we present InP tetrapod nanocrystals as a crystalline late intermediate in the synthetic pathway that warrants controlled growth. We isolate tetrapod intermediate species with well-defined surfaces of (110) and ([Formula: see text]) via the suppression of further growth. An additional precursor supply at low temperature induces [Formula: see text]-specific growth, whereas the [110]-directional growth occurs over the activation barrier of 65.7 kJ/mol at a higher temperature, thus finalizes into the (111)-faceted tetrahedron nanocrystals. We address the use of late intermediates with well-defined facets at the sub-10 nm scale for the tailored growth of covalent III-V nanocrystals and highlight the potential for the directed approach of nanocrystal synthesis.
© 2021. The Author(s).