Axial Composition Gradients and Phase Segregation Regulate the Aspect Ratio of Cu₂ZnSnS₄ Nanorods

Cu₂ZnSnS₄ (CZTS) is a promising material for solar energy conversion, but synthesis of phase-pure, anisotropic CZTS nanocrystals remains a challenge. We demonstrate that the initial concentration (loading) of cationic precursors has a dramatic effect on the morphology (aspect ratio) and composition (internal architecture) of hexagonal wurtzite CZTS nanorods. Our experiments strongly indicate that Cu is the most reactive of the metal cations; Zn is next, and Sn is the least reactive. Using this reactivity series, we are able to purposely fine-tune the morphology (dots versus rods) and degree of axial phase segregation of CZTS nanocrystals. These results will improve our ability to fabricate CZTS nanostructures for photovoltaics and photocatalysis