Near-Infrared-Emitting CuInS₂/ZnS Dot-in-Rod Colloidal Heteronanorods by Seeded Growth

Abstract

Synthesis protocols for anisotropic CuInX₂ (X = S, Se, Te)-based heteronanocrystals (HNCs) are scarce due to the difficulty in balancing the reactivities of multiple precursors and the high solid-state diffusion rates of the cations involved in the CuInX₂ lattice. In this work, we report a multistep seeded growth synthesis protocol that yields colloidal wurtzite CuInS₂/ZnS dot core/rod shell HNCs with photoluminescence in the NIR (∼800 nm). The wurtzite CuInS₂ NCs used as seeds are obtained by topotactic partial Cu⁺ for In³⁺ cation exchange in template Cu_{2- x}S NCs. The seed NCs are injected in a hot solution of zinc oleate and hexadecylamine in octadecene, 20 s after the injection of sulfur in octadecene. This results in heteroepitaxial growth of wurtzite ZnS primarily on the Sulfur-terminated polar facet of the CuInS₂ seed NCs, the other facets being overcoated only by a thin (∼1 monolayer) shell. The fast (∼21 nm/min) asymmetric axial growth of the nanorod proceeds by addition of [ZnS] monomer units, so that the polarity of the terminal (002) facet is preserved throughout the growth. The delayed injection of the CuInS₂ seed NCs is crucial to allow the concentration of [ZnS] monomers to build up, thereby maximizing the anisotropic heteroepitaxial growth rates while minimizing the rates of competing processes (etching, cation exchange, alloying). Nevertheless, a mild etching still occurred, likely prior to the onset of heteroepitaxial overgrowth, shrinking the core size from 5.5 to ∼4 nm. The insights provided by this work open up new possibilities in designing multifunctional Cu-chalcogenide based colloidal heteronanocrystals.