Synthesis and Formation Mechanism of Colloidal Janus-Type Cu_2–xS/CuInS₂ Heteronanorods via Seeded Injection

Colloidal heteronanocrystals allow for the synergistic combination of properties of different materials. For example, spatial separation of the photogenerated electron and hole can be achieved by coupling different semiconductors with suitable band offsets in one single nanocrystal, which is beneficial for improving the efficiency of photocatalysts and photovoltaic devices. From this perspective, axially segmented semiconductor heteronanorods with a type-II band alignment are particularly attractive since they ensure the accessibility of both photogenerated charge carriers. Here, a two-step synthesis route to Cu_2–xS/CuInS₂ Janus-type heteronanorods is presented. The heteronanorods are formed by injection of a solution of preformed Cu_2–xS seed nanocrystals in 1-dodecanethiol into a solution of indium oleate in oleic acid at 240 °C. By varying the reaction time, Janus-type heteronanocrystals with different sizes, shapes, and compositions are obtained. A mechanism for the formation of the heteronanocrystals is proposed. The first step of this mechanism consists of a thiolate-mediated topotactic, partial Cu⁺ for In³⁺ cation exchange that converts one of the facets of the seed nanocrystals into CuInS₂. This is followed by homoepitaxial anisotropic growth of wurtzite CuInS₂. The Cu_2–xS seed nanocrystals also act as sacrificial Cu⁺ sources, and therefore, single composition CuInS₂ nanorods are eventually obtained if the reaction is allowed to proceed to completion. The two-stage seeded growth method developed in this work contributes to the rational synthesis of Cu_2–xS/CuInS₂ heteronanocrystals with targeted architectures by allowing one to exploit the size and faceting of premade Cu_2–xS seed nanocrystals to direct the growth of the CuInS₂ segment.