In the syntheses of ternary I-III-VI2 compounds, such as CuInS2, it is often difficult to balance three precursor reactivities to achieve the desired size, shape, and atomic composition of nanocrystals. Cation exchange reactions offer an attractive two-step alternative, by producing a binary compound with the desired morphology and incorporating another atomic species postsynthetically. However, the kinetics of such cation exchange reactions, especially for anisotropic nanocrystals, are still not fully understood. Here, we present the cation exchange reaction from Cu-deficient djurleite Cu2-xS nanorods to wurtzite CuInS2, with size and shape retention. With reaction parameters in a broad temperature range between 40 °C and 160 °C, we were able to obtain various intermediates. Djurleite has a bulk phase transition temperature at 93 °C, which influences the cation exchange considerably. Below the phase transition temperature, indium is only incorporated into the surface of the nanorods, while, at temperatures above the phase transition temperature, we observe a Janus-type exchange mechanism and the formation of CuInS2 bands in the djurleite nanorods. The findings suggest that the diffusion above the phase transition temperature is strongly favored along the copper planes of the copper sulfide nanorods over the diffusion through the sulfur planes. This results in a difference of 37 kJ mol-1 in the activation energy of the cation exchange below and above the phase transition temperature.
Keywords: copper indium sulfide; copper sulfide; diffusion; djurleite; high chalcocite; janus structure; wurtzite.