From Binary Cu2S to Ternary Cu–In–S and Quaternary Cu–In–Zn–S Nanocrystals with Tunable Composition viaPartial Cation Exchange

We present an approach for the synthesis of ternary copper indium sulfide (CIS) and quaternary copper indium zinc sulfide (CIZS) nanocrystals (NCs) by means of partial cation exchange with In3+and Zn2+. The approach consists of a sequential three-step synthesis: first, binary Cu2S NCs were synthesized, followed by the homogeneous incorporation of In3+by an in situpartial cation-exchange reaction, leading to CIS NCs. In the last step, a second partial exchange was performed where Zn2+partially replaced the Cu+and In3+cations at the surface, creating a ZnS-rich shell with the preservation of the size and shape. By careful tuning reaction parameters (growth and exchange times as well as the initial Cu+:In3+:Zn2+ratios), control over both the size and composition was achieved. This led to a broad tuning of photoluminescence of the final CIZS NCs, ranging from 880 to 1030 nm without altering the NCs size. Cytotoxicity tests confirmed the biocompatibility of the synthesized CIZS NCs, which opens up opportunities for their application as near-infrared fluorescent markers in the biomedical field.