Tailoring Cu⁺ for Ga³⁺ Cation Exchange in Cu_2–xS and CuInS₂ Nanocrystals by Controlling the Ga Precursor Chemistry

Nanoscale cation exchange (CE) has resulted in colloidal nanomaterials that are unattainable by direct synthesis methods. Aliovalent CE is complex and synthetically challenging because the exchange of an unequal number of host and guest cations is required to maintain charge balance. An approach to control aliovalent CE reactions is the use of a single reactant to both supply the guest cation and extract the host cation. Here, we study the application of GaCl₃-L complexes [L = trioctylphosphine (TOP), triphenylphosphite (TPP), diphenylphosphine (DPP)] as reactants in the exchange of Cu⁺ for Ga³⁺ in Cu_2-xS nanocrystals. We find that noncomplexed GaCl₃ etches the nanocrystals by S^2- extraction, whereas GaCl₃-TOP is unreactive. Successful exchange of Cu⁺ for Ga³⁺ is only possible when GaCl₃ is complexed with either TPP or DPP. This is attributed to the pivotal role of the Cu_2-xS-GaCl₃-L activated complex that forms at the surface of the nanocrystal at the onset of the CE reaction, which must be such that simultaneous Ga³⁺ insertion and Cu⁺ extraction can occur. This requisite is only met if GaCl₃ is bound to a phosphine ligand, with a moderate bond strength, to allow facile dissociation of the complex at the nanocrystal surface. The general validity of this mechanism is demonstrated by using GaCl₃-DPP to convert CuInS₂ into (Cu,Ga,In)S₂ nanocrystals, which increases the photoluminescence quantum yield 10-fold, while blue-shifting the photoluminescence into the NIR biological window. This highlights the general applicability of the mechanistic insights provided by our work.