Diffusion-Limited Kinetics of Isovalent Cation Exchange in III–V Nanocrystals Dispersed in Molten Salt Reaction Media

The goal of this work is to determine the kinetic factors that govern isovalent cation exchange in III–V colloidal quantum dots using molten salts as the solvent and cation source. We focus on the reactions of InP + GaI₃→ In_1–xGa_xP and InAs + GaI₃→ In_1–xGa_xAs to create technologically important ternary III–V phases. We find that the molten salt reaction medium causes the transformation of nearly spherical InP nanocrystals to tetrahedron-shaped In_1–xGa_xP nanocrystals. Furthermore, we determine that the activation energy for the cation exchange reaction is 0.9 eV for incorporation of Ga into InP and 1.2 eV for incorporation of Ga into InAs, both much lower than the measured values in bulk semiconductors. Next, we use powder XRD simulations to constrain our understanding of the structure of the In_1–xGa_xP nanocrystals. Together our results reveal several important features of molten salt-mediated cation exchange and provide guidance for future development of these materials.