Thermodynamic Investigation of Increased Luminescence in Indium Phosphide Quantum Dots by Treatment with Metal Halide Salts

Increasing the quantum yields of InP quantum dots is important for their applications, particularly for use in consumer displays. While several methods exist to improve quantum yield, the addition of inorganic metal halide salts has proven promising. To further investigate this phenomenon, InP quantum dots dispersed in tetrahydrofuran were titrated with ZnCl₂, ZnBr₂, and InCl₃. The optical properties were observed, and the reactions were studied by using quantitative ¹H NMR and thermodynamic measurements from isothermal titration calorimetry. These measurements contradict the previously hypothesized reaction mechanism in which metal halide salts, acting as Z-type ligands, passivate undercoordinated anions on the surface of the quantum dots. This work provides evidence for a newly proposed mechanism wherein the metal halide salts undergo a ligand exchange with indium myristate. Thermodynamic measurements prove key to supporting this new mechanism, particularly in describing the organic ligand interactions on the surface. An Ising model was used to simulate the quantum dot surface and was fit by using thermodynamic and ¹H NMR data. Together, these data and the proposed exchange mechanism provide greater insight into the surface chemistry of quantum dots.