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

Journal
Journal of the American Chemical Society
Date
2020.10.23
Abstract

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 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 using thermodynamic and 1H NMR data. Together, these data and proposed exchange mechanism provide greater insight into the surface chemistry of quantum dots and viable improvements to InP quantum yields.

Reference
J. Am. Chem. Soc. 2020, 142, 18897?18906
DOI
http://dx.doi.org/10.1021/jacs.0c08954