Indium phosphide quantum dots are the main alternative for toxic and restricted Cd-based quantum dots for lighting and display applications, but in the absence of protecting ZnSe and/or ZnS shells, InP quantum dots suffer from low photoluminescence quantum yields. Traditionally, HF treatments have been used to improve the quantum yield of InP to ∼50%, but these treatments are dangerous and not well understood. Here, we develop a postsynthetic treatment that forms HF in situ from benzoyl fluoride, which can be used to strongly increase the quantum yield of InP core-only quantum dots. This treatment is water-free and can be performed safely. Simultaneous addition of the z-type ligand ZnCl 2 increases the photoluminescence quantum yield up to 85%. Structural analysis via XPS as well as solid state and solution NMR measurements shows that the in situ generated HF leads to a surface passivation by indium fluoride z-type ligands and removes polyphosphates, but not PO 3 and PO 4 species from the InP surface. With DFT calculations it is shown that InP QDs can be trap-free even when PO 3 and PO 4 species are present on the surface. These results show that both polyphosphate removal and z-type passivation are necessary to obtain high quantum yields in InP coreonly quantum dots. They further show that core-only InP QDs can achieve photoluminescence quantum yields rivalling those of InP/ZnSe/ZnS core/shell/shell QDs and the best core-only II−VI QDs.

Electrochemical charging of nanocrystal films opens up new possibilities for designing quantum dot-based device structures, but a solid theoretical framework of this process and its limitations is lacking. In this work, drift-diffusion simulations are employed to model the charging of nanocrystal films and gain insight into the electrochemical doping process. Through steady state simulations it is shown that the Fermi level and doping density in the nanocrystal film depend on the concentration of the electrolyte in addition to the value of the applied potential. Timeresolved simulations reveal that charging is often limited by transport of electrolyte ions. However, ion transport in the film is dominated by drift, rather than diffusion, and the concentration profile of ions differs substantially from concentration profiles of diffusing redox species at flat electrodes. Classical electrochemical theory cannot be used to model this type of mass transport limited behavior in films of nanocrystals, so a new model is developed. We show that the Randles−S ̌evcǐ ́k equation, which is derived for electrochemical species diffusing in solution, but is often applied to films as well, results in a significant underestimation of the diffusion coefficients of the charge compensating electrolyte ions.