Colloidal Dispersions of Sterically and Electrostatically Stabilized PbS Quantum Dots: Structure Factors, Second...

Electrostatically stabilized nanocrystals (NCs) and, in particular, quantum dots (QDs) hold promise for forming strongly coupled superlattices due to their compact and electronically conductive surface ligands. However, studies of the colloidal dispersion and interparticle interactions of electrostatically stabilized sub-10 nm NCs have been limited, hindering the optimization of their colloidal stability and self-assembly. In this study, we employed small-angle X-ray scattering (SAXS) experiments to investigate the interparticle interactions and arrangement of PbS QDs with thiostannate ligands (PbS-Sn₂S₆^4-) in polar solvents. The study reveals significant deviations from the ideal solution behavior in electrostatically stabilized QD dispersions. Our results demonstrate that PbS-Sn₂S₆^4- QDs exhibit long-range interactions within the solvent, in contrast to the short-range steric repulsion characteristic of PbS QDs with oleate ligands (PbS-OA). Introducing highly charged multivalent electrolytes screens electrostatic interactions between charged QDs, reducing the length scale of the repulsive interactions. Furthermore, we calculated the second virial (B₂) coefficients from SAXS data, providing insights into how surface chemistry, solvent, and size influence pair potentials. Finally, we explore the influence of long-range interparticle interactions of PbS-Sn₂S₆^4- QDs on the morphology of films produced by drying or spin-coating colloidal solutions. The long-range repulsive term of PbS-Sn₂S₆^4- QDs promotes the formation of amorphous films, and screening the electrostatic repulsion by the addition of an electrolyte enables the formation of crystalline domains. These findings highlight the critical role of NC-NC interactions in tailoring the properties of functional materials made of colloidal NCs.