Regulating Multiple Variables To Understand the Nucleation and Growth and Transformation of PbS Nanocrystal Superlattices.

Nanocrystals (NCs) can self-assemble into ordered superlattices with collective properties, but the ability for controlling NC assembly remains poorly understandable toward achievement of desired superlattice. This work regulates several key variables of PbS NC assembly (e.g., NC concentration and solubility, solvent type, evaporation rate, seed mediation and thermal treatment), and thoroughly exploits the nucleation and growth as well as subsequent superlattice transformation of NC assembles and underneath mechanisms. PbS NCs in toluene self-assemble into a single face-centered-cubic (fcc) and body-centered-cubic (bcc) superlattice, respectively, at concentrations ≤17.5 and ≥70 mg/mL, but an intermediate concentration between them causes the coexistence of the two superlattices. Differently, NCs in hexane or chloroform self-assemble into only a single bcc superlattice. Distinct controls of NC assembly in solvent with variable concentrations confirm the NC concentration/solubility mediated nucleation and growth of superlattice, in which an evaporation-induced local gradient of NC concentration causes simultaneous nucleation of the two superlattices. The observation for the dense packing planes of NCs in fast growing fcc rather than bcc reveals the difference of entropic driving forces responsible for the two distinct superlattices. Decelerating the solvent evaporation does not amend the superlattice symmetry, but improves the superlattice crystallinity. In addition to shrinking the superlattice volume, thermal treatment also transforms the bcc to an fcc superlattice at 175 °C. Through a seed-meditated growth, the concentration-dependent superlattice does not change lattice symmetry over the course of continuous growth, whereas the newly nucleated secondary small nuclei through a concentration change have relatively higher surface energy and quickly dissolve in solution, providing additional NC sources for the ripening of the primarily nucleated larger and stable seeds. The observations under multiple controls of assembly parameters not only provide insights into the nucleation and growth as well as transformation of various superlattice polymorphs but also lay foundation for controlled fabrication of desired superlattice with tailored property.