The Phase Behavior of Nanoparticle Superlattices in the Presence of a Solvent

Superlattices of nanoparticles coated by alkyl-chain ligands are usually prepared from a stable solution by evaporation, therefore the pathway of superlattice self-assembly critically depends on the amount of solvent present within it. This work addresses the role of the solvent on the structure and the relative stability of the different supercrystalline phases of single-component superlattices (simple cubic, body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed). The study is performed with a molecular theory for nanoparticle superlattices introduced in this work, which predicts the structure and thermodynamics of the supercrystals explicitly treating the presence and molecular details of the solvent and the ligands. The theory predicts a FCC–BCC transition with decreasing solvent content due to the competition between the translational entropy of the solvent and the entropy and internal energy of the ligands. This result provides an explanation for recent experimental observations by in situ X-ray scattering, which reported a FCC–BCC transition during solvent evaporation. The theory also predicts the effects of the length and surface coverage of the ligands and the radius of the core on the phase behavior in agreement with experimental evidence and previous molecular dynamics simulations. These results validate the use of the dimensionless softness parameter λ (ratio of ligand length to core radius) to predict the phase behavior of wet superlattices. Our results stress the importance of explicitly considering the presence of the solvent in order to reach a complete picture of the mechanisms that mediate the self-assembly of nanoparticle superlattices.