Controlled Self-Assembly and Tuning of Large PbS Nanoparticle Supercrystals

Abstract

Self-assembly of colloidal nanocrystals (NCs) into ordered superlattices (SLs) and supercrystals (SCs) enables new artificial NC solids for nanoelectronic and nanophotonic applications, which requires critical control of nucleation and growth conditions. Herein large SCs of PbS NCs up to ∼100 μm size were synthesized by two controlled self-assembly methods from NC solutions. Both translational symmetry and orientational ordering of the nanocrystals in the SCs were readily tuned by excess oleic acid ligands and antisolvents. Slow evaporation and the counterdiffusion method of solvents resulted in the formation of single SCs with two different SLs from the same PbS NCs: a face-centered cubic SL with weak yet complex orientational order or a body-centered cubic SL with strong and uniform particle orientation, respectively. The translational ordering was mainly determined by the effective shape of the NCs while the difference in orientational order was a result of the balance between ligand–ligand attraction and rotational entropy. The ease of the growth of large SC solids could lead to diverse NC systems and facilitate essential investigation of nanoparticle interactions and coupling based nanoelectronic and nanophotonic properties.