Dendrimer Ligand Directed Nanoplate Assembly
Citation
Elbert, K.C.; Vo, T.; Krook, N.M.; Zygmunt, W.; Park, J.; Yager, K.G.; Composto, R.J.; Glotzer, S.C.; Murray, C.B. "Dendrimer Ligand Directed Nanoplate Assembly"
ACS Nano 2019,
13 14241–14251.
doi: 10.1021/acsnano.9b07348Summary
Using electron microscopy and x-ray scattering, we investigate the role of ligands in the ordering of anisotropic nanoparticles.
Abstract
Many studies on nanocrystal (NC) self-assembly into ordered superlattices have focused mainly on attractive forces between the NCs, whereas the role of organic ligands on anisotropic NCs is only in its infancy. Herein, we report the use of a series of dendrimer ligands to direct the assembly of nanoplates into 2D and 3D geometries. It was found that the dendrimer-nanoplates consistently form a directionally offset architecture in 3D films. We present a theory to predict ligand surface distribution and Monte Carlo simulation results that characterize the ligand shell around the nanoplates. Bulky dendrimer ligands create a nontrivial corona around the plates that changes with ligand architecture. When this organic–inorganic effective shape is used in conjunction with thermodynamic perturbation theory to predict both lattice morphology and equilibrium relative orientations between NCs, a lock-and-key type of mechanism is found for the 3D assembly. We observe excellent agreement between our experimental results and theoretical model for 2D and 3D geometries, including the percent of offset between the layers of NCs. Such level of theoretical understanding and modeling will help guide future design frameworks to achieve targeted assemblies of NCs.
