Abstract

The ligand shell (LS) determines a number of nanoparticles’ properties. Nanoparticles’ cores can be accurately characterized; yet the structure of the LS, when composed of mixture of molecules, can be described only qualitatively (e.g., patchy, Janus, and random). Here we show that quantitative description of the LS’ morphology of monodisperse nanoparticles can be obtained using small-angle neutron scattering (SANS), measured at multiple contrasts, achieved by either ligand or solvent deuteration. Three-dimensional models of the nanoparticles’ core and LS are generated using an ab initio reconstruction method. Characteristic length scales extracted from the models are compared with simulations. We also characterize the evolution of the LS upon thermal annealing, and investigate the LS morphology of mixed-ligand copper and silver nanoparticles as well as gold nanoparticles coated with ternary mixtures. Our results suggest that SANS combined with multiphase modeling is a versatile approach for the characterization of nanoparticles’ LS.

Highlights

  • The ligand shell (LS) determines a number of nanoparticles’ properties

  • It was found that a balance between the enthalpy of phase separation and the conformational entropy leads to the formation of stripe-like domains

  • Nanoparticles must be colloidally stable in solvent, i.e., reaching ~0.1% v/v without aggregation

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Summary

Introduction

The ligand shell (LS) determines a number of nanoparticles’ properties. Nanoparticles’ cores can be accurately characterized; yet the structure of the LS, when composed of mixture of molecules, can be described only qualitatively (e.g., patchy, Janus, and random). SANS data were acquired for dPET-DDT and PET-dDDT using deuterated toluene as solvent. For the MUA-DDT nanoparticle (Fig. 2e), with no entropic contribution from chain length mismatch and large difference in polarity, phase-separated domains (Janus morphology) were identified.

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