We report on the self-assembly of gold nanoparticles coated with a soft poly(ethylene glycol) shell studied by X-ray cross-correlation analysis. Depending on the initial concentration of gold nanoparticles used, structurally heterogeneous films were formed. The films feature hot spots of dominating four- and sixfold local order with patch sizes of a few micrometres, containing 104–105 particles. The amplitude of the order parameters suggested that a minimum sample amount was necessary to form well ordered local structures. Furthermore, the increasing variation in order parameters with sample thickness demonstrated a high degree of structural heterogeneity. This wealth of information cannot be obtained by the conventional microscopy techniques that are commonly used to study nanocrystal superstructures, as illustrated by complementary scanning electron microscopy measurements.
