Unravelling three-dimensional adsorption geometries of PbSe nanocrystal monolayers at a liquid-air interface

The adsorption, self-organization and oriented attachment of PbSe nanocrystals (NCs) at liquid-air interfaces has led to remarkable nanocrystal superlattices with atomic order and a superimposed nanoscale geometry. Earlier studies examined the NC self-organization at the suspension/air interface with time-resolved in-situ X-ray scattering. Upon continuous evaporation of the solvent, the NC interfacial layer will finally contact the (ethylene glycol) liquid substrate on which the suspension was casted. In order to obtain structural information on the NC organization at this stage of the process, we examined the ethylene glycol/NC interface in detail for PbSe NCs of different sizes, combining in-situ grazing-incidence small-and-wide-angle X-ray scattering (GISAXS/GIWAXS), X-ray reflectivity (XRR) and analytical calculations of the adsorption geometry of these NCs. Here, we observe in-situ three characteristic adsorption geometries varying with the NC size. Based on the experimental evidence and simulations, we reveal fully three-dimensional arrangements of PbSe nanocrystals at the ethylene glycol-air interface with and without the presence of rest amounts of toluene. To understand the self-assembly of semiconductor nanocrystals, the formation mechanism of two-dimensional superlattices needs to be deciphered. Here the authors observe lead selenide nanocrystal organization at the ethylene glycol-air interface combining in-situ grazing-incidence small -and-wide-angle X-ray scattering, X-ray reflectivity and analytical calculations to obtain a three-dimensional picture of the adsorption geometry of the nanocrystals.