Observation of ordered organic capping ligands on semiconducting quantum dots via powder X-ray diffraction

Powder X-ray diffraction is one of the key techniques used to characterize the inorganic structure of colloidal nanocrystals. The comparatively low scattering factor of nuclei of the organic capping ligands and their propensity to be disordered has led investigators to typically consider them effectively invisible to this technique. In this report, we demonstrate that a commonly observed powder X-ray diffraction peak around q=1.4 angstrom -1 observed in many small, colloidal quantum dots can be assigned to well-ordered aliphatic ligands bound to and capping the nanocrystals. This conclusion differs from a variety of explanations ascribed by previous sources, the majority of which propose an excess of organic material. Additionally, we demonstrate that the observed ligand peak is a sensitive probe of ligand shell ordering. Changes as a function of ligand length, geometry, and temperature can all be readily observed by X-ray diffraction and manipulated to achieve desired outcomes for the final colloidal system. The degree of ligand ordering on colloidal inorganic nanocrystal surfaces has long been a topic of interest. Here, the authors show that a well-known powder X-ray diffraction feature observed in prior works, frequently assigned to excess ligands, corresponds to bound and ordered capping ligands.