Atomic structure of CdS magic-size clusters by X-ray absorption spectroscopy

Abstract: Magic-size clusters are ultra-small colloidal semiconductor systems that are intensively studied due to their monodisperse nature and sharp UV-vis absorption peak compared with regular quantum dots. However, the small size of such clusters (<2 nm), and the large surface-to-bulk ratio significantly limit characterisation techniques that can be utilised. Here we demonstrate how a combination of EXAFS and XANES can be used to obtain information about sample stoichiometry and cluster symmetry. Investigating two types of clusters that show sharp UV-vis absorption peaks at 311 nm and 322 nm, we found that both samples possess approximately 2:1 Cd:S ratio and have similar nearest-neighbour structural arrangements. However, both samples demonstrate a significant departure from the tetrahedral structural arrangement, with an average bond angle determined to be around 106.1 degree showing a bi-fold bond angle distribution. Our results suggest that both samples are quazi-isomers. Their core structure has identical chemical composition but a different atomic arrangement with distinct bond angle distributions.