Chiroptical Activity of Type II Core/Shell Cu₂S/CdSe Nanocrystals

Ligand-induced chirality in core/shell nanocrystals (NCs) has attracted extensive attention because of many valuable potential applications. However, the cause of chirality especially in semiconductor nanomaterials is still under debate despite the creation of chiral type I core/shell structures. Herein, we synthesized a kind of new Cu₂S/CdSe core/shell nanostructure to study the underlying reason. Four samples of Cu₂S/CdSe were synthesized utilizing successive ion layer adsorption and reaction to vary the thickness of the CdSe shell upon a Cu₂S core with 5 nm diameter. The chirality of type II Cu₂S/CdSe NCs is imparted by l-/d-cysteine and penicillamine, which could be modulated with an increasing thickness of the CdSe shell. To the best of our knowledge, this is the first report of chiral type II core/shell semiconductor NCs. The hybridization theory can explain the variation trend of g factors with every increase in shell thickness from four monolayers (4 ML) to 7 ML. The results indicate that the chiroptical activity of semiconductor NCs is mainly due to hybridization between the holes in the valence band of NCs and the highest occupied molecular orbitals of the chiral ligands. In addition, Cu₂S/CdSe NCs show a better chiroptical intensity in comparison with the type I structure according to previous work. The first design of chiral type II Cu₂S/CdSe core/shell NCs and a detailed investigation of chiral variation trend help to give a better understanding of the chiral interaction between ligands and core/shell semiconductor nanostructures.