Delocalized Surface Electronic States on Polar Facets of Semiconductor Nanocrystals

Wurtzite CdSe@CdS dot@platelet nanocrystals with (001) and (00-1) polar facets as the basal planes and (100) family of nonpolar facets as the side planes are applied for studying surface defects on semiconductor nanocrystals. When they are terminated with cadmium ions coordinated with carboxylate ligands, a single set of absorption features and band-edge photoluminescence (PL) with near unity PL quantum yield and monoexponential PL decay dynamics (lifetime ∼28 ns) are observed. In addition to these spectral signatures, when the surface is converted to sulfur-terminated, a second set of sharp absorption features with decent extinction coefficients and a secondary band-edge PL with low PL quantum yield and long-lifetime (>78 ns) PL decay dynamics are reproducibly recorded. Photochemical analysis confirms that the secondary UV-vis and PL spectral features are quantitatively correlated with each other. Chemical analysis and X-ray photoelectron spectroscopy measurements confirm that such secondary spectral features are well correlated with the sulfide (such as -SH) and disulfide (such as -S-S-) surface sites of a basal plane, which likely form surface hole electronic states delocalized on the entire basal plane. Results suggest that, for studying surface defects on semiconductor nanocrystals, it is essential to prepare a nearly monodisperse surface structure in terms of facets and surface chemical bonding.