From Wurtzite Nanoplatelets to Zinc Blende Nanorods: Simultaneous Control of Shape and Phase in Ultrathin ZnS Nanocrystals

Ultrathin semiconductor nanocrystals (NCs) with at least one dimension below their exciton Bohr radius receive a rapidly increasing attention due to their unique physicochemical properties. These superior properties highly depend on the shape and crystal phase of semiconductor NCs. Here, we demonstrate not only the synthesis of well-defined ultrathin ZnS nanoplatelets (NPLs) with excitonic absorption and emission, but also the shape/phase transformation between wurtzite (WZ) NPLs and zinc blende (ZB) nanorods (NRs). UV-vis absorption spectra of WZ-ZnS NPLs clearly exhibit a sharp excitonic peak that is not observed in ZB-ZnS NRs. Besides, the photoluminescence characterization shows that WZ-ZnS NPLs have a narrow excitonic emission peak, while ZB-ZnS NRs exhibit a broad collective emission band consisting of four emission peaks. The appearance of excitonic features in the absorption spectra of ZnS NPLs is explained by interband electronic transitions, which is simulated in the framework of atomic effective pseudopotentials (AEP).