Phosphine-Free, Highly Emissive, Water-Soluble Mn:ZnSe/ZnS Core–Shell Nanorods: Synthesis, Characterization, and in Vitro Bioimaging of HEK293 and HeLa Cells

Phosphine-free, highly luminescent one-dimensional Mn2+ ion-doped ZnSe(core)/ZnS(shell) nanorods (NRs) were synthesized by heating-up method (core) followed by hot injection route (shell). Effect of Mn2+ doping and shell thickness on structural and optical properties is reported. The NRs were formed with wurtzite-structured Mn:ZnSe core (diameter 2.52 nm) encapsulated epitaxially by a wurtzite-structured ZnS shell (thickness of 3.51 nm) with 3.1% lattice mismatch that alters the band alignment of the overall core–shell structure. A redshift was observed in optical absorption and photoluminescence (PL) emission due to an overall size increase with increasing shell thickness. Because of the reduction of defects/traps by surface passivation, the maximum photoluminescence quantum yield (QY) was obtained to be 49.35%. The exciton radiative lifetime for the core–shell NRs (1.678 ms) was more prolonged than that of the core (0.573 ms). A clear dependence of QY and lifetime was established on the Mn2+ content and ZnS shell thickness. The core–shell structure with thickest shell showed good photostability. Water solubility was achieved by ligand exchange with bifunctional 11-mercaptoundecanoic acid without modifying the optical and microstructural properties. These core–shell NRs were successfully tested for bioimaging of human HEK293 and HeLa cells with good permeability to cells. Toxicity was observed to be 3% for the 100 μg/mL dose.