To Battle Surface Traps on CdSe/CdS Core/Shell Nanocrystals: Shell Isolation versus Surface Treatment

Electronic traps at the inorganic–organic interface of colloidal quantum dots (QDs) are detrimental to their luminescent properties. Several types of interface traps were identified for single-crystalline CdSe/CdS core/shell QDs, which were all found to be extrinsic to either the core/shell structure or their optical performance. The electron trapspresumably excess or unpassivated Cd surface sitesare shallow ones and could be readily isolated from the electron wave function of the excitons with more than ∼2 monolayers of CdS shell. There were two identifiable deep hole traps within the bandgap of the QDs, i.e., the surface adsorbed H2S and unpassivated surface S sites. The surface adsorbed H2S could be removed by either degassing processes or photochemical decomposition of H2S without damaging the QDs. The unpassivated surface S sites could be removed by surface treatment with cadmium carboxylates. Understanding of the surface traps enabled establishment of new phosphine-free synthetic schemes for either single-precursor or successive-ion-layer-adsorption-and-reaction approach, which yielded CdSe/CdS core/shell QDs with near-unity photoluminescence quantum yield and monoexponential photoluminescence decay dynamics with 2–10 monolayers of CdS shell.