Thermodynamic silver doping of core/shell colloidal quantum wells imparted with paramagnetic properties emitting at near-infrared

Abstract

Two-dimensional (2D) core/shell nanoplatelets (NPLs) synthesized via the hot-injection method provide excellent thermal and chemical stability for high-temperature doping, where an expanded and flexible lattice is required. Here, a thermodynamic approach toward silver doping of these NPLs is proposed and demonstrated, which previously proved to be challenging due to the fast self-purification of the dopants with the introduction of the shell. Maintaining the doping procedure in the reversible regime ensured the integrity of the NPLs and allowed a high level of doping; however, the equilibrium condition is further complicated by environmental factors that affect the chemical activity of the cations and the surface composition of the NPLs. Two main deterioration mechanisms in the irreversible regime were observed: ZnS-shelled NPLs suffered preferential etching, while CdS-shelled NPLs underwent cleavage and fragmentation. Alloying of the shell minimized both mechanisms for CdZnS-shelled NPLs and preserved the metastable state of the NPLs, including their 2D shape and crystalline structure. Distribution of silver ions in the lattice of the NPLs directly affected the recombination dynamics and enabled fine-tuning of the near-infrared emission beside the exciton confinement. These silver-doped CdZnS-shelled NPLs are shown further to exhibit enhanced paramagnetic properties with Zeeman splitting and Brillouin-like bound-exciton polarization as a function of the magnetic field, critical for spintronic applications