Selective Excitation of Lanthanide Co-Dopants in Colloidal Lead-Free Halide Perovskite Nanocrystals as a Multilevel Anti-Counterfeiting Approach

Doping lead-free halide perovskite nanocrystals with trivalent lanthanide ions has emerged as a promising strategy for engineering their optical properties in various photonic applications. Here, we report the design and synthesis of a series of lead-free double halide perovskite (Cs₂Na(In/Y/Gd)Cl₆) nanocrystals co-doped with a pair of different lanthanides (e.g., Tb³⁺, Dy³⁺, and Eu³⁺) as emission centers, and ns² ions (Sb³⁺ or Bi³⁺) as sensitizers. The tunability of the delayed photoluminescence spectral density was achieved through the selective excitation of lanthanide dopants either via ligand-to-metal charge transfer (e.g., Eu³⁺) or via ns² ion s-p transitions (e.g., Dy³⁺ or Tb³⁺). The intensities of the narrow lanthanide f-f emission bands can, therefore, be tuned by modulating the excitation wavelength and/or dopant ratio, allowing for the accurate engineering of the emission color coordinates and spectral density. We also demonstrated time-resolved tuning of the photoluminescence spectral density for the investigated nanocrystal host lattices co-doped with transition-metal (Mn²⁺) and lanthanide ions, owing to a large difference between the decay dynamics for Mn²⁺ d-d and lanthanide f-f transitions. The rational co-doping of double halide perovskite nanocrystals reported in this work provides a new strategy for generating pre-designed multilevel luminescent signatures for protection against counterfeiting.