Tunable Luminescence in Sb3+-Doped Cs3LnCl6 Perovskites for Wide-Coverage Emission and Anti-Counterfeiting Applications

Zero-dimensional (0D) rare-earth-based metal halides show great potential in photonic and optoelectronic applications owing to their high stability, strong exciton confinement, and tunable energy levels. However, the weak absorption and narrow 4f-4f transitions of rare-earth ions limit their performance. To address this, a series of Sb³⁺-doped Cs₃LnCl₆ (Ln: Yb, La, Eu, Ho, Ce, Er, Tb, Sm, Y) nanocrystals were synthesized via a hot-injection method to study the role of Sb³⁺ doping. Sb³⁺ incorporation induces strong broadband self-trapped exciton (STE) emission from Jahn-Teller-distorted [SbCl₆]^3- units and enables efficient energy transfer from STEs to rare-earth ions. As a result, the photoluminescence intensity and spectral tunability are improved, accompanied by bandgap narrowing and enhanced light absorption. Different lanthanide hosts exhibit distinct luminescence behaviors: La-based materials show dominant STE emission, while Tb-, Er-, Yb-, Ho-, and Sm-based systems display STE-mediated energy transfer and enhanced f-f emission. In Eu- and Ce-based hosts, unique mechanisms involving Eu²⁺/Eu³⁺ conversion and Ce³⁺ → STE energy transfer are observed. Moreover, composition-dependent emissions in Sb³⁺-doped Cs₃Tb/EuCl₆ enable a dual-mode color and spectral encoding strategy for optical anti-counterfeiting. This study highlights the versatile role of Sb³⁺ in tuning electronic structures and energy transfer, offering new insights for designing high-performance rare-earth halide materials for advanced optoelectronic applications.