Lattice doping of lanthanide ions in CsZrCl nanocrystals enabling phase transition and tunable photoluminescence.

Dopants can endow lead-free perovskite nanocrystals with novel photoelectric properties. However, understanding the effect of dopants on the structure and energy transfer of lead-free perovskite nanocrystals remains limited. In this work, we synthesize zero-dimensional CsZrCl nanocrystals with a blue light quantum yield of up to 75.6% by an improved hot-injection method. And we introduce trace amounts of lanthanide ions (Ln) (<∼8%) in the lattice of nanocrystals and establish an effective energy transfer channel from self-trapped excitons (STEs) to various Ln ions (Tb, Eu, Dy, Sm, and Pr), which can achieve tunable photoluminescence between red, green and blue. Interestingly, with increasing Ln concentrations (>∼10%), the phase transition from the cubic phase CsZrCl:Ln to the monoclinic phase CsLnCl:Zr occurred, while Zr ions began to act as dopants. And a new energy transfer channel from dopant [ZrCl] to host Ln ions was established in the CsLnCl host accompanied by enhanced broadband photoluminescence excitation (PLE) and photoluminescence (PL). In particular, the photoluminescence quantum yield (PLQY) of Tb ions increases from 0.77% to 54% upon the phase transition (under 276 nm excitation). Our study provides new insights into the effects of dopants on the structure of perovskite nanocrystals and is beneficial to the design of a variety of light-emitting materials for optoelectronic applications.