Lattice Engineering via Transition Metal Ions for Boosting Photoluminescence Quantum Yields of Lead-Free Layered Double Perovskite Nanocrystals

Lead-free layered double perovskite nanocrystals (NCs), i.e., Cs₄M(II)M(III)₂Cl₁₂, have recently attracted increasing attention for potential optoelectronic applications due to their low toxicity, direct bandgap nature, and high structural stability. However, the low photoluminescence quantum yield (PLQY, <1%) or even no observed emissions at room temperature have severely blocked the further development of this type of lead-free halide perovskites. Herein, two new layered perovskites, Cs₄CoIn₂Cl₁₂ (CCoI) and Cs₄ZnIn₂Cl₁₂ (CZnI), are successfully synthesized at the nanoscale based on previously reported Cs₄CuIn₂Cl₁₂ (CCuI) NCs, by tuning the M(II) site with different transition metal ions for lattice tailoring. Benefiting from the formation of more self-trapped excitons (STEs) in the distorted lattices, CCoI and CZnI NCs exhibit significantly strengthened STE emissions toward white light compared to the case of almost non-emissive CCuI NCs, by achieving PLQYs of 4.3% and 11.4% respectively. The theoretical and experimental results hint that CCoI and CZnI NCs possess much lower lattice deformation energies than that of reference CCuI NCs, which are favorable for the recombination of as-formed STEs in a radiative way. This work proposes an effective strategy of lattice engineering to boost the photoluminescent properties of lead-free layered double perovskites for their future warm white light-emitting applications.