Effect of Mn2+ doping and DDAB-assisted postpassivation on the structural and optical properties of CsPb(Cl/Br)3 halide perovskite nanocrystals

Cesium lead halide perovskite (CsPbX₃; X = Cl, Br, I) nanocrystals showing intense band-edge emission and high photoluminescence quantum yield are known to be a potential candidate for application in optoelectronic devices. However, controlling toxicity due to the presence of Pb²⁺in lead-based halide perovskites is a major challenge for the environment that needs to be tackled cautiously. In this work, we have partially replaced Pb²⁺with Mn²⁺ions in the CsPb(Cl/Br)₃nanocrystals and investigated their impact on the structural and optical properties. The Rietveld refinement shows that CsPbCl₂Br nanocrystals possess a cubic crystal structure withPm3̅mspace group, the Mn²⁺doping results in the contraction of the unit cell. The CsPb(Cl/Br)₃: Mn nanocrystals show a substantial change in the optical properties with an additional emission band at ∼588 nm through a d-d transition, changing the emission color from blue to pink. Here, a didodecyldimethylammonium bromide (DDAB) ligand that triggers both anion and ligand exchange in the CsPb(Cl/Br)₃: Mn nanocrystals have been used to regulate the exchange reaction and tune the emission color of halide perovskites by changing the peak position and the PL intensities of band-edge and Mn²⁺defect states. We have also shown that oleic acid helps in the desorption of oleylamine capping from the CsPb(Cl/Br)₃: Mn nanocrystal surfaces and DDAB, resulting in the substitution of Cl^-with Br^-as well as provides capping with shorter branched length ligand which led to increase in the overall PL intensity by many folds.