Zhou, Zhu, Zhong, Tian, Huang, Chen, Chen (2019) Chlorine-additive-promoted incorporation of Mn2+ dopants into CsPbCl3 perovskite nanocrystals Nanoscale 11(26) 12465-12470
Effective Mn2+ doping in a CsPbCl3 lattice utilizing manganese acetate and trimethylchlorosilane is achieved via a one-pot hot-injection synthesis method. This strongly contrasts to the previous case, where only the MnCl2 precursor was suitable for Mn2+ doping by considering the matching of bond dissociation energies between Mn-Cl and Pb-Cl. The Mn doping concentration and luminescence quantum yield are highly dependent on trimethylchlorosilane content. A new doping mechanism is proposed, where the incorporation of Mn2+ into CsPbCl3 is achieved via directly inserting [MnCl6]4- octahedra into the perovskite structure during the nucleation/growth processes instead of Mn-to-Pb cation exchange. Accordingly, increasing Cl- content in the reaction solution indeed promotes the doping of other divalent transition metal ions such as Ni2+, Cu2+ and Zn2+ in CsPbCl3 and improve the quantum yield of CsPbCl3 nanocrystals up to ∼20% compared to the undoped counterparts (∼1%).